WO2021172420A1 - Curable resin composition, cured film, laminate, cured film production method and semiconductor device - Google Patents
Curable resin composition, cured film, laminate, cured film production method and semiconductor device Download PDFInfo
- Publication number
- WO2021172420A1 WO2021172420A1 PCT/JP2021/007075 JP2021007075W WO2021172420A1 WO 2021172420 A1 WO2021172420 A1 WO 2021172420A1 JP 2021007075 W JP2021007075 W JP 2021007075W WO 2021172420 A1 WO2021172420 A1 WO 2021172420A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- preferable
- compound
- resin composition
- acid
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 181
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- 239000004065 semiconductor Substances 0.000 title claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 160
- 229920005989 resin Polymers 0.000 claims abstract description 91
- 239000011347 resin Substances 0.000 claims abstract description 91
- 239000004642 Polyimide Substances 0.000 claims abstract description 79
- 229920001721 polyimide Polymers 0.000 claims abstract description 79
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 49
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 49
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 45
- 229920002577 polybenzoxazole Polymers 0.000 claims abstract description 43
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims description 301
- -1 oxime compound Chemical class 0.000 claims description 271
- 239000010410 layer Substances 0.000 claims description 127
- 239000003431 cross linking reagent Substances 0.000 claims description 86
- 229910052751 metal Inorganic materials 0.000 claims description 84
- 239000002184 metal Substances 0.000 claims description 84
- 238000010438 heat treatment Methods 0.000 claims description 58
- 238000011161 development Methods 0.000 claims description 33
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 16
- 239000011229 interlayer Substances 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 238000003384 imaging method Methods 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 234
- 239000010408 film Substances 0.000 description 160
- 125000003118 aryl group Chemical group 0.000 description 98
- 125000000217 alkyl group Chemical group 0.000 description 92
- 238000000034 method Methods 0.000 description 86
- 239000000203 mixture Substances 0.000 description 83
- 239000002253 acid Substances 0.000 description 66
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 65
- 239000000463 material Substances 0.000 description 52
- 150000003254 radicals Chemical class 0.000 description 51
- 125000001931 aliphatic group Chemical group 0.000 description 49
- 125000000962 organic group Chemical group 0.000 description 49
- 125000002947 alkylene group Chemical group 0.000 description 48
- 239000000243 solution Substances 0.000 description 43
- 125000001424 substituent group Chemical group 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 36
- 150000003839 salts Chemical class 0.000 description 36
- 125000003545 alkoxy group Chemical group 0.000 description 35
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 34
- 125000005843 halogen group Chemical group 0.000 description 34
- 239000003960 organic solvent Substances 0.000 description 33
- 230000018109 developmental process Effects 0.000 description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 32
- 239000002904 solvent Substances 0.000 description 32
- 239000003505 polymerization initiator Substances 0.000 description 31
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- 239000007787 solid Substances 0.000 description 29
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 28
- 229910052731 fluorine Inorganic materials 0.000 description 27
- 125000004122 cyclic group Chemical group 0.000 description 25
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 24
- 239000007788 liquid Substances 0.000 description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000126 substance Substances 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 21
- 150000002334 glycols Chemical class 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 230000008569 process Effects 0.000 description 21
- 239000004094 surface-active agent Substances 0.000 description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- 239000003963 antioxidant agent Substances 0.000 description 20
- 235000006708 antioxidants Nutrition 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 20
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 20
- 125000001153 fluoro group Chemical group F* 0.000 description 20
- 239000003112 inhibitor Substances 0.000 description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 18
- 150000004985 diamines Chemical class 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- DQYSALLXMHVJAV-UHFFFAOYSA-M 3-heptyl-2-[(3-heptyl-4-methyl-1,3-thiazol-3-ium-2-yl)methylidene]-4-methyl-1,3-thiazole;iodide Chemical compound [I-].CCCCCCCN1C(C)=CS\C1=C\C1=[N+](CCCCCCC)C(C)=CS1 DQYSALLXMHVJAV-UHFFFAOYSA-M 0.000 description 17
- 230000003078 antioxidant effect Effects 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 125000000753 cycloalkyl group Chemical group 0.000 description 16
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 16
- 230000035945 sensitivity Effects 0.000 description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 16
- 125000005647 linker group Chemical group 0.000 description 15
- 239000003504 photosensitizing agent Substances 0.000 description 15
- 125000004429 atom Chemical group 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 14
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
- 125000003342 alkenyl group Chemical group 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000001723 curing Methods 0.000 description 13
- 229920001296 polysiloxane Polymers 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 230000004913 activation Effects 0.000 description 12
- 235000013877 carbamide Nutrition 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 238000010030 laminating Methods 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 239000007870 radical polymerization initiator Substances 0.000 description 12
- NQPJDJVGBDHCAD-UHFFFAOYSA-N 1,3-diazinan-2-one Chemical class OC1=NCCCN1 NQPJDJVGBDHCAD-UHFFFAOYSA-N 0.000 description 11
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 125000005370 alkoxysilyl group Chemical group 0.000 description 11
- 150000004696 coordination complex Chemical class 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 125000000623 heterocyclic group Chemical group 0.000 description 11
- 230000005012 migration Effects 0.000 description 11
- 238000013508 migration Methods 0.000 description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 description 11
- 125000004430 oxygen atom Chemical group O* 0.000 description 11
- 125000000565 sulfonamide group Chemical group 0.000 description 11
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 10
- 125000003710 aryl alkyl group Chemical group 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical class O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 10
- 150000002923 oximes Chemical class 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 150000001408 amides Chemical class 0.000 description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- 125000004093 cyano group Chemical group *C#N 0.000 description 9
- 125000006165 cyclic alkyl group Chemical group 0.000 description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 102000012335 Plasminogen Activator Inhibitor 1 Human genes 0.000 description 8
- 108010022233 Plasminogen Activator Inhibitor 1 Proteins 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 239000012986 chain transfer agent Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 150000003609 titanium compounds Chemical class 0.000 description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 8
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 7
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 125000004849 alkoxymethyl group Chemical group 0.000 description 7
- 125000005907 alkyl ester group Chemical group 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 229940116333 ethyl lactate Drugs 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000010954 inorganic particle Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- FFOPEPMHKILNIT-UHFFFAOYSA-N Isopropyl butyrate Chemical compound CCCC(=O)OC(C)C FFOPEPMHKILNIT-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000000732 arylene group Chemical group 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 6
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 6
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 5
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 125000005529 alkyleneoxy group Chemical group 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 5
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 125000002971 oxazolyl group Chemical group 0.000 description 5
- 125000003226 pyrazolyl group Chemical group 0.000 description 5
- 238000007363 ring formation reaction Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000012719 thermal polymerization Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 4
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 4
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical class NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 4
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical class NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 4
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 4
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical compound OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- 125000004663 dialkyl amino group Chemical group 0.000 description 4
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 4
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 4
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 4
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 150000004714 phosphonium salts Chemical class 0.000 description 4
- 125000004193 piperazinyl group Chemical group 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- 150000003462 sulfoxides Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 4
- 150000003536 tetrazoles Chemical group 0.000 description 4
- 125000005000 thioaryl group Chemical group 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 150000003852 triazoles Chemical group 0.000 description 4
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 3
- KLZYRCVPDWTZLH-UHFFFAOYSA-N 2,3-dimethylsuccinic acid Chemical compound OC(=O)C(C)C(C)C(O)=O KLZYRCVPDWTZLH-UHFFFAOYSA-N 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- ICPWFHKNYYRBSZ-UHFFFAOYSA-M 2-methoxypropanoate Chemical compound COC(C)C([O-])=O ICPWFHKNYYRBSZ-UHFFFAOYSA-M 0.000 description 3
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- FCTYHYDLMFYYLG-UHFFFAOYSA-N Fc1cccc(F)c1[Ti]c1c(F)cccc1F Chemical compound Fc1cccc(F)c1[Ti]c1c(F)cccc1F FCTYHYDLMFYYLG-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DIQMPQMYFZXDAX-UHFFFAOYSA-N Pentyl formate Chemical compound CCCCCOC=O DIQMPQMYFZXDAX-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- 125000005011 alkyl ether group Chemical group 0.000 description 3
- 125000005103 alkyl silyl group Chemical group 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000005013 aryl ether group Chemical group 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- IWPATTDMSUYMJV-UHFFFAOYSA-N butyl 2-methoxyacetate Chemical compound CCCCOC(=O)COC IWPATTDMSUYMJV-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 3
- WHRLOJCOIKOQGL-UHFFFAOYSA-N ethyl 2-methoxypropanoate Chemical compound CCOC(=O)C(C)OC WHRLOJCOIKOQGL-UHFFFAOYSA-N 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 3
- 229940117955 isoamyl acetate Drugs 0.000 description 3
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 3
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical group C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 3
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical group C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 3
- 235000001510 limonene Nutrition 0.000 description 3
- 229940087305 limonene Drugs 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- PPFNAOBWGRMDLL-UHFFFAOYSA-N methyl 2-ethoxyacetate Chemical compound CCOCC(=O)OC PPFNAOBWGRMDLL-UHFFFAOYSA-N 0.000 description 3
- YVWPDYFVVMNWDT-UHFFFAOYSA-N methyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OC YVWPDYFVVMNWDT-UHFFFAOYSA-N 0.000 description 3
- AKWHOGIYEOZALP-UHFFFAOYSA-N methyl 2-methoxy-2-methylpropanoate Chemical compound COC(=O)C(C)(C)OC AKWHOGIYEOZALP-UHFFFAOYSA-N 0.000 description 3
- 229940057867 methyl lactate Drugs 0.000 description 3
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- CYIRLFJPTCUCJB-UHFFFAOYSA-N propyl 2-methoxypropanoate Chemical compound CCCOC(=O)C(C)OC CYIRLFJPTCUCJB-UHFFFAOYSA-N 0.000 description 3
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229960001860 salicylate Drugs 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 150000000000 tetracarboxylic acids Chemical group 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 125000004001 thioalkyl group Chemical group 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- WVUYYXUATWMVIT-UHFFFAOYSA-N 1-bromo-4-ethoxybenzene Chemical compound CCOC1=CC=C(Br)C=C1 WVUYYXUATWMVIT-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- CCUWGJDGLACFQT-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O CCUWGJDGLACFQT-UHFFFAOYSA-N 0.000 description 2
- YUDUFRYTKFGQCL-UHFFFAOYSA-N 2,2,3,3-tetrafluorobutanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(O)=O YUDUFRYTKFGQCL-UHFFFAOYSA-N 0.000 description 2
- KJDGGLOKWHMBOX-UHFFFAOYSA-N 2,2,3-trimethylbutanedioic acid Chemical compound OC(=O)C(C)C(C)(C)C(O)=O KJDGGLOKWHMBOX-UHFFFAOYSA-N 0.000 description 2
- WUHHVDQBQZVSJV-UHFFFAOYSA-N 2,2-dibutylpropanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CCCC WUHHVDQBQZVSJV-UHFFFAOYSA-N 0.000 description 2
- BTUDGPVTCYNYLK-UHFFFAOYSA-N 2,2-dimethylglutaric acid Chemical compound OC(=O)C(C)(C)CCC(O)=O BTUDGPVTCYNYLK-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 2
- KECOIASOKMSRFT-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(O)C(N)=CC(S(=O)(=O)C=2C=C(N)C(O)=CC=2)=C1 KECOIASOKMSRFT-UHFFFAOYSA-N 0.000 description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 2
- ZDRNVPNSQJRIRN-UHFFFAOYSA-N 2-amino-5-[2-(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C(O)=C1 ZDRNVPNSQJRIRN-UHFFFAOYSA-N 0.000 description 2
- JDFAWEKPFLGRAK-UHFFFAOYSA-N 2-amino-5-[2-(4-amino-3-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(N)C(O)=CC=1C(C)(C)C1=CC=C(N)C(O)=C1 JDFAWEKPFLGRAK-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- DQEUFPARIOFOAI-UHFFFAOYSA-N 2-propan-2-ylpropanedioic acid Chemical compound CC(C)C(C(O)=O)C(O)=O DQEUFPARIOFOAI-UHFFFAOYSA-N 0.000 description 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical group C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 2
- DUHQIGLHYXLKAE-UHFFFAOYSA-N 3,3-dimethylglutaric acid Chemical compound OC(=O)CC(C)(C)CC(O)=O DUHQIGLHYXLKAE-UHFFFAOYSA-N 0.000 description 2
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 2
- XAWFHZMTJUGGEE-UHFFFAOYSA-N 3-ethyl-3-methylpentanedioic acid Chemical compound OC(=O)CC(C)(CC)CC(O)=O XAWFHZMTJUGGEE-UHFFFAOYSA-N 0.000 description 2
- UJBOOUHRTQVGRU-UHFFFAOYSA-N 3-methylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1 UJBOOUHRTQVGRU-UHFFFAOYSA-N 0.000 description 2
- ZSSJQYMNCUJSBR-UHFFFAOYSA-N 4,5-dimethoxy-1,3-bis(methoxymethyl)imidazolidin-2-one Chemical compound COCN1C(OC)C(OC)N(COC)C1=O ZSSJQYMNCUJSBR-UHFFFAOYSA-N 0.000 description 2
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 2
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 2
- LFEWXDOYPCWFHR-UHFFFAOYSA-N 4-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C=C1 LFEWXDOYPCWFHR-UHFFFAOYSA-N 0.000 description 2
- SGPJBCCVSFQQED-UHFFFAOYSA-N 4-[(4-aminophenyl)-[[dimethyl(trimethylsilyloxy)silyl]oxy-dimethylsilyl]oxy-methylsilyl]oxysilylaniline Chemical compound C=1C=C(N)C=CC=1[Si](C)(O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C)O[SiH2]C1=CC=C(N)C=C1 SGPJBCCVSFQQED-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical group C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 2
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ILKOAJGHVUCDIV-UHFFFAOYSA-N FC1=CC=C(N2C=CC=C2)C(F)=C1[Ti]C(C=1F)=C(F)C=CC=1N1C=CC=C1 Chemical compound FC1=CC=C(N2C=CC=C2)C(F)=C1[Ti]C(C=1F)=C(F)C=CC=1N1C=CC=C1 ILKOAJGHVUCDIV-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- HMSWAIKSFDFLKN-UHFFFAOYSA-N Hexacosane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCC HMSWAIKSFDFLKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical group C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 125000004036 acetal group Chemical group 0.000 description 2
- IPSOQTFPIWIGJT-UHFFFAOYSA-N acetic acid;1-propoxypropane Chemical compound CC(O)=O.CCCOCCC IPSOQTFPIWIGJT-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000005042 acyloxymethyl group Chemical group 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000002521 alkyl halide group Chemical group 0.000 description 2
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 2
- 229960002255 azelaic acid Drugs 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000005998 bromoethyl group Chemical group 0.000 description 2
- 125000005997 bromomethyl group Chemical group 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 235000005513 chalcones Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical class NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- JLEKJZUYWFJPMB-UHFFFAOYSA-N ethyl 2-methoxyacetate Chemical compound CCOC(=O)COC JLEKJZUYWFJPMB-UHFFFAOYSA-N 0.000 description 2
- IJUHLFUALMUWOM-UHFFFAOYSA-N ethyl 3-methoxypropanoate Chemical compound CCOC(=O)CCOC IJUHLFUALMUWOM-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 229940117360 ethyl pyruvate Drugs 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- JJWZFUFNJNGKAF-UHFFFAOYSA-N hexacosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCCCCCC(O)=O JJWZFUFNJNGKAF-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 150000007975 iminium salts Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 2
- YKNWIILGEFFOPE-UHFFFAOYSA-N n-pentacosane Natural products CCCCCCCCCCCCCCCCCCCCCCCCC YKNWIILGEFFOPE-UHFFFAOYSA-N 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000012487 rinsing solution Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 description 2
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 2
- 125000004953 trihalomethyl group Chemical group 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PJRNHEWJJHSJGH-UHFFFAOYSA-N (1-benzylcyclohexa-2,4-dien-1-yl)thiourea Chemical compound C(C1=CC=CC=C1)C1(CC=CC=C1)NC(=S)N PJRNHEWJJHSJGH-UHFFFAOYSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- WHIRALQRTSITMI-UJURSFKZSA-N (1s,5r)-6,8-dioxabicyclo[3.2.1]octan-4-one Chemical compound O1[C@@]2([H])OC[C@]1([H])CCC2=O WHIRALQRTSITMI-UJURSFKZSA-N 0.000 description 1
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 1
- CSUUDNFYSFENAE-UHFFFAOYSA-N (2-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC=C1C(=O)C1=CC=CC=C1 CSUUDNFYSFENAE-UHFFFAOYSA-N 0.000 description 1
- YSWBUABBMRVQAC-UHFFFAOYSA-N (2-nitrophenyl)methanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1[N+]([O-])=O YSWBUABBMRVQAC-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- IQGIEMYBDGDBMR-UHFFFAOYSA-N (3-methyl-5-prop-2-enoyloxypentyl) prop-2-enoate Chemical compound C=CC(=O)OCCC(C)CCOC(=O)C=C IQGIEMYBDGDBMR-UHFFFAOYSA-N 0.000 description 1
- MRUDPRFGMHTPFJ-UHFFFAOYSA-N (3-oxobutan-2-ylideneamino) acetate Chemical compound CC(=O)ON=C(C)C(C)=O MRUDPRFGMHTPFJ-UHFFFAOYSA-N 0.000 description 1
- SKCKRZWCOYHBEC-UHFFFAOYSA-N (3-oxobutan-2-ylideneamino) benzoate Chemical compound CC(=O)C(C)=NOC(=O)C1=CC=CC=C1 SKCKRZWCOYHBEC-UHFFFAOYSA-N 0.000 description 1
- JFFCVOSCPLKMLG-UHFFFAOYSA-N (3-oxobutan-2-ylideneamino) propanoate Chemical compound CCC(=O)ON=C(C)C(C)=O JFFCVOSCPLKMLG-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- QAEDNLDMOUKNMI-UHFFFAOYSA-O (4-hydroxyphenyl)-dimethylsulfanium Chemical compound C[S+](C)C1=CC=C(O)C=C1 QAEDNLDMOUKNMI-UHFFFAOYSA-O 0.000 description 1
- NVFDHSAAXWUULH-UHFFFAOYSA-N (4-hydroxyphenyl)-dimethylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C[S+](C)C1=CC=C(O)C=C1 NVFDHSAAXWUULH-UHFFFAOYSA-N 0.000 description 1
- GHBWHFQCCGTKIH-UHFFFAOYSA-N (4-hydroxyphenyl)-methyl-[(2-methylphenyl)methyl]sulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=C(O)C=CC=1[S+](C)CC1=CC=CC=C1C GHBWHFQCCGTKIH-UHFFFAOYSA-N 0.000 description 1
- CGCQHMFVCNWSOV-UHFFFAOYSA-N (4-morpholin-4-ylphenyl)-phenylmethanone Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C1=CC=CC=C1 CGCQHMFVCNWSOV-UHFFFAOYSA-N 0.000 description 1
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- FPZXQVCYHDMIIA-UHFFFAOYSA-N 1,1-diphenylthiourea Chemical compound C=1C=CC=CC=1N(C(=S)N)C1=CC=CC=C1 FPZXQVCYHDMIIA-UHFFFAOYSA-N 0.000 description 1
- LPYIWBZHBGLIGW-UHFFFAOYSA-N 1,2,3,4,5-pentamethylcyclopenta-1,3-diene;titanium Chemical compound [Ti].CC1C(C)=C(C)C(C)=C1C LPYIWBZHBGLIGW-UHFFFAOYSA-N 0.000 description 1
- VRKVWGGGHMMERE-UHFFFAOYSA-N 1,2-bis(methoxymethyl)benzene Chemical compound COCC1=CC=CC=C1COC VRKVWGGGHMMERE-UHFFFAOYSA-N 0.000 description 1
- VBYLUPVOJYUVQF-UHFFFAOYSA-N 1,2-dimethoxy-3,4-bis(methoxymethyl)benzene Chemical compound COCc1ccc(OC)c(OC)c1COC VBYLUPVOJYUVQF-UHFFFAOYSA-N 0.000 description 1
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- XKALZGSIEJZJCZ-UHFFFAOYSA-N 1,3-bis(methoxymethyl)urea Chemical compound COCNC(=O)NCOC XKALZGSIEJZJCZ-UHFFFAOYSA-N 0.000 description 1
- KREOCUNMMFZOOS-UHFFFAOYSA-N 1,3-di(propan-2-yl)thiourea Chemical compound CC(C)NC(S)=NC(C)C KREOCUNMMFZOOS-UHFFFAOYSA-N 0.000 description 1
- KAJICSGLHKRDLN-UHFFFAOYSA-N 1,3-dicyclohexylthiourea Chemical compound C1CCCCC1NC(=S)NC1CCCCC1 KAJICSGLHKRDLN-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- NXRIDTLKJCKPOG-UHFFFAOYSA-N 1,4-dihydroimidazole-5-thione Chemical compound S=C1CN=CN1 NXRIDTLKJCKPOG-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ZNNRTWIXUUGIFI-UHFFFAOYSA-N 1,5-bis[4-(diethylamino)phenyl]penta-1,4-dien-3-one Chemical compound C1=CC(N(CC)CC)=CC=C1C=CC(=O)C=CC1=CC=C(N(CC)CC)C=C1 ZNNRTWIXUUGIFI-UHFFFAOYSA-N 0.000 description 1
- JWTSVUUPJIIXTO-UHFFFAOYSA-N 1,5-bis[4-(dimethylamino)phenyl]penta-1,4-dien-3-one Chemical compound C1=CC(N(C)C)=CC=C1C=CC(=O)C=CC1=CC=C(N(C)C)C=C1 JWTSVUUPJIIXTO-UHFFFAOYSA-N 0.000 description 1
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- VUVPNTYTOUGMDG-UHFFFAOYSA-N 1-(2-hydroxyethyl)-3-prop-2-enylthiourea Chemical compound OCCNC(=S)NCC=C VUVPNTYTOUGMDG-UHFFFAOYSA-N 0.000 description 1
- HIYIGPNHCGAADM-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]-2,3-dimethylbenzene Chemical group CC=1C(=C(C=CC=1COC)C1=CC=C(C=C1)COC)C HIYIGPNHCGAADM-UHFFFAOYSA-N 0.000 description 1
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- LRWQENBAFMBIJR-UHFFFAOYSA-N 1-adamantylthiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)N)C3 LRWQENBAFMBIJR-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- BBPMQQKHHDHOMI-UHFFFAOYSA-N 1-iminopentan-3-one Chemical compound CCC(=O)CC=N BBPMQQKHHDHOMI-UHFFFAOYSA-N 0.000 description 1
- IJKXOHKQUXHVBA-UHFFFAOYSA-N 1-methyl-3-(3-trimethoxysilylpropyl)thiourea Chemical compound CNC(=S)NCCC[Si](OC)(OC)OC IJKXOHKQUXHVBA-UHFFFAOYSA-N 0.000 description 1
- KYWXRBNOYGGPIZ-UHFFFAOYSA-N 1-morpholin-4-ylethanone Chemical compound CC(=O)N1CCOCC1 KYWXRBNOYGGPIZ-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical group C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- CKUJONFLPBQEKM-UHFFFAOYSA-N 2,2,6,6-tetramethylheptanedioic acid Chemical compound OC(=O)C(C)(C)CCCC(C)(C)C(O)=O CKUJONFLPBQEKM-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- GOHPTLYPQCTZSE-UHFFFAOYSA-N 2,2-dimethylsuccinic acid Chemical compound OC(=O)C(C)(C)CC(O)=O GOHPTLYPQCTZSE-UHFFFAOYSA-N 0.000 description 1
- WCZNKVPCIFMXEQ-UHFFFAOYSA-N 2,3,5,6-tetramethylbenzene-1,4-diamine Chemical compound CC1=C(C)C(N)=C(C)C(C)=C1N WCZNKVPCIFMXEQ-UHFFFAOYSA-N 0.000 description 1
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- LFEXGBPVZBXATF-UHFFFAOYSA-N 2,3-dimethylbenzenesulfonamide Chemical compound CC1=CC=CC(S(N)(=O)=O)=C1C LFEXGBPVZBXATF-UHFFFAOYSA-N 0.000 description 1
- BHKAWXZKFKVZLK-UHFFFAOYSA-N 2,3-ditert-butyl-6-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(C(C)(C)C)=C1O BHKAWXZKFKVZLK-UHFFFAOYSA-N 0.000 description 1
- CCZNFGBAORROPB-UHFFFAOYSA-N 2,4,6-tris(dibromomethyl)-1,3,5-triazine Chemical compound BrC(Br)C1=NC(C(Br)Br)=NC(C(Br)Br)=N1 CCZNFGBAORROPB-UHFFFAOYSA-N 0.000 description 1
- LNRJBPCTMHMOFA-UHFFFAOYSA-N 2,4,6-tris(dichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)C1=NC(C(Cl)Cl)=NC(C(Cl)Cl)=N1 LNRJBPCTMHMOFA-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- RWAOPZVGICHCOI-UHFFFAOYSA-N 2,4-diaminobenzene-1,3-diol Chemical compound NC1=CC=C(O)C(N)=C1O RWAOPZVGICHCOI-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- RLXBOUUYEFOFSW-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-diol Chemical compound NC1=CC(O)=C(N)C=C1O RLXBOUUYEFOFSW-UHFFFAOYSA-N 0.000 description 1
- BWAPJIHJXDYDPW-UHFFFAOYSA-N 2,5-dimethyl-p-phenylenediamine Chemical compound CC1=CC(N)=C(C)C=C1N BWAPJIHJXDYDPW-UHFFFAOYSA-N 0.000 description 1
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-UHFFFAOYSA-N 0.000 description 1
- KUMMBDBTERQYCG-UHFFFAOYSA-N 2,6-bis(hydroxymethyl)-4-methylphenol Chemical compound CC1=CC(CO)=C(O)C(CO)=C1 KUMMBDBTERQYCG-UHFFFAOYSA-N 0.000 description 1
- DWKBMLWYFNGDCN-UHFFFAOYSA-N 2,6-bis(methoxymethyl)phenol Chemical compound COCC1=CC=CC(COC)=C1O DWKBMLWYFNGDCN-UHFFFAOYSA-N 0.000 description 1
- SFXPLYOSNTZJFW-UHFFFAOYSA-N 2,6-bis[[4-(diethylamino)phenyl]methylidene]-4-methylcyclohexan-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C=C(CC(C)C1)C(=O)C1=CC1=CC=C(N(CC)CC)C=C1 SFXPLYOSNTZJFW-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DQMOHZLFVGYNAN-UHFFFAOYSA-N 2-(2-phenylethenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=CC=2C=CC=CC=2)=N1 DQMOHZLFVGYNAN-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WJKHYAJKIXYSHS-UHFFFAOYSA-N 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(Cl)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 WJKHYAJKIXYSHS-UHFFFAOYSA-N 0.000 description 1
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- MPNIGZBDAMWHSX-UHFFFAOYSA-N 2-(4-methylphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(C)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MPNIGZBDAMWHSX-UHFFFAOYSA-N 0.000 description 1
- FXYQVUGCQHGGEX-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-4-methyl-6-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O FXYQVUGCQHGGEX-UHFFFAOYSA-N 0.000 description 1
- PXMKSNKSDOKQGZ-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-6-(2-methylbutan-2-yl)-4-(2-methylpropyl)phenol Chemical compound CCC(C)(C)C1=CC(CC(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O PXMKSNKSDOKQGZ-UHFFFAOYSA-N 0.000 description 1
- ADFWZEGSIXNYRT-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-6-(2-methylpropyl)-4-propylphenol Chemical compound CCCC1=CC(CC(C)C)=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 ADFWZEGSIXNYRT-UHFFFAOYSA-N 0.000 description 1
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- MCNPOZMLKGDJGP-UHFFFAOYSA-N 2-[2-(4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MCNPOZMLKGDJGP-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- WPMUMRCRKFBYIH-UHFFFAOYSA-N 2-[4,6-bis(2-hydroxy-4-octoxyphenyl)-1,3,5-triazin-2-yl]-5-octoxyphenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(OCCCCCCCC)=CC=2)O)=NC(C=2C(=CC(OCCCCCCCC)=CC=2)O)=N1 WPMUMRCRKFBYIH-UHFFFAOYSA-N 0.000 description 1
- KPXQQALZZHREIU-UHFFFAOYSA-N 2-[4,6-bis(2-hydroxyphenyl)triazin-5-yl]phenol Chemical class OC1=CC=CC=C1C1=NN=NC(C=2C(=CC=CC=2)O)=C1C1=CC=CC=C1O KPXQQALZZHREIU-UHFFFAOYSA-N 0.000 description 1
- PIGBIZGGEUNVCV-UHFFFAOYSA-N 2-[4,6-bis[4-(3-butoxy-2-hydroxypropoxy)-2-hydroxyphenyl]-1,3,5-triazin-2-yl]-5-(3-butoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCC)=CC=C1C1=NC(C=2C(=CC(OCC(O)COCCCC)=CC=2)O)=NC(C=2C(=CC(OCC(O)COCCCC)=CC=2)O)=N1 PIGBIZGGEUNVCV-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- YUZSJKBFHATJHV-UHFFFAOYSA-N 2-[4-[2-[4-(2-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C(=CC=CC=3)N)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 YUZSJKBFHATJHV-UHFFFAOYSA-N 0.000 description 1
- FJYCAYKHNVQCJW-UHFFFAOYSA-N 2-[4-[4-(2-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C(=CC=CC=3)N)=CC=2)C=C1 FJYCAYKHNVQCJW-UHFFFAOYSA-N 0.000 description 1
- MSHXOTKVSBHKBZ-UHFFFAOYSA-N 2-[6-(2-hydroxyphenyl)triazin-4-yl]phenol Chemical class OC1=C(C=CC=C1)C1=CC(=NN=N1)C1=C(C=CC=C1)O MSHXOTKVSBHKBZ-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- BXVXPASMKWYBFD-UHFFFAOYSA-N 2-[[2-hydroxy-3-(hydroxymethyl)-5-methylphenyl]methyl]-6-(hydroxymethyl)-4-methylphenol Chemical compound CC1=CC(CO)=C(O)C(CC=2C(=C(CO)C=C(C)C=2)O)=C1 BXVXPASMKWYBFD-UHFFFAOYSA-N 0.000 description 1
- YCKZAOPKIOWTEH-UHFFFAOYSA-N 2-[[4-(dimethylamino)phenyl]methylidene]-3h-inden-1-one Chemical compound C1=CC(N(C)C)=CC=C1C=C1C(=O)C2=CC=CC=C2C1 YCKZAOPKIOWTEH-UHFFFAOYSA-N 0.000 description 1
- ZGYHBLSTEXSDOB-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;titanium Chemical compound [Ti].OCCN(CCO)CCO.OCCN(CCO)CCO ZGYHBLSTEXSDOB-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- KZLDGFZCFRXUIB-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC(C=2C=C(N)C(O)=CC=2)=C1 KZLDGFZCFRXUIB-UHFFFAOYSA-N 0.000 description 1
- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 1
- NPUFCLGAODQFLG-UHFFFAOYSA-N 2-amino-5-(4-aminophenyl)cyclohexa-2,4-diene-1,1-diol Chemical group C1C(O)(O)C(N)=CC=C1C1=CC=C(N)C=C1 NPUFCLGAODQFLG-UHFFFAOYSA-N 0.000 description 1
- RCYNJDVUURMJOZ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-hydroxyphenyl)methyl]phenol Chemical compound C1=C(O)C(N)=CC=C1CC1=CC=C(N)C(O)=C1 RCYNJDVUURMJOZ-UHFFFAOYSA-N 0.000 description 1
- UZSDRHVOBLQYCX-UHFFFAOYSA-N 2-amino-6-hydroxybenzoic acid Chemical compound NC1=CC=CC(O)=C1C(O)=O UZSDRHVOBLQYCX-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- MVQXBXLDXSQURK-UHFFFAOYSA-N 2-aminoethanesulfonamide Chemical compound NCCS(N)(=O)=O MVQXBXLDXSQURK-UHFFFAOYSA-N 0.000 description 1
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 1
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 description 1
- UXGVMFHEKMGWMA-UHFFFAOYSA-N 2-benzofuran Chemical group C1=CC=CC2=COC=C21 UXGVMFHEKMGWMA-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- QEMUVGKPNFMGAZ-UHFFFAOYSA-N 2-benzylsulfanyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(SCC=2C=CC=CC=2)=N1 QEMUVGKPNFMGAZ-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- TUXAJHDLJHMOQB-UHFFFAOYSA-N 2-diazonio-4-sulfonaphthalen-1-olate Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC([N+]#N)=C([O-])C2=C1 TUXAJHDLJHMOQB-UHFFFAOYSA-N 0.000 description 1
- VJKZIQFVKMUTID-UHFFFAOYSA-N 2-diazonio-5-sulfonaphthalen-1-olate Chemical compound N#[N+]C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1[O-] VJKZIQFVKMUTID-UHFFFAOYSA-N 0.000 description 1
- ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 2-dodecanoyloxyethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCC ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 0.000 description 1
- DORYOOVLRDMOQO-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid propan-2-olate titanium(4+) Chemical compound CC([O-])C.[Ti+4].C(CCCCCCCCCCC)C1=C(C=CC=C1)S(=O)(=O)O.C(CCCCCCCCCCC)C1=C(C=CC=C1)S(=O)(=O)O.C(CCCCCCCCCCC)C1=C(C=CC=C1)S(=O)(=O)O.CC([O-])C.CC([O-])C.CC([O-])C DORYOOVLRDMOQO-UHFFFAOYSA-N 0.000 description 1
- KKOHCQAVIJDYAF-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KKOHCQAVIJDYAF-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- ALQPJHSFIXARGX-UHFFFAOYSA-N 2-ethynylaniline Chemical compound NC1=CC=CC=C1C#C ALQPJHSFIXARGX-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical class OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- 125000006290 2-hydroxybenzyl group Chemical group [H]OC1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QLRHSRISTOFCRV-UHFFFAOYSA-N 2-hydroxynaphthalene-1-sulfonamide Chemical compound C1=CC=C2C(S(=O)(=O)N)=C(O)C=CC2=C1 QLRHSRISTOFCRV-UHFFFAOYSA-N 0.000 description 1
- XYKPEDAFWPOVCY-UHFFFAOYSA-N 2-methoxy-4,6-bis(tribromomethyl)-1,3,5-triazine Chemical compound COC1=NC(C(Br)(Br)Br)=NC(C(Br)(Br)Br)=N1 XYKPEDAFWPOVCY-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- GOTIJEQQGSMAIN-UHFFFAOYSA-N 2-methyl-4,6-bis(tribromomethyl)-1,3,5-triazine Chemical compound CC1=NC(C(Br)(Br)Br)=NC(C(Br)(Br)Br)=N1 GOTIJEQQGSMAIN-UHFFFAOYSA-N 0.000 description 1
- LETDRANQSOEVCX-UHFFFAOYSA-N 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 LETDRANQSOEVCX-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- SNOJPWLNAMAYSX-UHFFFAOYSA-N 2-methylpropan-1-ol;titanium Chemical compound [Ti].CC(C)CO.CC(C)CO.CC(C)CO.CC(C)CO SNOJPWLNAMAYSX-UHFFFAOYSA-N 0.000 description 1
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- SYUYTOYKQOAVDW-UHFFFAOYSA-N 2-nitrosonaphthalen-1-ol Chemical compound C1=CC=C2C(O)=C(N=O)C=CC2=C1 SYUYTOYKQOAVDW-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- HAZQZUFYRLFOLC-UHFFFAOYSA-N 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=2C=CC=CC=2)=N1 HAZQZUFYRLFOLC-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 description 1
- RCUOAHPSDFRHOR-UHFFFAOYSA-N 2-phenylsulfanyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(SC=2C=CC=CC=2)=N1 RCUOAHPSDFRHOR-UHFFFAOYSA-N 0.000 description 1
- WNYJRJRHKRZXEO-UHFFFAOYSA-N 2-propan-2-ylbenzene-1,4-diamine Chemical compound CC(C)C1=CC(N)=CC=C1N WNYJRJRHKRZXEO-UHFFFAOYSA-N 0.000 description 1
- DOSGQNSHFPTAOA-UHFFFAOYSA-N 2-propyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound CCCC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DOSGQNSHFPTAOA-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- GSSXLFACIJSBOM-UHFFFAOYSA-N 2h-pyran-2-ol Chemical group OC1OC=CC=C1 GSSXLFACIJSBOM-UHFFFAOYSA-N 0.000 description 1
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical group CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical group C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 1
- KOKYZJXQQKRSJC-UHFFFAOYSA-N 3,3-diacetylheptane-2,4,6-trione;titanium Chemical compound [Ti].CC(=O)CC(=O)C(C(C)=O)(C(C)=O)C(C)=O KOKYZJXQQKRSJC-UHFFFAOYSA-N 0.000 description 1
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 description 1
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- KEPGNQLKWDULGD-UHFFFAOYSA-N 3-(3-prop-2-enoyloxypropoxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCCCOCCCOC(=O)C=C KEPGNQLKWDULGD-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- BQGXXEGJJMEZMZ-UHFFFAOYSA-N 3-(n-ethyl-3-hydroxy-4-nitrosoanilino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCN(CC)C1=CC=C(N=O)C(O)=C1 BQGXXEGJJMEZMZ-UHFFFAOYSA-N 0.000 description 1
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 description 1
- PQFRTJPVZSPBFI-UHFFFAOYSA-N 3-(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=CC=CC(C(F)(F)F)=C1N PQFRTJPVZSPBFI-UHFFFAOYSA-N 0.000 description 1
- ZZYZUFNSKAIYCJ-UHFFFAOYSA-N 3-[(3-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1C(N)CCCC1CC1CC(N)CCC1 ZZYZUFNSKAIYCJ-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- XUDUTRMKKYUAKI-UHFFFAOYSA-N 3-[1-(1-phenylethyl)piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound C1CC(N2C(NC3=CC=CC=C32)=O)CCN1C(C)C1=CC=CC=C1 XUDUTRMKKYUAKI-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- MFTFTIALAXXIMU-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MFTFTIALAXXIMU-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- GIMFLOOKFCUUOQ-UHFFFAOYSA-N 3-amino-4-hydroxy-1,2-dihydropyrimidin-6-one Chemical compound NN1CN=C(O)C=C1O GIMFLOOKFCUUOQ-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- KFFUEVDMVNIOHA-UHFFFAOYSA-N 3-aminobenzenethiol Chemical compound NC1=CC=CC(S)=C1 KFFUEVDMVNIOHA-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- LVYXPOCADCXMLP-UHFFFAOYSA-N 3-butoxy-n,n-dimethylpropanamide Chemical compound CCCCOCCC(=O)N(C)C LVYXPOCADCXMLP-UHFFFAOYSA-N 0.000 description 1
- KNWLMUXHNAQOJM-UHFFFAOYSA-N 3-ethyl-3-(3-ethylheptyl)oxetane Chemical compound CCCCC(CC)CCC1(CC)COC1 KNWLMUXHNAQOJM-UHFFFAOYSA-N 0.000 description 1
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 1
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical compound NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 1
- 125000006291 3-hydroxybenzyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(=C1[H])C([H])([H])* 0.000 description 1
- YSIKHBWUBSFBRZ-UHFFFAOYSA-N 3-methoxypropanoic acid Chemical compound COCCC(O)=O YSIKHBWUBSFBRZ-UHFFFAOYSA-N 0.000 description 1
- HAHWYTLUKCIGPH-UHFFFAOYSA-N 3-methylbutyl 2-(diethylamino)benzoate Chemical compound CCN(CC)C1=CC=CC=C1C(=O)OCCC(C)C HAHWYTLUKCIGPH-UHFFFAOYSA-N 0.000 description 1
- ARXVXVOLXMVYIT-UHFFFAOYSA-N 3-methylbutyl 2-(dimethylamino)benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1N(C)C ARXVXVOLXMVYIT-UHFFFAOYSA-N 0.000 description 1
- TXTQURPQLVHJRE-UHFFFAOYSA-N 3-nitrobenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 TXTQURPQLVHJRE-UHFFFAOYSA-N 0.000 description 1
- HRMCXDSWURAYFR-UHFFFAOYSA-N 3-phenoxyphthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=CC=CC=2)=C1C(O)=O HRMCXDSWURAYFR-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- ACQPQXVMVLINFH-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol;4-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1.CC(C)(C)C1=CC=CC(O)=C1O ACQPQXVMVLINFH-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- LATROIIBXZFCTH-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(methoxymethyl)imidazolidin-2-one Chemical compound COCN1C(O)C(O)N(COC)C1=O LATROIIBXZFCTH-UHFFFAOYSA-N 0.000 description 1
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 1
- KUMOYHHELWKOCB-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol;dihydrochloride Chemical compound Cl.Cl.NC1=CC(N)=C(O)C=C1O KUMOYHHELWKOCB-UHFFFAOYSA-N 0.000 description 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- RQBIGPMJQUKYAH-UHFFFAOYSA-N 4-(3,4-diaminophenoxy)benzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1OC1=CC=C(N)C(N)=C1 RQBIGPMJQUKYAH-UHFFFAOYSA-N 0.000 description 1
- QQWWWAQUMVHHQN-UHFFFAOYSA-N 4-(4-amino-4-phenylcyclohexa-1,5-dien-1-yl)aniline Chemical group C1=CC(N)=CC=C1C1=CCC(N)(C=2C=CC=CC=2)C=C1 QQWWWAQUMVHHQN-UHFFFAOYSA-N 0.000 description 1
- ONBVHGIWMYBABS-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3-difluoroaniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C(F)=C1F ONBVHGIWMYBABS-UHFFFAOYSA-N 0.000 description 1
- QNJWXYRVQVNUQC-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(2-phenylphenyl)aniline Chemical group C1(=C(C=CC=C1)C1=C(C=CC(=C1)N)C1=CC=C(N)C=C1)C1=CC=CC=C1 QNJWXYRVQVNUQC-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- BGQWVIOOEFRPOV-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-[4-hydroxy-3,5-bis(hydroxymethyl)phenyl]propan-2-yl]-2,6-bis(hydroxymethyl)phenol Chemical compound OCC1=C(O)C(CO)=CC(C(C=2C=C(CO)C(O)=C(CO)C=2)(C(F)(F)F)C(F)(F)F)=C1 BGQWVIOOEFRPOV-UHFFFAOYSA-N 0.000 description 1
- IJJNNSUCZDJDLP-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 IJJNNSUCZDJDLP-UHFFFAOYSA-N 0.000 description 1
- ASNOFHCTUSIHOM-UHFFFAOYSA-N 4-[10-(4-aminophenyl)anthracen-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=C(N)C=C1 ASNOFHCTUSIHOM-UHFFFAOYSA-N 0.000 description 1
- MVMOMSLTZMMLJR-UHFFFAOYSA-N 4-[2-(1,3-benzothiazol-2-yl)ethenyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C=CC1=NC2=CC=CC=C2S1 MVMOMSLTZMMLJR-UHFFFAOYSA-N 0.000 description 1
- DQOPDYYQICTYEY-UHFFFAOYSA-N 4-[2-(1,3-benzoxazol-2-yl)ethenyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C=CC1=NC2=CC=CC=C2O1 DQOPDYYQICTYEY-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 description 1
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical compound C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- LTKJRDQWPMBSFN-UHFFFAOYSA-N 4-[3-(4-aminophenyl)-1,1,2,2,3,3-hexafluoropropyl]aniline Chemical compound C1=CC(N)=CC=C1C(F)(F)C(F)(F)C(F)(F)C1=CC=C(N)C=C1 LTKJRDQWPMBSFN-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- GACNZKUFHGKSEX-UHFFFAOYSA-N 4-[4-(4-aminophenyl)-1,1,2,2,3,3,4,4-octafluorobutyl]aniline Chemical compound C1=CC(N)=CC=C1C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1=CC=C(N)C=C1 GACNZKUFHGKSEX-UHFFFAOYSA-N 0.000 description 1
- HBLYIUPUXAWDMA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]-2,6-bis(trifluoromethyl)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=C(C(F)(F)F)C=C(C(C=2C=C(C(OC=3C=CC(N)=CC=3)=C(C=2)C(F)(F)F)C(F)(F)F)(C(F)(F)F)C(F)(F)F)C=C1C(F)(F)F HBLYIUPUXAWDMA-UHFFFAOYSA-N 0.000 description 1
- VCFYKCXKADGLPS-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)-3,5-dimethylphenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]-2,6-dimethylphenoxy]aniline Chemical compound CC1=CC(C(C=2C=C(C)C(OC=3C=CC(N)=CC=3)=C(C)C=2)(C(F)(F)F)C(F)(F)F)=CC(C)=C1OC1=CC=C(N)C=C1 VCFYKCXKADGLPS-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- PDYQWKUIJVOAON-UHFFFAOYSA-N 4-[4-[2-[4-[4-amino-3-(trifluoromethyl)phenoxy]phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]-2-(trifluoromethyl)aniline Chemical compound C1=C(C(F)(F)F)C(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=C(C(N)=CC=3)C(F)(F)F)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 PDYQWKUIJVOAON-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- IWFSADBGACLBMH-UHFFFAOYSA-N 4-[4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenyl]phenoxy]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C(=CC(N)=CC=3)C(F)(F)F)=CC=2)C=C1 IWFSADBGACLBMH-UHFFFAOYSA-N 0.000 description 1
- LACZRKUWKHQVKS-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F LACZRKUWKHQVKS-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- JHIUAEPQGMOWHS-UHFFFAOYSA-N 4-[4-hydroxy-3,5-bis(methoxymethyl)phenyl]-2,6-bis(methoxymethyl)phenol Chemical compound COCC1=C(O)C(COC)=CC(C=2C=C(COC)C(O)=C(COC)C=2)=C1 JHIUAEPQGMOWHS-UHFFFAOYSA-N 0.000 description 1
- FPAKXKXRPMFMLR-UHFFFAOYSA-N 4-[5-(4-aminophenyl)-1,1,2,2,3,3,4,4,5,5-decafluoropentyl]aniline Chemical compound C1=CC(N)=CC=C1C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1=CC=C(N)C=C1 FPAKXKXRPMFMLR-UHFFFAOYSA-N 0.000 description 1
- BOTFKTVSBXEXKF-UHFFFAOYSA-N 4-[7-(4-aminophenyl)-1,1,2,2,3,3,4,4,5,5,6,6,7,7-tetradecafluoroheptyl]aniline Chemical compound C1=CC(N)=CC=C1C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1=CC=C(N)C=C1 BOTFKTVSBXEXKF-UHFFFAOYSA-N 0.000 description 1
- XUWFAPDKIXEUPR-UHFFFAOYSA-N 4-[[3-[[4-(diethylamino)phenyl]methylidene]cyclopentylidene]methyl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C=C(CC1)CC1=CC1=CC=C(N(CC)CC)C=C1 XUWFAPDKIXEUPR-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- ABJQKDJOYSQVFX-UHFFFAOYSA-N 4-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=C(O)C2=C1 ABJQKDJOYSQVFX-UHFFFAOYSA-N 0.000 description 1
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 description 1
- ACQVEWFMUBXEMR-UHFFFAOYSA-N 4-bromo-2-fluoro-6-nitrophenol Chemical compound OC1=C(F)C=C(Br)C=C1[N+]([O-])=O ACQVEWFMUBXEMR-UHFFFAOYSA-N 0.000 description 1
- HHHDJHHNEURCNV-UHFFFAOYSA-N 4-chlorobenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=C(Cl)C=C1 HHHDJHHNEURCNV-UHFFFAOYSA-N 0.000 description 1
- ZWMAYLMVFSCMMS-UHFFFAOYSA-N 4-ethynyl-n,n-dimethylaniline Chemical group CN(C)C1=CC=C(C#C)C=C1 ZWMAYLMVFSCMMS-UHFFFAOYSA-N 0.000 description 1
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 1
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 5-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=CC2=C1O ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 0.000 description 1
- FSBRKZMSECKELY-UHFFFAOYSA-N 5-aminonaphthalen-2-ol Chemical compound OC1=CC=C2C(N)=CC=CC2=C1 FSBRKZMSECKELY-UHFFFAOYSA-N 0.000 description 1
- FPKNJPIDCMAIDW-UHFFFAOYSA-N 5-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(N)=CC=CC2=C1C(O)=O FPKNJPIDCMAIDW-UHFFFAOYSA-N 0.000 description 1
- XVOBQVZYYPJXCK-UHFFFAOYSA-N 5-aminonaphthalene-2-carboxylic acid Chemical compound OC(=O)C1=CC=C2C(N)=CC=CC2=C1 XVOBQVZYYPJXCK-UHFFFAOYSA-N 0.000 description 1
- YDEUKNRKEYICTH-UHFFFAOYSA-N 5-aminoquinolin-8-ol Chemical compound C1=CC=C2C(N)=CC=C(O)C2=N1 YDEUKNRKEYICTH-UHFFFAOYSA-N 0.000 description 1
- RZWRYPGAUIOOMK-UHFFFAOYSA-N 5-nitroso-8-quinolinol Chemical compound C1=CN=C2C(O)=CC=C(N=O)C2=C1 RZWRYPGAUIOOMK-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- QYFYIOWLBSPSDM-UHFFFAOYSA-N 6-aminonaphthalen-1-ol Chemical compound OC1=CC=CC2=CC(N)=CC=C21 QYFYIOWLBSPSDM-UHFFFAOYSA-N 0.000 description 1
- SERBLGFKBWPCJD-UHFFFAOYSA-N 6-aminonaphthalen-2-ol Chemical compound C1=C(O)C=CC2=CC(N)=CC=C21 SERBLGFKBWPCJD-UHFFFAOYSA-N 0.000 description 1
- CKSZZOAKPXZMAT-UHFFFAOYSA-N 6-aminonaphthalene-1-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(N)=CC=C21 CKSZZOAKPXZMAT-UHFFFAOYSA-N 0.000 description 1
- NZTPZUIIYNYZKT-UHFFFAOYSA-N 6-aminonaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(N)=CC=C21 NZTPZUIIYNYZKT-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- SANIRTQDABNCHF-UHFFFAOYSA-N 7-(diethylamino)-3-[7-(diethylamino)-2-oxochromene-3-carbonyl]chromen-2-one Chemical compound C1=C(N(CC)CC)C=C2OC(=O)C(C(=O)C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=CC2=C1 SANIRTQDABNCHF-UHFFFAOYSA-N 0.000 description 1
- ZYSOYLBBCYWEMB-UHFFFAOYSA-N 7-aminonaphthalen-1-ol Chemical compound C1=CC=C(O)C2=CC(N)=CC=C21 ZYSOYLBBCYWEMB-UHFFFAOYSA-N 0.000 description 1
- WSUYONLKFXZZRV-UHFFFAOYSA-N 7-aminonaphthalen-2-ol Chemical compound C1=CC(O)=CC2=CC(N)=CC=C21 WSUYONLKFXZZRV-UHFFFAOYSA-N 0.000 description 1
- BFBAHPDPLUEECU-UHFFFAOYSA-N 7-aminonaphthalene-1-carboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=CC(N)=CC=C21 BFBAHPDPLUEECU-UHFFFAOYSA-N 0.000 description 1
- NBPYPKQPLKDTKB-UHFFFAOYSA-N 7-aminonaphthalene-2-carboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(N)=CC=C21 NBPYPKQPLKDTKB-UHFFFAOYSA-N 0.000 description 1
- SNCJAJRILVFXAE-UHFFFAOYSA-N 9h-fluorene-2,7-diamine Chemical compound NC1=CC=C2C3=CC=C(N)C=C3CC2=C1 SNCJAJRILVFXAE-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 102100033806 Alpha-protein kinase 3 Human genes 0.000 description 1
- 101710082399 Alpha-protein kinase 3 Proteins 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- SYSPOOPLPCVGLD-UHFFFAOYSA-N C1(=CC=C(C=C1)S(=O)(=O)OC(C(C=N)=O)C)C Chemical compound C1(=CC=C(C=C1)S(=O)(=O)OC(C(C=N)=O)C)C SYSPOOPLPCVGLD-UHFFFAOYSA-N 0.000 description 1
- VXOUILHMFVRYJI-UHFFFAOYSA-N CCCCOC(OCCCC)(OCCCC)CC(OCCCC)C(OCCCC)(OCCCC)NC1=NC(N)=NC(N)=N1 Chemical compound CCCCOC(OCCCC)(OCCCC)CC(OCCCC)C(OCCCC)(OCCCC)NC1=NC(N)=NC(N)=N1 VXOUILHMFVRYJI-UHFFFAOYSA-N 0.000 description 1
- SZXLVCZMNIWFSR-UHFFFAOYSA-M COC(OC(C=C1)=CC=C1[S+](C)C)=O.CS([O-])(=O)=O Chemical compound COC(OC(C=C1)=CC=C1[S+](C)C)=O.CS([O-])(=O)=O SZXLVCZMNIWFSR-UHFFFAOYSA-M 0.000 description 1
- WCWSKZNPFCFJBW-UHFFFAOYSA-N CSC(C=C1)=CC=C1O.CS(OCC1=CC=CC=C1)(=O)=O Chemical compound CSC(C=C1)=CC=C1O.CS(OCC1=CC=CC=C1)(=O)=O WCWSKZNPFCFJBW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- BJQWYEJQWHSSCJ-UHFFFAOYSA-N Heptacosane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCC BJQWYEJQWHSSCJ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical group C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- IFAWYXIHOVRGHQ-UHFFFAOYSA-N Nonadecandioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCC(O)=O IFAWYXIHOVRGHQ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- HJRBEHGGICYUDN-UHFFFAOYSA-N O=S.[B+3] Chemical class O=S.[B+3] HJRBEHGGICYUDN-UHFFFAOYSA-N 0.000 description 1
- HZYYJGBYLVDXGY-UHFFFAOYSA-N OC(COC1=CC(=C(C=C1)N1NC(=C(C(=N1)C1=C(C=C(C=C1)C)C)C1=C(C=CC=C1)O)C1=C(C=C(C=C1)C)C)O)COCCCCCCCCCCCCC Chemical class OC(COC1=CC(=C(C=C1)N1NC(=C(C(=N1)C1=C(C=C(C=C1)C)C)C1=C(C=CC=C1)O)C1=C(C=C(C=C1)C)C)O)COCCCCCCCCCCCCC HZYYJGBYLVDXGY-UHFFFAOYSA-N 0.000 description 1
- MAOLXURNLQQKOZ-UHFFFAOYSA-N OC1=C(C=CC(=C1)OCCC)C1=NC(=NC(=N1)C1=C(C=C(C=C1)OCCC)O)C1=C(C=C(C=C1)C)C.OC1=C(C=CC(=C1)O)C1=NC(=NC(=N1)C1=C(C=C(C=C1)C)C)C1=C(C=C(C=C1)C)C Chemical compound OC1=C(C=CC(=C1)OCCC)C1=NC(=NC(=N1)C1=C(C=C(C=C1)OCCC)O)C1=C(C=C(C=C1)C)C.OC1=C(C=CC(=C1)O)C1=NC(=NC(=N1)C1=C(C=C(C=C1)C)C)C1=C(C=C(C=C1)C)C MAOLXURNLQQKOZ-UHFFFAOYSA-N 0.000 description 1
- BWCVHEUMKZNMHY-UHFFFAOYSA-N OC1=CC=C(C=C1)[S+](CC1=C(C=CC=C1)C)C.CS(=O)(=O)[O-] Chemical compound OC1=CC=C(C=C1)[S+](CC1=C(C=CC=C1)C)C.CS(=O)(=O)[O-] BWCVHEUMKZNMHY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229920002035 Pluronic® L 10 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229930183415 Suberin Natural products 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- 229920002359 Tetronic® Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- DPQRMIPRAHPPNE-UHFFFAOYSA-N [(1-oxo-1-phenylpropan-2-ylidene)amino] acetate Chemical compound CC(=O)ON=C(C)C(=O)C1=CC=CC=C1 DPQRMIPRAHPPNE-UHFFFAOYSA-N 0.000 description 1
- ZNZDJSGUWLGTLA-UHFFFAOYSA-N [(1-oxo-1-phenylpropan-2-ylidene)amino] benzoate Chemical compound C=1C=CC=CC=1C(=O)C(C)=NOC(=O)C1=CC=CC=C1 ZNZDJSGUWLGTLA-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- PICGUDVETMNGMN-UHFFFAOYSA-N [2,3-bis(hydroxymethyl)phenyl]-phenylmethanone Chemical compound OCc1cccc(C(=O)c2ccccc2)c1CO PICGUDVETMNGMN-UHFFFAOYSA-N 0.000 description 1
- WIMRPMLPJZLCAM-UHFFFAOYSA-N [2,3-bis(methoxymethyl)phenyl]-phenylmethanone Chemical compound COCc1cccc(C(=O)c2ccccc2)c1COC WIMRPMLPJZLCAM-UHFFFAOYSA-N 0.000 description 1
- RYSWVYFTSSTNMY-UHFFFAOYSA-N [2-(hydroxymethyl)-3,4-dimethoxyphenyl]methanol Chemical compound COC1=CC=C(CO)C(CO)=C1OC RYSWVYFTSSTNMY-UHFFFAOYSA-N 0.000 description 1
- UAGDZLRBMHVJNS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl] 2-(hydroxymethyl)benzoate Chemical compound OCc1ccccc1OC(=O)c1ccccc1CO UAGDZLRBMHVJNS-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- ZCWHTBJAXKQNAO-UHFFFAOYSA-N [2-(methoxymethyl)phenyl] 2-(methoxymethyl)benzoate Chemical compound COCc1ccccc1OC(=O)c1ccccc1COC ZCWHTBJAXKQNAO-UHFFFAOYSA-N 0.000 description 1
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- HIVQCJOGAHNXBO-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] propanoate Chemical compound CCC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C HIVQCJOGAHNXBO-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- KGUYZCLKIAMWTP-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-(2-ethenylphenyl)methanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=CC=C1C=C KGUYZCLKIAMWTP-UHFFFAOYSA-N 0.000 description 1
- CNFQQUXCFJEREO-UHFFFAOYSA-N [4-[4-(hydroxymethyl)-2,3-dimethylphenyl]phenyl]methanol Chemical group CC=1C(=C(C=CC=1CO)C1=CC=C(C=C1)CO)C CNFQQUXCFJEREO-UHFFFAOYSA-N 0.000 description 1
- SFHGONLFTNHXDX-UHFFFAOYSA-N [4-[4-(hydroxymethyl)phenyl]phenyl]methanol Chemical group C1=CC(CO)=CC=C1C1=CC=C(CO)C=C1 SFHGONLFTNHXDX-UHFFFAOYSA-N 0.000 description 1
- IIOBAWYKQQMMEQ-UHFFFAOYSA-N [B+3].I Chemical compound [B+3].I IIOBAWYKQQMMEQ-UHFFFAOYSA-N 0.000 description 1
- IRXUPISPXFFGEO-UHFFFAOYSA-N [B+3].S Chemical class [B+3].S IRXUPISPXFFGEO-UHFFFAOYSA-N 0.000 description 1
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical compound [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 description 1
- XQAXKRLKNVVHSS-UHFFFAOYSA-J [Ti+4].Cc1cc([O-])c(C)c(C)c1C.Cc1cc([O-])c(C)c(C)c1C.Cc1cc([O-])c(C)c(C)c1C.Cc1cc([O-])c(C)c(C)c1C Chemical compound [Ti+4].Cc1cc([O-])c(C)c(C)c1C.Cc1cc([O-])c(C)c(C)c1C.Cc1cc([O-])c(C)c(C)c1C.Cc1cc([O-])c(C)c(C)c1C XQAXKRLKNVVHSS-UHFFFAOYSA-J 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Substances CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- WFDIJRYMOXRFFG-XPULMUKRSA-N acetyl acetate Chemical compound [14CH3]C(=O)OC([14CH3])=O WFDIJRYMOXRFFG-XPULMUKRSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000003855 acyl compounds Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000005138 alkoxysulfonyl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000002729 alkyl fluoride group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical compound [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229960004909 aminosalicylic acid Drugs 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000005427 anthranyl group Chemical group 0.000 description 1
- 230000002744 anti-aggregatory effect Effects 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical class [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 125000003286 aryl halide group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- PAQKRBLMHQTWAS-UHFFFAOYSA-N azane;n-hydroxy-n-naphthalen-1-ylnitrous amide Chemical compound N.C1=CC=C2C(N(N=O)O)=CC=CC2=C1 PAQKRBLMHQTWAS-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- ZVSKZLHKADLHSD-UHFFFAOYSA-N benzanilide Chemical compound C=1C=CC=CC=1C(=O)NC1=CC=CC=C1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- JGFLAAWSLCPCDY-UHFFFAOYSA-N benzene;cyclopenta-1,3-diene;iron Chemical compound [Fe].C1C=CC=C1.C1=CC=CC=C1 JGFLAAWSLCPCDY-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- ZDKRMIJRCHPKLW-UHFFFAOYSA-N benzyl methanesulfonate Chemical compound CS(=O)(=O)OCC1=CC=CC=C1 ZDKRMIJRCHPKLW-UHFFFAOYSA-N 0.000 description 1
- UCAZCFGVGXXBPN-UHFFFAOYSA-N benzyl trifluoromethanesulfonate methyl (4-methylsulfanylphenyl) carbonate Chemical compound COC(OC(C=C1)=CC=C1SC)=O.O=S(C(F)(F)F)(OCC1=CC=CC=C1)=O UCAZCFGVGXXBPN-UHFFFAOYSA-N 0.000 description 1
- YJPLHYFFLWBLDW-UHFFFAOYSA-N benzyl-(4-hydroxyphenyl)-methylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=C(O)C=CC=1[S+](C)CC1=CC=CC=C1 YJPLHYFFLWBLDW-UHFFFAOYSA-N 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- AEWGGPYHSLODJJ-UHFFFAOYSA-N bis(3-amino-4-hydroxyphenyl)methanone Chemical compound C1=C(O)C(N)=CC(C(=O)C=2C=C(N)C(O)=CC=2)=C1 AEWGGPYHSLODJJ-UHFFFAOYSA-N 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- HEYYMASVKJXRDV-UHFFFAOYSA-N bis[(3-ethyloxetan-3-yl)methyl] benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2(CC)COC2)C=CC=1C(=O)OCC1(CC)COC1 HEYYMASVKJXRDV-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000005382 boronyl group Chemical group 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- MTKOCRSQUPLVTD-UHFFFAOYSA-N butan-1-olate;titanium(2+) Chemical compound CCCCO[Ti]OCCCC MTKOCRSQUPLVTD-UHFFFAOYSA-N 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- CFOYWRHIYXMDOT-UHFFFAOYSA-N carbimazole Chemical compound CCOC(=O)N1C=CN(C)C1=S CFOYWRHIYXMDOT-UHFFFAOYSA-N 0.000 description 1
- 229960001704 carbimazole Drugs 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical group C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 1
- 125000005578 chrysene group Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- ZQWRZCZEOLZBQF-UHFFFAOYSA-N cyclopentane-1,3-diamine Chemical compound NC1CCC(N)C1 ZQWRZCZEOLZBQF-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004986 diarylamino group Chemical group 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- HOWGUJZVBDQJKV-UHFFFAOYSA-N docosane Chemical compound CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- WNIHNYUROPJCLW-UHFFFAOYSA-N ethyl 2-ethoxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)OCC WNIHNYUROPJCLW-UHFFFAOYSA-N 0.000 description 1
- AYCOCJMEYVYNPM-UHFFFAOYSA-N ethyl 7-(dimethylamino)-2-oxochromene-3-carboxylate Chemical compound C1=C(N(C)C)C=C2OC(=O)C(C(=O)OCC)=CC2=C1 AYCOCJMEYVYNPM-UHFFFAOYSA-N 0.000 description 1
- YDMWUMUNUXUYKT-UHFFFAOYSA-N ethyl [(1-oxo-1-phenylpropan-2-ylidene)amino] carbonate Chemical compound CCOC(=O)ON=C(C)C(=O)C1=CC=CC=C1 YDMWUMUNUXUYKT-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002192 heptalenyl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003427 indacenyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- BHIWKHZACMWKOJ-UHFFFAOYSA-N isobutyric acid methyl ester Natural products COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- HITOXZPZGPXYHY-UJURSFKZSA-N levoglucosenone Chemical compound O=C1C=C[C@H]2CO[C@@H]1O2 HITOXZPZGPXYHY-UJURSFKZSA-N 0.000 description 1
- HITOXZPZGPXYHY-UHFFFAOYSA-N levoglucosenone Natural products O=C1C=CC2COC1O2 HITOXZPZGPXYHY-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- KBOPZPXVLCULAV-UHFFFAOYSA-N mesalamine Chemical compound NC1=CC=C(O)C(C(O)=O)=C1 KBOPZPXVLCULAV-UHFFFAOYSA-N 0.000 description 1
- 229960004963 mesalazine Drugs 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- JDQLUYWHCUWSJE-UHFFFAOYSA-N methanolate;titanium(3+) Chemical compound [Ti+3].[O-]C.[O-]C.[O-]C JDQLUYWHCUWSJE-UHFFFAOYSA-N 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-O methylsulfide anion Chemical compound [SH2+]C LSDPWZHWYPCBBB-UHFFFAOYSA-O 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- GXMIHVHJTLPVKL-UHFFFAOYSA-N n,n,2-trimethylpropanamide Chemical compound CC(C)C(=O)N(C)C GXMIHVHJTLPVKL-UHFFFAOYSA-N 0.000 description 1
- MORLSCQKZAPYFM-UHFFFAOYSA-N n,n-dimethylethanesulfonamide Chemical compound CCS(=O)(=O)N(C)C MORLSCQKZAPYFM-UHFFFAOYSA-N 0.000 description 1
- WCFDSGHAIGTEKL-UHFFFAOYSA-N n,n-dimethylmethanesulfonamide Chemical compound CN(C)S(C)(=O)=O WCFDSGHAIGTEKL-UHFFFAOYSA-N 0.000 description 1
- DKLYDESVXZKCFI-UHFFFAOYSA-N n,n-diphenylacetamide Chemical compound C=1C=CC=CC=1N(C(=O)C)C1=CC=CC=C1 DKLYDESVXZKCFI-UHFFFAOYSA-N 0.000 description 1
- YALAVAYMNJCEBU-UHFFFAOYSA-N n-(2-chloro-3-formylpyridin-4-yl)-2,2-dimethylpropanamide Chemical compound CC(C)(C)C(=O)NC1=CC=NC(Cl)=C1C=O YALAVAYMNJCEBU-UHFFFAOYSA-N 0.000 description 1
- UAOIEEWQVAXCFY-UHFFFAOYSA-N n-(3,4-dimethylphenyl)acetamide Chemical compound CC(=O)NC1=CC=C(C)C(C)=C1 UAOIEEWQVAXCFY-UHFFFAOYSA-N 0.000 description 1
- YUOMCRCBTBNCCS-JUKUECOXSA-N n-[(2s)-1-[[(5s)-5-[(4-aminophenyl)sulfonyl-(2-methylpropyl)amino]-6-hydroxyhexyl]amino]-1-oxo-3,3-diphenylpropan-2-yl]-6-methylpyridine-3-carboxamide Chemical compound N([C@H](C(=O)NCCCC[C@@H](CO)N(CC(C)C)S(=O)(=O)C=1C=CC(N)=CC=1)C(C=1C=CC=CC=1)C=1C=CC=CC=1)C(=O)C1=CC=C(C)N=C1 YUOMCRCBTBNCCS-JUKUECOXSA-N 0.000 description 1
- ZBOYHAZRFJBUEL-UHFFFAOYSA-N n-[2-(4-benzhydryloxypiperidin-1-yl)ethyl]-3-hydroxy-5-(pyridin-3-ylmethoxy)naphthalene-2-carboxamide Chemical compound C1=CC=C2C=C(C(=O)NCCN3CCC(CC3)OC(C=3C=CC=CC=3)C=3C=CC=CC=3)C(O)=CC2=C1OCC1=CC=CN=C1 ZBOYHAZRFJBUEL-UHFFFAOYSA-N 0.000 description 1
- RFOFSJSIPINUPM-UHFFFAOYSA-N n-[5-[1,1,1,3,3,3-hexafluoro-2-[4-hydroxy-3-(methanesulfonamido)phenyl]propan-2-yl]-2-hydroxyphenyl]methanesulfonamide Chemical compound C1=C(O)C(NS(=O)(=O)C)=CC(C(C=2C=C(NS(C)(=O)=O)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 RFOFSJSIPINUPM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DQMWMUMCNOJLSI-UHFFFAOYSA-N n-carbamothioylbenzamide Chemical compound NC(=S)NC(=O)C1=CC=CC=C1 DQMWMUMCNOJLSI-UHFFFAOYSA-N 0.000 description 1
- MBMOGJGVYAHBLN-UHFFFAOYSA-N n-cyclohexylbutane-1-sulfonamide Chemical compound CCCCS(=O)(=O)NC1CCCCC1 MBMOGJGVYAHBLN-UHFFFAOYSA-N 0.000 description 1
- IFRSZVJWYIYNAE-UHFFFAOYSA-N n-dodecylmethanesulfonamide Chemical compound CCCCCCCCCCCCNS(C)(=O)=O IFRSZVJWYIYNAE-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- CLXHPJUNPZCTCP-UHFFFAOYSA-N n-methoxymethanesulfonamide Chemical compound CONS(C)(=O)=O CLXHPJUNPZCTCP-UHFFFAOYSA-N 0.000 description 1
- LMTGCJANOQOGPI-UHFFFAOYSA-N n-methyl-n-phenylacetamide Chemical compound CC(=O)N(C)C1=CC=CC=C1 LMTGCJANOQOGPI-UHFFFAOYSA-N 0.000 description 1
- ZYURHZPYMFLWSH-UHFFFAOYSA-N n-octacosane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCC ZYURHZPYMFLWSH-UHFFFAOYSA-N 0.000 description 1
- HDLRSIQOZFLEPK-UHFFFAOYSA-N naphthalene-1,2,5,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(=O)O)=CC=C21 HDLRSIQOZFLEPK-UHFFFAOYSA-N 0.000 description 1
- DSCIZKMHZPGBNI-UHFFFAOYSA-N naphthalene-1,3,5,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C2=CC(C(=O)O)=CC(C(O)=O)=C21 DSCIZKMHZPGBNI-UHFFFAOYSA-N 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical class [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- BTHGHFBUGBTINV-UHFFFAOYSA-N naphthalene-2,3,6-tricarboxylic acid Chemical compound C1=C(C(O)=O)C(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 BTHGHFBUGBTINV-UHFFFAOYSA-N 0.000 description 1
- SWBLLSQMOMPTMC-UHFFFAOYSA-N naphthalene-2-sulfonamide Chemical compound C1=CC=CC2=CC(S(=O)(=O)N)=CC=C21 SWBLLSQMOMPTMC-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000005582 pentacene group Chemical group 0.000 description 1
- VHDHONCVIHDOAO-UHFFFAOYSA-N pentacosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHDHONCVIHDOAO-UHFFFAOYSA-N 0.000 description 1
- GUVXZFRDPCKWEM-UHFFFAOYSA-N pentalene group Chemical group C1=CC=C2C=CC=C12 GUVXZFRDPCKWEM-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ROTJZTYLACIJIG-UHFFFAOYSA-N pentane-1,3,5-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CCC(O)=O ROTJZTYLACIJIG-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 description 1
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical group C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical group 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical group N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-O selenonium Chemical class [SeH3+] SPVXKVOXSXTJOY-UHFFFAOYSA-O 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 description 1
- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
Definitions
- the present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
- Resins such as polyimide, polybenzoxazole, and polyamide-imide have excellent heat resistance and insulating properties, and are therefore applied to various applications.
- the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film and a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
- resins such as polyimide, polybenzoxazole, and polyamide-imide are cured containing at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors.
- a curable resin composition is applied to a base material by, for example, coating to form a photosensitive film, and then exposed, developed, heated or the like as necessary to apply the cured product onto the base material. Can be formed.
- the polyimide precursor, the polybenzoxazole precursor, and the polyamide-imide precursor are cyclized by, for example, heating, and become polyimide, polybenzoxazole, and polyamide-imide in the cured product, respectively.
- the curable resin composition can be applied by a known coating method or the like, for example, the degree of freedom in designing the shape, size, application position, etc. of the applied curable resin composition at the time of application is high. It can be said that it has excellent manufacturing adaptability.
- the industrial application development of the above-mentioned curable resin composition is expected more and more.
- Patent Document 1 describes a polyimide precursor having a specific structure: 100 parts by mass, a photopolymerization initiator: 1 to 20 parts by mass, and a functional group selected from the group consisting of a hydroxyl group, an ether group and an ester group.
- a negative photosensitive resin composition containing one or more monocarboxylic acid compounds having 2 to 30 carbon atoms: 0.01 to 10 parts by mass is described.
- Improvement of resolution is required in the formation of a pattern made of a curable resin composition.
- the present invention relates to a curable resin composition having excellent resolution at the time of pattern formation, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and a method for producing the cured film.
- An object of the present invention is to provide a semiconductor device including the cured film or the laminate.
- At least one resin selected from the group, as well as Contains organometallic complexes The total molar amount of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor is 0.08 to 1.68 mmol / g.
- the molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol / g.
- the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamide-imide precursor is 0.062 to 1.186 mmol / g.
- Curable resin composition. ⁇ 2> The curable resin composition according to ⁇ 1>, further comprising a photopolymerization initiator.
- ⁇ 4> The curable resin composition according to any one of ⁇ 1> to ⁇ 3>, further comprising a cross-linking agent.
- ⁇ 5> The curable resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the organometallic complex is a metallocene compound.
- ⁇ 6> The curability according to any one of ⁇ 1> to ⁇ 5>, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium and hafnium.
- Resin composition ⁇ 7>
- the curable resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the organometallic complex has a photoradical polymerization initiation ability.
- ⁇ 8> The curable resin composition according to any one of ⁇ 1> to ⁇ 7>, which is used for forming a photosensitive film to be used for negative development.
- ⁇ 9> The curable resin composition according to any one of ⁇ 1> to ⁇ 8>, which is used for forming an interlayer insulating film for a rewiring layer.
- ⁇ 10> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 9>.
- ⁇ 11> A laminate containing two or more layers of the cured film according to ⁇ 10> and containing a metal layer between any of the cured films.
- a method for producing a cured film which comprises a film forming step of applying the curable resin composition according to any one of ⁇ 1> to ⁇ 9> to a substrate to form a film.
- the method for producing a cured film according to ⁇ 12> which comprises an exposure step of exposing the film and a developing step of developing the film.
- the method for producing a cured film according to ⁇ 13> wherein the exposure light used for the above exposure includes light having a wavelength of 405 nm.
- ⁇ 16> The method for producing a cured film according to any one of ⁇ 12> to ⁇ 15>, which comprises a heating step of heating the film at 50 to 450 ° C.
- a semiconductor device comprising the cured film according to ⁇ 10> or the laminate according to ⁇ 11>.
- a curable resin composition having excellent resolution at the time of pattern formation a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and the like. And a semiconductor device including the cured film or the laminate is provided.
- the present invention is not limited to the specified embodiments.
- the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
- the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
- the notation not describing substitution and non-substitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
- the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
- (meth) acrylate means both “acrylate” and “methacrylate”, or either
- (meth) acrylic means both “acrylic” and “methacrylic", or
- (meth) acryloyl means both “acryloyl” and “methacrylic", or either.
- Me in the structural formula represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- the total solid content means the total mass of all the components of the composition excluding the solvent.
- the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
- GPC measurement gel permeation chromatography
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
- the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive film, the direction from the base material to the photosensitive film is referred to as “upper”.
- the opposite direction is referred to as "down”.
- the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
- the content of each component in the composition means the total content of all the compounds corresponding to the component.
- the temperature is 23 ° C.
- the atmospheric pressure is 101,325 Pa (1 atm)
- the relative humidity is 50% RH.
- the combination of preferred embodiments is a more preferred embodiment.
- the curable resin composition of the present invention comprises a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor containing a benzoxazole structure, and at least one of a cyclic imide structure and a cyclic isoimide structure.
- the total molar content of the cyclic isoimide structure is 0.08 to 1.68 mmol / g, and the molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor is 0.22 to 3 It is .97 mmol / g, and the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamideimide precursor is 0.062 to 1.186 mmol / g.
- the curable resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and is used for forming a film to be subjected to exposure and development using a developing solution containing an organic solvent. Is preferable. Further, the curable resin composition of the present invention is preferably used for forming a photosensitive film to be used for negative development.
- the negative type development means the development in which the non-exposed part is removed by the development in the exposure and the development
- the positive type development means the development in which the exposed part is removed by the development.
- the exposure method, the developer, and the developing method include, for example, the exposure method described in the exposure step in the description of the method for producing a cured film described later, the developer and the developing method described in the developing step. Is used.
- the curable resin composition of the present invention is excellent in exposure sensitivity and chemical resistance of the obtained pattern.
- the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
- an organic titanium compound or the like is added to the curable resin composition.
- the organometallic complex may aggregate in the film and the resolution may decrease.
- a resin containing a cyclic imide structure, a cyclic isoimide structure or a benzoxazole structure at a specific content is used as the resin in the resin composition. It is considered that the organometallic complex contained in the composition is dispersed in the film in a nearly uniform state by the strong interaction between these structures and the organometallic complex. As a result, it is presumed that the resin composition of the present invention has excellent resolution.
- the curable resin composition of the present invention comprises a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor containing a benzoxazole structure, and at least one of a cyclic imide structure and a cyclic isoimide structure. It contains at least one resin (specific resin) selected from the group consisting of polyamide-imide precursors containing.
- the curable resin composition of the present invention preferably contains, as the specific resin, a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure. Further, the specific resin preferably has a radically polymerizable group.
- the curable resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described below as a photosensitizer, and is described later. It is more preferable to contain the radical cross-linking agent described above, and it is further preferable to contain the photoradical polymerization initiator described below as the photosensitizer, the radical cross-linking agent described below, and the sensitizer described below. From such a curable resin composition, for example, a negative photosensitive film is formed. Further, the specific resin may have a polarity converting group such as an acid-decomposable group.
- the curable resin composition preferably contains a photoacid generator described later as a photosensitizer. From such a curable resin composition, for example, a chemically amplified positive type photosensitive film or a negative type photosensitive film is formed.
- the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the polyimide precursor is 0.08 to 1.68 mmol from the viewpoint of resolution.
- / G preferably 0.10 to 1.00 mmol / g, more preferably 0.12 to 0.80 mmol / g, and further preferably 0.15 to 0.60 mmol / g. preferable.
- the polyimide precursor preferably contains at least a cyclic imide structure.
- the polyimide precursor may have at least one of a cyclic imide structure and a cyclic isoimide structure in the side chain, but preferably has at least one in the main chain.
- the main chain of a resin means a relatively longest molecular chain in a molecule.
- the resin composition contains a polybenzoxazole precursor as a specific resin
- the molar content of the benzoxazole structure in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol / from the viewpoint of resolution. It is g, preferably 0.25 to 3.00 mmol / g, more preferably 0.28 to 2.50 mmol / g, and even more preferably 0.30 to 2.00 mmol / g. ..
- the polybenzoxazole precursor may have a benzoxazole structure in the side chain, but is preferably in the main chain.
- the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the above-mentioned polyamide-imide precursor is 0.062 to 1 from the viewpoint of resolution. .186 mmol / g, preferably 0.070 to 1.000 mmol / g, more preferably 0.080 to 0.800 mmol / g, and 0.090 to 0.700 mmol / g. Is more preferable.
- the polyamide-imide precursor preferably contains at least a cyclic imide structure.
- the polyamide-imide precursor may have at least one of a cyclic imide structure and a cyclic isoimide structure in the side chain, but preferably has at least one in the main chain.
- polyimide precursor The type of the polyimide precursor used in the present invention is not particularly specified, but it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2).
- a 1 and A 2 independently represent an oxygen atom or NH
- R 111 represents a divalent organic group
- R 115 represents a tetravalent organic group
- R 113 represents a tetravalent organic group
- R 114 independently represent a hydrogen atom or a monovalent organic group.
- a 1 and A 2 in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
- R 111 in the formula (2) represents a divalent organic group.
- the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms.
- a cyclic aliphatic group of 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
- a group represented by -Ar-L-Ar- is exemplified.
- Ar is an aromatic group independently
- L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, ⁇ CO ⁇ , —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above.
- R 111 is preferably derived from diamine.
- the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof.
- the diamine containing the above is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable.
- aromatic groups include:
- diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl;
- diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/0385898 are also preferable.
- a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/0385898 is also preferably used.
- R 111 is preferably represented by —Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film.
- Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, ⁇ CO ⁇ , —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above.
- Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO 2 - are preferred.
- the aliphatic hydrocarbon group here is preferably an alkylene group.
- R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance.
- a divalent organic group represented by the formula (61) is more preferable.
- Equation (51) In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, methyl group or trifluoro. It is a methyl group.
- the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
- R 58 and R 59 are independently fluorine atoms or trifluoromethyl groups, respectively.
- Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
- diamines can also be preferably used.
- R 115 in the formula (2) represents a tetravalent organic group.
- a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
- * independently represents a binding site with another structure.
- R 112 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —CO ⁇ , —S—, —SO.
- 2- , NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. More preferably, it is a group selected from-, -S- and SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2-, -O-, -CO. It is more preferably a divalent group selected from the group consisting of-, -S- and SO 2-.
- R 115 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
- the tetracarboxylic dianhydride is preferably represented by the following formula (O).
- R 115 represents a tetravalent organic group.
- a preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
- tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-.
- PMDA pyromellitic dianhydride
- 3,3', 4,4'-biphenyltetracarboxylic dianhydride 3,3', 4,4'-.
- tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.
- R 111 and R 115 has an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.
- R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and both contain a polymerizable group.
- the polymerizable group is a group capable of a cross-linking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable.
- the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group and an amino.
- the group is mentioned.
- a group having an ethylenically unsaturated bond is preferable.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
- R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
- * represents a binding site with another structure.
- R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a polyalkyleneoxy group. Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group.
- polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
- the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
- the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
- the carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
- the said alkylene group may have a substituent.
- Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
- the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
- the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance.
- a group in which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable.
- the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
- R 113 and R 114 are independently hydrogen atoms or monovalent organic groups.
- the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one.
- Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
- the acidic group is preferably an OH group. It is also more preferable that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.
- R 113 or R 114 is preferably a monovalent organic group.
- the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
- the alkyl group preferably has 1 to 30 carbon atoms.
- the alkyl group may be linear, branched or cyclic.
- linear or branched alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group.
- Isobutyl group isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) Ethoxy group is mentioned.
- the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
- Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
- Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a boronyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
- aromatic group examples include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene.
- the benzene ring is most preferred.
- R 113 is a hydrogen atom or R 114 is a hydrogen atom
- R 113 is a hydrogen atom
- R 114 is a hydrogen atom
- the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond.
- the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
- At least one of R 113 and R 114 may be a polarity converting group such as an acid degradable group.
- the acid-degradable group is not particularly limited as long as it is decomposed by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group.
- a tertiary alkyl ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity.
- the acid-degradable group examples include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl.
- examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
- the polyimide precursor has a fluorine atom in the structural unit.
- the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
- the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine component an embodiment in which bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like is used can be mentioned.
- the repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened. Equation (2-A) In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group , at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.
- a 1, A 2, R 111 , R 113 and R 114 each independently have the same meaning as A 1, A 2, R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same .
- R 112 has the same meaning as R 112 in formula (5), and preferred ranges are also the same.
- the polyimide precursor may contain one type of repeating structural unit represented by the formula (2), but may contain two or more types. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).
- the polyimide precursor is selected from the group consisting of repeating units represented by any of the following formulas (2-1) to (2-6) as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure. It is preferable to include at least one repeating unit, and the repeating unit represented by the following formula (2-1), the repeating unit represented by the following formula (2-2), and the following formula (2-3). It is more preferable to include at least one repeating unit selected from the group consisting of repeating units represented by.
- R 111 , R 113 , R 114 , R 115 , A 1 and A 2 are R 111 , R 113 and R in the above formula (2), respectively. It is synonymous with 114 , R 115 , A 1 and A 2 , and the preferred embodiment is also the same.
- the total content of the repeating units represented by any of the formulas (2-1) to (2-6) is such that the total content of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor is within the above range. It may be the amount.
- An embodiment in which the amount is 50 mol% or more of all repeating units can be mentioned.
- the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
- the upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor except the terminal are the repeating units represented by the formula (2) and the formulas (2-1) to (2-). It may be any of the repeating units represented by any of 6).
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000.
- the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
- the degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more.
- the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
- the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
- the polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. show.
- R 123 and R 124 are synonymous with R 113 in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
- R 121 represents a divalent organic group.
- the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferable.
- the aliphatic group a linear aliphatic group is preferable.
- R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
- a dicarboxylic acid residue a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
- a dicarboxylic acid containing an aliphatic group a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable.
- a dicarboxylic acid composed of is more preferable.
- the number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10.
- the linear aliphatic group is preferably an alkylene group.
- dicarboxylic acid containing a linear aliphatic group examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadiponic acid, 3-methyladiponic acid, pimellinic acid, 2,2,6,6-tetramethylpimelic acid, suberin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hex
- Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
- dicarboxylic acid containing an aromatic group a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only the following aromatic groups and two -COOH is more preferable.
- A is -CH 2- , -O-, -S-, -SO 2- , -CO-, -NHCO-, -C (CF 3 ) 2- , and -C (CH 3 ) 2- Represents a divalent group selected from the group consisting of, and each independently represents a binding site with another structure.
- dicarboxylic acid containing an aromatic group examples include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
- R 121 may have a structure derived from a dicarboxylic acid or a dicarboxylic acid halide containing a benzoxazole structure.
- a benzoxazole structure is introduced into the benzoxazole precursor. Examples of the above structure include the following structures. In the following structures, * independently represents a binding site with another structure.
- R 122 represents a tetravalent organic group.
- the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferable range is also the same.
- R 122 is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from the bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'.
- bisaminophenol derivatives having the following aromatic groups are preferable.
- X 1 represents -O-, -S-, -C (CF 3 ) 2- , -CH 2- , -SO 2- , -NHCO-, and * and # represent other structures, respectively.
- R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, it is also preferable that R 122 has a structure represented by the above formula.
- any two of the four * and # in total are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, and preferably R 122 in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R 122 are attached in the formula (3) , And two # are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bound, or two * are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bound.
- the site is a site and the two #s are the binding sites with the oxygen atom to which R 122 in the formula (3) is bonded, and the two * are the oxygen to which the R 122 in the formula (3) is bonded. It is more preferable that the binding site is a binding site with an atom and the two #s are the binding sites with a nitrogen atom to which R 122 in the formula (3) is bonded.
- R 1 is a hydrogen atom, an alkylene, a substituted alkylene, -O-, -S-, -SO 2- , -CO-, -NHCO-, a single bond, or the following formula (A-). It is an organic group selected from the group of sc).
- R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
- R 3 is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
- the ortho position of the phenolic hydroxy groups i.e., to have also substituent R 3 is believed to closer the distance of the carbonyl carbon and hydroxy group of the amide bond, at a low temperature It is particularly preferable in that the effect of increasing the cyclization rate when cured is further enhanced.
- R 2 is an alkyl group and R 3 is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.
- R 1 is an alkylene or a substituted alkylene.
- the alkylene and the substituted alkylene according to R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH 2- and -CH (CH 3 ).
- -, -C (CH 3 ) 2 has sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperature. It is more preferable in that an excellent polybenzoxazole precursor can be obtained.
- the polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
- the polybenzoxazole precursor is a repeating unit having a benzoxazole structure, which is a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), and the following formula (3). It is preferable to include at least one repeating unit selected from the group consisting of the repeating units represented by -3). Equation (3-1) in to Formula (3-3), R 121, R 122, respectively R 123 and R 124 has the same meaning as R 121, R 122, R 123 and R 124 in formula (3) , The preferred embodiment is also the same.
- the content of the repeating unit represented by the formula (3-1), the repeating unit represented by the formula (3-2), and the repeating unit represented by the formula (3-3) is a polybenzoxazole precursor.
- the content of the benzoxazole structure in the above range may be set to the above range.
- the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit because it can suppress the occurrence of warpage due to ring closure.
- SL diamine residue represented by the following formula (SL) as another type of repeating structural unit because it can suppress the occurrence of warpage due to ring closure.
- Z has an a structure and a b structure
- R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
- at least one of R 3s, R 4s , R 5s , and R 6s is an aromatic group
- the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
- the polymerization of the a structure and the b structure may be block polymerization or random polymerization.
- the mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.
- preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
- the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
- the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is used as the repeating structural unit. It is also preferable to include it. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (2).
- the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in the compositions described below. It is preferably 22,000 to 28,000.
- the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
- the degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more.
- the upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
- the polyamide-imide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
- PAI-2 R 117 represents a trivalent organic group
- R 111 represents a divalent organic group
- a 2 represents an oxygen atom or -NH-
- R 113 represents a hydrogen atom or monovalent. Represents an organic group of.
- R 117 is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroarophatic group, or a single bond or a linking group.
- Examples of the above-mentioned linked groups are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms.
- the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
- a group in which two or more of the above are combined is more preferable.
- a group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
- an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
- halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
- the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
- preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
- arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
- R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
- a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
- the halogenated tricarboxylic acid compound used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.
- the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a carbon number of carbon atoms.
- a tricarboxylic acid compound containing 6 to 20 aromatic groups or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or carbon by a single bond or a linking group is preferable.
- a tricarboxylic acid compound containing a group in which two or more aromatic groups of the number 6 to 20 are combined is more preferable.
- the tricarboxylic acid compound examples include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
- Or phthalic acid anhydride and benzoic acid are single-bonded, with -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or phenylene group. Examples thereof include linked compounds. These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (eg, trimellitic anhydride). There may be.
- each R 111, A 2, R 113 have the same meaning as R 111, A 2, R 113 in formula (2) described above, preferable embodiments are also the same.
- the polyamide-imide precursor may further contain other repeating units.
- Other repeating units include a repeating unit represented by the above formula (2), a repeating unit represented by any of the formulas (2-1) to (2-6), and the following formula (PAI-1). Examples include the repeating unit represented by.
- R 116 represents a divalent organic group and R 111 represents a divalent organic group.
- R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group. Examples of the above-mentioned linked groups are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms.
- the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
- a group in which two or more of the above are combined is more preferable.
- a group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
- an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
- halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
- the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
- preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
- arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
- R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
- a compound having two carboxy groups is referred to as a dicarboxylic acid compound
- a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.
- the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
- Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds. Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.
- the dicarboxylic acid compound or the dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms.
- a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms is preferable.
- a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.
- dicarboxylic acid compound examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, glutaric acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-.
- R 111 has the same meaning as R 111 in the above equation (2), preferable embodiments thereof are also the same.
- the polyamide-imide precursor preferably contains a repeating unit represented by any of the following formulas (PAI-3) and (PAI-4) as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure. It is more preferable to include a repeating unit represented by the following formula (PAI-3).
- PAI-3 a repeating unit represented by the following formula (PAI-3) or formula (PAI-4)
- R 111 and R 117 are synonymous with R 111 and R 117 in formula (PAI-2), respectively, and so are preferred embodiments.
- the content of the repeating unit represented by any of the formulas (PAI-3) and (PAI-4) is such that the total content of the cyclic imide structure and the cyclic isoimide structure in the polyamide-imide precursor is within the above range. And it is sufficient.
- the polyamide-imide precursor has a fluorine atom in the structural unit.
- the fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
- the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure.
- the diamine component an embodiment in which bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like is used can be mentioned.
- An embodiment in which the content is 50 mol% or more of all repeating units can be mentioned.
- the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
- the upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) and the formula (PAI-1). Repeating unit, repeating unit represented by any of the formulas (PAI-3) and (PAI-4), repeating unit represented by the formula (2), formulas (2-1) to (2-6). It may be any of the repeating units represented by either. Further, as another embodiment of the polyamide-imide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a formula (PAI-3).
- the total content of the repeating units is 50 mol% or more of all the repeating units.
- the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
- the upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) and the formula (PAI-1). It may be either a repeating unit or a repeating unit represented by any of the formulas (PAI-3) and (PAI-4).
- the weight average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. ..
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
- the degree of dispersion of the molecular weight of the polyamide-imide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
- the degree of dispersion of the molecular weight means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
- a polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
- the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
- an organic solvent in the reaction.
- the organic solvent may be one kind or two or more kinds.
- the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
- non-halogen catalyst a known amidation catalyst containing no halogen atom can be used without particular limitation.
- a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used.
- carbodiimide compounds such as salts and urea compounds.
- the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.
- the organic solvent may be one kind or two or more kinds.
- the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
- a dicarboxylic acid or a dicarboxylic acid derivative which may be halogenated by a halogenating agent or may not be halogenated and a non-halogenated catalyst may be used
- a diamine which may be halogenated by a halogenating agent or may not be halogenated and a non-halogenated catalyst may be used
- the total molar content of the cyclic imide structure and the cyclic isoimide structure or the molar content of the benzoxazole structure described above can be adjusted by appropriately setting the reaction time, the reaction temperature, and the pH at the time of the reaction. ..
- the end of the polyimide precursor or the like is used as an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound or a monoactive ester compound. It is preferable to seal. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-.
- a step of precipitating a solid may be included in the production of the polyimide precursor or the like.
- the polyimide precursor or the like in the reaction solution can be precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
- the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.
- the content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 50% by mass or more.
- the content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
- the composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
- the curable resin composition of the present invention preferably contains at least two kinds of resins.
- the curable resin composition of the present invention may contain two or more kinds of the specific resin and another resin described later in total, or may contain two or more kinds of the specific resin, but is specific. It is preferable to contain two or more kinds of resins.
- the curable resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimide precursors having different structures derived from dianhydride (R 115 in the above formula (2)). It is preferable to contain the polyimide precursor of.
- the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in at least one type of polyimide precursor may be within the above range.
- the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in all the polyimide precursors is preferably in the above range with respect to the case where the total amount of all the polyimide precursors is 1 g, and the curable resin composition. It is more preferable that each of the polyimide precursors contained in the product contains a cyclic imide structure and a cyclic isoimide structure in the above range.
- the molar content of the benzoxazole structure contained in at least one polybenzoxazole precursor may be within the above range.
- the total molar content of the benzoxazole structure contained in all the polybenzoxazole precursors is preferably in the above range with respect to the case where the total amount of all the polybenzoxazole precursors is 1 g, and the curable resin composition. It is more preferable that each of the polyimide precursors contained in the above contains at least one of a cyclic imide structure and a cyclic isoimide structure in the above range.
- the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in at least one kind of polyamide-imide precursor is within the above range. It is preferable that the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in all the polyamide-imide precursors is in the above range with respect to the case where the total amount of all the polyamide-imide precursors is 1 g. It is more preferable that each of the polyamide-imide precursors contained in the curable resin composition contains at least one of a cyclic imide structure and a cyclic isoimide structure in the above range.
- the curable resin composition of the present invention contains an organometallic complex.
- the organic metal complex may be an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, and is a compound in which an organic group is coordinated with respect to the metal atom. More preferably, it is a metallocene compound.
- the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have a substituent as ⁇ 5-ligands.
- the organic group is not particularly limited, but a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom is preferable.
- the hetero atom an oxygen atom, a sulfur atom and a nitrogen atom are preferable.
- at least one of the organic groups is preferably a cyclic group, and at least two are more preferably cyclic groups.
- the cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
- the cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferable.
- the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.
- the metal contained in the organic metal complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, and is at least one metal selected from the group consisting of titanium, zirconium and hafnium. More preferably, it is more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.
- the organometallic complex may contain two or more metal atoms or may contain only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one type of metal atom or may contain two or more types of metal atoms.
- the organic metal complex is preferably a ferrocene compound, a titanosen compound, a zirconocene compound or a hafnosen compound, more preferably a titanosen compound, a zirconocene compound or a hafnosen compound, and further preferably a titanosen compound or a zirconocene compound.
- Titanocene compounds are particularly preferred.
- an embodiment in which the organometallic complex has an ability to initiate photoradical polymerization is also one of the preferred embodiments of the present invention.
- the organometallic complex is dispersed in the film in a nearly uniform state by using the specific resin. Therefore, when the organometallic complex has the ability to initiate photoradical polymerization, it is considered that the aggregation of the organometallic complex due to the aggregation of the organic metal complex suppresses the aggregation of the local radical polymerization initiator. It is considered that the degree of polymerization of the specific resin or the cross-linking agent tends to be close to uniform in the film by suppressing the aggregation of the radical polymerization initiator.
- having the ability to initiate photoradical polymerization means that free radicals capable of initiating radical polymerization can be generated by irradiation with light. For example, when a composition containing a radical cross-linking agent and an organic metal complex is irradiated with light in a wavelength range in which the organic metal complex absorbs light and the radical cross-linking agent does not absorb light, radicals are generated. By confirming the presence or absence of the disappearance of the cross-linking agent, the presence or absence of the photoradical polymerization initiation ability can be confirmed.
- the organometallic complex has a photoradical polymerization initiating ability
- the organometallic complex is preferably a metallocene compound, more preferably a titanosen compound, a zirconocene compound or a hafnosen compound, and is a titanosen compound or a zirconocene compound. Is more preferable, and a titanosen compound is particularly preferable.
- the organic metal complex is at least one selected from the group consisting of a titanosen compound, a tetraalkoxytitanium compound, a titanium acylate compound, a titanium chelate compound, a zirconocene compound and a hafnosen compound. It is preferably a compound of a species, more preferably at least one compound selected from the group consisting of a titanosen compound, a zirconocene compound and a hafnosen compound, and more preferably at least one selected from the group consisting of a titanosen compound and a zirconocene compound. It is more preferably a species compound, and particularly preferably a titanosen compound.
- the molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.
- a compound represented by the following formula (P) is preferably mentioned.
- M is a metal atom and R is an independent substituent.
- the R is preferably independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.
- an iron atom, a titanium atom, a zirconium atom or a hafnium atom is preferable, a titanium atom, a zirconium atom or a hafnium atom is more preferable, a titanium atom or a zirconium atom is further preferable, and titanium. Atoms are particularly preferred.
- the aromatic group in R in the formula (P) include an aromatic group having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, a phenyl group, a 1-naphthyl group, or an aromatic group. , 2-naphthyl group and the like.
- an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, an octyl group, and an isopropyl group.
- T-Butyl group Isopentyl group, 2-Ethylhexyl group, 2-Methylhexyl group, Cyclopentyl group and the like.
- the halogen atom in R include F, Cl, Br, and I.
- an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, an octyl group, and the like.
- examples thereof include an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclopentyl group and the like.
- the R may further have a substituent.
- substituents include halogen atom (F, Cl, Br, I), hydroxy group, carboxy group, amino group, cyano group, aryl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxy.
- substituents include a carbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group and a diarylamino group.
- organic metal complex examples are not particularly limited, but are tetraisopropoxytitanium, tetrakis (2-ethylhexyloxy) titanium, diisopropoxybis (ethylacetacetate) titanium, and diisopropoxybis (acetylacetate).
- the content of the organometallic complex is preferably 0.1 to 30% by mass with respect to the total solid content of the curable resin composition of the present invention.
- the lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more.
- the upper limit is more preferably 25% by mass or less.
- the organometallic complex one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
- the composition of the present invention may contain the above-mentioned specific resin and another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
- other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, and acrylic resin.
- acrylic resin by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
- the composition may be prepared by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the cross-linking agent described later or in addition to the cross-linking agent described later. It is possible to improve the coatability, the solvent resistance of the organic film, and the like.
- the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more. ..
- the content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
- the content of the other resin may be low.
- the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less.
- the lower limit of the content is not particularly limited, and may be 0% by mass or more.
- the composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
- the curable resin composition of the present invention preferably contains a solvent.
- a solvent a known solvent can be arbitrarily used.
- the solvent is preferably an organic solvent.
- the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
- esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
- alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)
- 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
- 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, ethyl 2-alkyl
- ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
- Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.
- ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
- cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
- sulfoxides for example, dimethyl sulfoxide is preferable.
- N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
- Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
- the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
- the mixed solvent to be mixed is preferable.
- the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
- a combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and ⁇ -butyrolactone is also preferable.
- the solvent content is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass.
- the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
- the solvent may contain only one type, or may contain two or more types. When two or more kinds of solvents are contained, the total is preferably in the above range.
- the composition of the present invention preferably contains a photosensitizer. It is assumed that the photosensitizer does not contain the above-mentioned organometallic complex and a compound having a photoradical polymerization initiation ability.
- the composition of the present invention preferably contains a photopolymerization initiator.
- the composition of the present invention preferably contains a photopolymerization initiator as the photosensitizer.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators.
- a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
- the compound corresponding to the organometallic complex does not correspond to the photosensitizer and the photoradical polymerization initiator.
- the composition of the present invention does not substantially contain a radical polymerization initiator other than the above-mentioned organometallic complex.
- the fact that the composition of the present invention does not substantially contain a radical polymerization initiator other than the organometallic complex means that the content of the radical polymerization initiator other than the organometallic complex is based on the total mass of the organometallic complex. It is said that it is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass.
- the composition of the present invention contains an organometallic complex having a radical polymerization initiatoring ability
- the composition of the present invention contains the above-mentioned organometallic complex and a photoradical polymerization initiator. According to such an aspect, as described above, the generation of development residue, the disconnection of the pattern, and the like can be suppressed, and the exposure sensitivity can be improved.
- the composition of the present invention preferably contains a photoradical polymerization initiator. Since the composition of the present invention contains a specific resin, it is considered that aggregation of the organometallic complex is suppressed.
- the composition of the present invention contains an organometallic complex and a photoradical polymerization initiator
- the content of the organometallic complex with respect to the total content of the organometallic complex and the photoradical polymerization initiator is 20 to 80% by mass. It is preferably 30 to 70% by mass, and more preferably 30 to 70% by mass.
- an oxime compound described later is preferable.
- the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable.
- the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
- a known compound can be arbitrarily used as the photoradical polymerization initiator.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like.
- paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
- Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification.
- KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
- Nippon Kayaku Co., Ltd. is also preferably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.
- IRGACURE 184 (IRGACURE is a registered trademark)
- DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
- the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
- acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
- the photoradical polymerization initiator is more preferably an oxime compound.
- the exposure latitude can be improved more effectively.
- the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
- the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
- an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator.
- IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
- a radical polymerization initiator 2) is also preferably used.
- TR-PBG-304 manufactured by Changshu Powerful Electronics New Materials Co., Ltd.
- ADEKA ARCLUDS NCI-831 ADEKA ARCULDS NCI-930
- DFI-091 manufactured by Daito Chemix Co., Ltd.
- an oxime compound having the following structure can also be used.
- an oxime compound having a fluorene ring can also be used.
- Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 6636081.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
- an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
- Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
- the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl.
- More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
- At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.
- the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
- 2-benzyl such as benzophenone
- benzoin ether compounds such as benzoin alkyl ether
- benzoin compounds such as benzoin and alkyl benzoin
- benzyl derivatives such as benzyl dimethyl ketal.
- a compound represented by the following formula (I) can also be used.
- RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
- R I01 is a group represented by formula (II), the same as R I00
- the groups, R I02 to R I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.
- R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
- the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.
- the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.
- the composition of the present invention preferably contains a photoacid generator as a photosensitizer.
- a photoacid generator for example, acid is generated in the exposed part of the photosensitive film, the solubility of the exposed part in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed part is removed by the developing solution.
- a positive pattern can be obtained.
- the composition contains a photoacid generator and a cross-linking agent other than the radical cross-linking agent described later, for example, the cross-linking reaction of the cross-linking agent is promoted by the acid generated in the exposed part, and the exposed part becomes It is also possible to make it more difficult to be removed by the developing solution than the non-exposed portion. According to such an aspect, a negative type pattern can be obtained.
- the photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
- onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
- examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.
- the quinone diazide compound includes a polyhydroxy compound in which quinone diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone diazide sulfonic acid is ester-bonded and a sulfonamide bond.
- Examples include those bound by at least one of the above. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
- the quinone diazide either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used.
- the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
- the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
- a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed.
- a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.
- the naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
- Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.
- Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
- the photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
- oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-) It is preferably an oxime sulfonate compound represented by 105).
- X 3 is an alkyl group, an alkoxyl group, or a halogen atom. If X 3 there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X 3 may have a substituent.
- the halogen atom in the X 3, a chlorine atom or a fluorine atom is preferable.
- m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X 3 may be the same or different.
- R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W.
- W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. It represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
- oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-209692A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.
- R s1 represents an alkyl group, an aryl group, or a heteroaryl group
- R s2 which may be present in a plurality of groups, independently represents a hydrogen atom, an alkyl group, and an aryl
- R s6 which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
- Xs represents O or S.
- ns 1 or 2
- ms represents an integer of 0-6.
- an alkyl group represented by R s1 preferably having 1 to 30 carbon atoms
- an aryl group preferably having 6 to 30 carbon atoms
- a heteroaryl group carbon
- numbers 4 to 30 may have a substituent T.
- R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable.
- R s2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
- the alkyl group or aryl group represented by R s2 may have a substituent T.
- Xs represents O or S, and is preferably O.
- the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
- ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
- the alkyl group represented by R s6 preferably having 1 to 30 carbon atoms
- the alkyloxy group preferably having 1 to 30 carbon atoms
- ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
- the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
- the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
- R t1 represents an alkyl group, an aryl group or a heteroaryl group
- R t7 represents a hydrogen atom or a bromine atom
- R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups
- R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups
- R t2 represents a hydrogen atom or a methyl group.
- R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
- R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, or a phenyl group.
- it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
- R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
- R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
- the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
- Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692A and paragraphs of JP2015-194674A.
- the compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
- oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
- Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Represents an aryl group or a heteroaryl group.
- R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
- Ru2a represents an alkyl or aryl group.
- Xu is -O-, -S-, -NH- , -NR u5-, -CH 2- , -CR u6 H- or CR u6 R u7.
- Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the R u1 ⁇ R u4. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
- R u1 ⁇ R u4 a hydrogen atom, preferably a halogen atom or an alkyl group, also aspects to form the at least two aryl groups bonded to each other of R u1 ⁇ R u4 preferred.
- Ru1 to Ru4 are hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
- the compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
- the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
- Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP2011-209692 and paragraph numbers 0195 to 0207 of JP2015-194674. These contents are incorporated herein by reference.
- the following b-9, b-16, b-31, and b-33 are preferable.
- a commercially available product may be used as the photoacid generator.
- Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-69 (any of which).
- Fujifilm Wako Pure Chemical Industries, Ltd. Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 (all manufactured by BASF) (Made by Midori Chemical Industries, Ltd.) and the like.
- an organic halogenated compound can also be applied.
- the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-46-4605, JP-A-A. 48-36281, JP-A-55-3270, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P.
- S-triazine compounds S-triazine compounds
- an organic borate compound can also be applied.
- the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech '98. Proceeding Compound 19-22, 1998, Chicago" and the like.
- Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.
- a disulfone compound can also be applied as a photoacid generator.
- examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.
- onium salt compound examples include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.K. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365549, etc., US Pat. No. 4,069, Phosphonium salts described in 055, 4,069,056, European Patents 104, 143, US Patents 339,049, 410,201, JP-A-2. -150848, Iodonium salt described in JP-A-2-296514, European Patent Nos.
- onium salts examples include onium salts represented by the following general formulas (RI-I) to (RI-III).
- Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 carbon number.
- Z11 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability
- Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable.
- Ar 21 and Ar 22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms.
- Z 21 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
- R 31 , R 32 , and R 33 each represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms which may independently have 1 to 6 substituents.
- an aryl group from the viewpoint of reactivity and stability.
- Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
- Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms.
- Z31 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of properties, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
- the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. It is more preferably 2 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.
- the curable resin composition of the present invention may contain a photobase generator as a photosensitizer.
- a photobase generator as a photosensitizer.
- the curable resin composition contains a photobase generator and a cross-linking agent described later, for example, the cyclization of the specific resin is promoted by the base generated in the exposed portion, and the cross-linking reaction of the cross-linking agent is promoted. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion due to such an action. According to such an aspect, a negative type relief pattern can be obtained.
- the photobase generator is not particularly limited as long as it generates a base by exposure, and known ones can be used.
- M. Shirai, and M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A.M. Sarker, and D. Neckers, Chem. Mater. , 11, 170 (1999); Tachi, M. et al. Shirai, and M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.
- Ionic compounds whose base components are neutralized by forming salts and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.
- carbamate derivatives, amide derivatives, imide derivatives, ⁇ -cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like are more preferable examples.
- the basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines. From the viewpoint of the imidization ratio, the basic substance preferably has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid.
- the pKa is preferably 1 or more, and more preferably 3 or more.
- the upper limit of the pKa is not particularly limited, but is preferably 20 or less.
- pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid
- Determination of Organic Structures by Physical Methods author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; You can refer to the values described in Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959).
- ACD / pKa manufactured by ACD / Labs
- the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and the nitrogen atom of the base portion generated in the photobase generator. It is preferable that there is no charge on the top.
- the photobase generator it is preferable that the generated base is latent using a covalent bond, and the mechanism of base generation is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cleaved. It is preferable that the base is generated.
- the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved.
- the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
- the photobase generator is preferably a photobase generator containing a salt in the structure.
- the base generated as described above is latent using a covalent bond, and the generated base has an amide bond, a carbamate bond, and an oxime bond. It is preferably latent using.
- the photobase generator according to the present invention include a photobase generator having a cinnamic acid amide structure as disclosed in JP-A-2009-08452 and JP-A-2009 / 123122, JP-A-2006-189591.
- Examples thereof include a photobase generator having an oxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.
- the photobase generator the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205.
- Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204319A, and the compounds described in paragraph number 0052 of International Publication No. 2010/064631.
- a commercially available product may be used as the photobase generator.
- Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG. -166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( (Made by Tokyo Chemical Industry Co., Ltd.) and the like.
- the content thereof is preferably 0.1 to 30% by mass, preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. Is more preferable, and 2 to 15% by mass is further preferable. Only one type of photobase generator may be contained, or two or more types may be contained. When two or more photobase generators are contained, the total is preferably in the above range.
- the composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator.
- a thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the cross-linking agent can be allowed to proceed in the heating step described later, so that the solvent resistance can be further improved.
- thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
- the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. More preferably, it is 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.
- the composition of the present invention may contain a thermoacid generator.
- the thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
- the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
- the thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
- the acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
- aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
- alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
- haloalkyl sulfonic acid such as sulfonic acid is preferable.
- thermoacid generator include those described in paragraph 0055 of JP2013-072935A.
- thermoacid generator the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.
- the content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
- the content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
- 0.01 part by mass or more By containing 0.01 part by mass or more, the cross-linking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved.
- 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.
- the curable resin composition of the present invention may further contain an onium salt.
- the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it preferably contains an onium salt.
- the type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
- an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability
- a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
- the onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
- an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
- the onium salt used in the present invention may be a thermobase generator described later.
- the thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
- Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262.
- onium salts used in the field of polyimide precursors can be used without particular limitation.
- the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
- the onium salt one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
- the curable resin composition of the present invention may further contain a thermosetting agent.
- a thermosetting agent when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain a thermosetting agent.
- the other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
- Examples of the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators. Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
- Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
- the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
- Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
- the cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
- the single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring.
- a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
- Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb 1 and Rb 2 may be coupled to each other to form a ring.
- Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
- a cyclohexyl group which may be used is more preferable.
- an alkyl group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms
- an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6.
- alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
- arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable).
- an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24).
- 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable).
- 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is further preferable).
- a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
- Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
- the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
- Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
- Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb 13 is preferably an arylalkyl group.
- Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
- Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
- 2 to 8 are more preferable, 2 to 3 are more preferable
- aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable
- 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
- Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.
- the compound represented by the formula (B1-1) is also preferable.
- Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in the formula (B1-1).
- Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 7).
- Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
- the molecular weight of the nonionic thermobase generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
- the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
- thermo base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.
- the content of the other thermosetting agent is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
- the thermobase generator one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
- the curable resin composition of the present invention preferably contains a cross-linking agent.
- the cross-linking agent include radical cross-linking agents and other cross-linking agents.
- the curable resin composition of the present invention preferably further contains a radical cross-linking agent.
- the radical cross-linking agent is a compound having a radically polymerizable group.
- a group containing an ethylenically unsaturated bond is preferable.
- the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
- the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
- the radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but a compound having two or more ethylenically unsaturated bonds is more preferable.
- the compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
- the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent.
- the compound having 3 or more ethylenically unsaturated bonds a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable.
- the compound having is more preferable.
- the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds.
- a compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
- the curable resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable.
- the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
- the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
- radical cross-linking agent examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, which are preferably unsuitable.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogeno group.
- Substitution reaction products of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
- radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
- examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
- a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
- Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
- a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
- radical cross-linking agent other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like.
- Compounds having two or more radicals and cardo resins can also be used.
- dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable
- SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
- SR-209 manufactured by Sartmer which is a bifunctional methacrylate having four ethyleneoxy chains.
- DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.
- TPA-330 a trifunctional acrylate having 3 isobutyleneoxy chains
- urethane oligomer UAS-10 are examples of the radical cross-linking agent.
- UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals (manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
- radical cross-linking agent examples include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
- radical cross-linking agent compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.
- the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
- the radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
- a radical cross-linking agent provided with is more preferable.
- the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
- examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
- the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
- the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The acid value is measured according to the description of JIS K 0070: 1992.
- bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
- Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene.
- Glycol diacrylate polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives Dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates
- the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
- a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent.
- the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
- the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention.
- the lower limit is more preferably 5% by mass or more.
- the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
- One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.
- the curable resin composition of the present invention preferably contains another cross-linking agent different from the radical cross-linking agent described above.
- the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer.
- the compound has a plurality of groups in the molecule for which the reaction to be formed is promoted, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of an acid or a base.
- a compound having a plurality of groups promoted by the above in the molecule is preferable.
- the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator which is a photosensitizer in the exposure step.
- a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable.
- a compound having a structure directly bonded to a nitrogen atom is more preferable.
- an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to a methylol group or an alkoxymethyl group.
- examples thereof include compounds having a substituted structure.
- the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
- the cross-linking agent using melamine is a melamine-based cross-linking agent
- the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
- the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent.
- a cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
- the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and preferably contains a glycoluril-based cross-linking agent and melamine, which will be described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.
- melamine-based cross-linking agent examples include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like.
- urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl.
- Glycoluryl-based cross-linking agent such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneureated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea, Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea,
- benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
- Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like can be mentioned.
- a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
- Compounds to which the seed groups are directly attached are also preferably used. Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate.
- suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
- DML-34X DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, Honshu) Nikalac (registered trademark, the same applies
- the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
- Epoxy compound (compound having an epoxy group)
- the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
- the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.
- the epoxy compound preferably contains a polyethylene oxide group.
- the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
- epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propantriglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, containing silicones.
- oxetane compound compound having an oxetanyl group
- examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
- examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
- the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
- Benzoxazine compound (compound having a benzoxazolyl group) Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
- benzoxazine compound examples include BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly.
- examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.
- the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
- the other cross-linking agent may contain only one type, or may contain two or more types. When two or more other cross-linking agents are contained, the total is preferably in the above range.
- the curable resin composition of the present invention is at least one selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. It is preferable to further contain a compound.
- the sulfonamide structure is a structure represented by the following formula (S-1).
- R represents a hydrogen atom or an organic group
- R may be bonded to another structure to form a ring structure
- * may independently form a binding site with another structure. show.
- the R is preferably the same group as R 2 in the following formula (S-2).
- the compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but a compound having one sulfonamide structure is preferable.
- the compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
- R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of R 1 , R 2 and R 3 are bonded to each other. It may form a ring structure. It is preferable that R 1 , R 2 and R 3 are independently monovalent organic groups.
- R 1 , R 2 and R 3 include a hydrogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, and a carboxy group.
- examples thereof include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
- the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
- a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
- examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
- an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
- As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
- Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
- aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
- the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
- heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, and a pyrimididine ring.
- R 1 is an aryl group and R 2 and R 3 are independently hydrogen atoms or alkyl groups are preferable.
- Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanylamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1.
- the thiourea structure is a structure represented by the following formula (T-1).
- R 4 and R 5 each independently represent a hydrogen atom or a monovalent organic group, and R 4 and R 5 may be combined to form a ring structure, where R 4 is.
- the ring structure may be formed by combining with other structures to which * is bonded, R 5 may be combined with other structures to which * is bonded to form a ring structure, and * may be independently and others. Represents the site of connection with the structure of.
- R 4 and R 5 are independently hydrogen atoms.
- R 4 and R 5 include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, and a carbonyl group.
- examples thereof include an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
- the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
- a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
- examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
- an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
- As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
- Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
- aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
- the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
- heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, and a pyrimididine ring.
- the compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferable.
- the compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
- R 4 to R 7 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R 4 to R 7 are bonded to each other to form a ring structure. You may.
- R 4 and R 5 have the same meanings as R 4 and R 5 in formula (T-1), a preferable embodiment thereof is also the same.
- R 6 and R 7 are independently monovalent organic groups.
- the preferred embodiment of the monovalent organic group in R 6 and R 7 is the same as the preferred embodiment of the monovalent organic group in R 4 and R 5 in the formula (T-1). ..
- Examples of compounds having a thiourea structure include N-acetylthiourea, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl) thiourea, 1-adamantyl thiourea, N-benzoyl thiourea, N, N'-.
- Diphenylthiourea 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1- (3- (trimethoxysilyl) propyl) -3-methylthiourea, trimethyl Examples thereof include thiourea, tetramethylthiourea, N, N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydranthin.
- the total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, preferably 0.1 to 5% by mass, based on the total mass of the curable resin composition of the present invention. It is more preferably%, and further preferably 0.2 to 3% by mass.
- the curable resin composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more compounds. When only one type is contained, the content of the compound is preferably within the above range, and when two or more types are contained, the total amount thereof is preferably within the above range.
- the curable resin composition of the present invention preferably further contains a migration inhibitor.
- a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the photosensitive film.
- the migration inhibitor is not particularly limited, but has a heterocycle (pyrol ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, etc.
- triazole-based compounds such as 1,2,4-triazole and benzotriazole
- tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
- an ion trap agent that traps anions such as halogen ions can also be used.
- Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
- the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.
- the migration inhibitor include the following compounds.
- the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.
- the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.
- the curable resin composition of the present invention preferably contains a polymerization inhibitor.
- polymerization inhibitor examples include hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol (t-butylcatechol), 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4 -Methylphenol, 5-
- the content of the polymerization inhibitor is 0.01 to 20.0% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass.
- the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
- the curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- the metal adhesion improver include silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, ⁇ -ketoester compounds, amino compounds and the like. And so on.
- silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
- Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent.
- Et represents an ethyl group.
- silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
- Aluminum-based adhesive aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetone), ethyl acetoacetate aluminum diisopropirate, and the like.
- the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.
- the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
- the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
- the curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
- the metal adhesiveness improving agent the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.
- the content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further, with respect to 100 parts by mass of the heterocyclic polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer after the heating step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured product after the heating step are good.
- the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
- the curable resin composition of the present invention contains various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and an inorganic particle, if necessary, as long as the effects of the present invention can be obtained.
- additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and an inorganic particle, if necessary, as long as the effects of the present invention can be obtained.
- Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, anti-aggregation agent and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
- the curable resin composition of the present invention may contain a sensitizer.
- the sensitizer absorbs specific active radiation and becomes an electron-excited state.
- the sensitizer in the electron-excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur.
- a thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
- sensitizer examples include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal).
- the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
- the sensitizer may be used alone or in combination of two or more.
- the curable resin composition of the present invention may contain a chain transfer agent.
- Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pp. 683-684.
- As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
- a thiol compound can be preferably used.
- the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention.
- 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
- the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
- a surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability.
- the surfactant various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.
- the following surfactants are also preferable.
- the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit
- the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
- the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
- a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant.
- Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.
- the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving property, and has good solubility in the composition.
- silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.).
- TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Co., Ltd.), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
- hydrocarbon-based surfactant examples include Pionin A-76, New Calgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
- organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.
- W001 manufactured by Yusho Co., Ltd.
- anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
- the content of the surfactant is 0.001 to 2.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass.
- the surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.
- the curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.
- a higher fatty acid derivative such as behenic acid or behenic acid amide
- the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. Is preferable.
- the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
- the resin composition of the present invention may contain inorganic particles.
- specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
- the average particle size of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, further preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferable.
- the mechanical properties of the cured film may deteriorate.
- the average particle size of the inorganic particles exceeds 2.0 ⁇ m, the resolution may decrease due to scattering of exposure light.
- the composition of the present invention may contain an ultraviolet absorber.
- an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
- salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like
- benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-.
- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxy-4-octoxybenzophenone and the like can be mentioned.
- benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3).
- Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.
- the triazine-based ultraviolet absorber 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin
- the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
- the composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
- the resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
- Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
- Specific examples of the organic titanium compound are shown in I) to VII) below:
- I) Titanium chelate compound Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained.
- Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)).
- Titanium diisopropoxyside bis titanium diisopropoxyside bis (etramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
- Titanium Alkoxy Titanium Compounds For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide.
- Titanium Tetramethoxypropoxyside Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis ⁇ 2,2- (Aryloxymethyl) Butokiside ⁇ ] etc.
- Titanocene compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5-2, 2).
- Titanium oxide compound For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
- Titanium tetraacetylacetone compound For example, titanium tetraacetylacetone.
- Titanate Coupling Agent For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
- the organic titanium compound at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing.
- -Pyrrole-1-yl) phenyl) titanium is preferred.
- the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the precursor of the cyclized resin. ..
- the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition is excellent.
- the composition of the present invention may contain an antioxidant.
- an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material.
- the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
- the phenol compound any phenol compound known as a phenolic antioxidant can be used.
- Preferred phenolic compounds include hindered phenolic compounds.
- a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
- a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
- a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
- a phosphorus-based antioxidant can also be preferably used.
- a phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like.
- antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like.
- the antioxidant the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used.
- the composition of the present invention may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned.
- Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
- Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
- preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).
- R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms
- R 6 represents an alkylene group having 2 or more carbon atoms
- R 7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom
- k represents an integer of 1 to 4.
- the compound represented by the general formula (3) suppresses oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin.
- metal oxidation can be suppressed by the rust preventive action on the metal material.
- R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-. Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent.
- alkyl ether and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of metal adhesion due to interaction with resin and metal complex formation. preferable.
- Examples of the compound represented by the following general formula (3) include the following, but the compound is not limited to the following structure.
- the amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin. If the amount added is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the elongation characteristics after reliability and the adhesion to the metal material, and if it is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of lowering the sensitivity of the resin composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
- the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
- Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.
- the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties.
- the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
- a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention.
- Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.
- the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
- the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
- ion exchange treatment and the like are preferably mentioned.
- a conventionally known storage container can be used as the storage container for the curable resin composition of the present invention.
- a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a layered bottle. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
- the curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
- the curable resin composition of the present invention can be prepared by mixing each of the above components.
- the mixing method is not particularly limited, and a conventionally known method can be used.
- the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less. On the other hand, from the viewpoint of productivity, 5 ⁇ m or less is preferable, 3 ⁇ m or less is more preferable, and 1 ⁇ m or less is further preferable.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
- the filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
- filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable. In addition to filtration using a filter, impurities may be removed using an adsorbent.
- Filter filtration and impurity removal treatment using an adsorbent may be combined.
- a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- the cured film of the present invention is a cured film obtained by curing the resin composition of the present invention.
- the cured film is preferably a patterned cured film.
- the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
- the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable.
- the first cured film and the second cured film are both cured films of the present invention.
- both the first cured film and the second cured film have the resin composition of the present invention.
- a preferred embodiment is a film obtained by curing an object.
- the resin composition of the present invention used for forming the first cured film and the resin composition of the present invention used for forming the second cured film may have the same composition. However, the compositions may have different compositions.
- the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
- Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
- Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above.
- the cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics.
- the method for producing a cured film of the present invention is a film forming step of applying the resin composition of the present invention to a substrate to form a film (resin film). It is preferable to include it.
- the method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film. By the above exposure step and development step, a pattern of a cured film can be obtained. Further, the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C.
- (b) Exposure step of exposing the film after the film forming step (c) The exposed film Development step for developing
- Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.
- the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
- the steps (a), the steps (a) to (c), or (a) are further performed.
- )-(D) it is preferable to carry out each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order.
- a metal layer on the portion provided with the cured film, between the cured films, or both.
- the production method includes a film forming step (layer forming step) in which the resin composition is applied to a substrate to form a film (layered).
- the type of the base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin film, There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, and electrode plates of plasma display panels (PDPs). Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a mold base material are more preferable.
- these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
- a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
- HMDS hexamethyldisilazane
- the base material for example, a plate-shaped base material (board) is used.
- the shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
- the size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
- the resin layer or the metal layer serves as a base material.
- Coating is preferable as a means for applying the resin composition to the base material.
- the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
- the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable.
- a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the base material.
- a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is preferable.
- the method, the inkjet method and the like are preferable.
- the spin coating method for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Further, depending on the viscosity of the photosensitive resin composition and the film thickness to be set, it is preferable to apply the photosensitive resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds.
- a plurality of rotation speeds can be combined and applied. Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate. Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention. Further, a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like. Further, a pre-wetting step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
- EBR edge bead rinse
- the production method of the present invention may include a step of drying to remove the solvent after the film forming step (layer forming step).
- the preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C.
- the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
- the production method of the present invention may include an exposure step of exposing the film (resin composition layer).
- the exposure amount is not particularly specified as long as the resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 It is more preferable to irradiate.
- the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm. Further, the exposure light preferably contains light having a wavelength of 365 nm or 405 nm, and more preferably contains light having a wavelength of 405 nm.
- the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
- the resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays.
- a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
- the exposure method is not particularly limited as long as it exposes at least a part of the film (photosensitive film) made of the curable resin composition, but an exposure using a photomask or a laser direct imaging method is used. Exposure and the like can be mentioned.
- an embodiment in which the exposure in the exposure step is an exposure by a laser direct imaging method is also one of the preferred embodiments.
- the production method of the present invention may include a developing step of developing (developing the above-mentioned film) the exposed film (resin composition layer). By developing, the unexposed portion (non-exposed portion) is removed.
- the developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used.
- the developing steps include a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, a step in which the developer is vibrated by ultrasonic waves or the like, and a combination thereof. Processes can be adopted.
- Development is performed using a developing solution.
- the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
- As the developing solution a developing solution containing an organic solvent or an alkaline aqueous solution can be used.
- the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
- the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
- the organic solvent may be, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate.
- the developer is a developer containing an organic solvent
- cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention.
- the developing solution contains an organic solvent, one kind or a mixture of two or more kinds of organic solvents can be used.
- the developer is a developer containing an organic solvent
- 50% by mass or more of the developer is preferably an organic solvent
- 70% by mass or more is more preferably an organic solvent
- 90% by mass or more is organic. It is more preferably a solvent.
- the developing solution may be 100% by mass of an organic solvent.
- the developer may further contain other components.
- other components include known surfactants and known defoamers.
- the developing solution is an alkaline aqueous solution
- examples of the basic compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate and the like, and TMAH is preferable. ..
- TMAH tetramethylammonium hydroxide
- KOH potassium hydroxide
- sodium carbonate sodium carbonate
- TMAH is preferable.
- the content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developing solution. Is more preferable.
- the method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the developer, the method of supplying the developer on the base material using a nozzle, paddle development, or continuous development.
- the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoint of the permeability of the developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable, and the developing solution to the image area is supplied.
- the method of supplying with a spray nozzle is more preferable. Further, after the developing solution is continuously supplied by the straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, the developing solution is continuously supplied by the straight nozzle again, and then the base material is spun to use the developing solution as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times. Further, as a method of supplying the developer in the developing process, a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, and a step in which the developer is superposed on the base material. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
- the development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes.
- the temperature of the developing solution at the time of development is not particularly specified, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.
- rinsing After the treatment with the developing solution, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
- the rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with the solvent contained in the resin composition.
- the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA.
- water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
- the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, still more preferably 5 seconds to 1 minute.
- the temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
- the esters include, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyl, butyl butyrate.
- alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid)
- toluene, xylene, anisole, limonene and the like dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols.
- glycols and the like and amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
- the rinsing liquid contains an organic solvent
- one type or a mixture of two or more types of organic solvent can be used.
- cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferable, cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA and PGME are more preferable, and cyclohexanone and PGMEA are more preferable. More preferred.
- the rinsing liquid contains an organic solvent
- 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable.
- the rinse liquid may be 100% by mass of an organic solvent.
- the rinse solution may further contain other components.
- other components include known surfactants and known defoamers.
- the method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinse liquid, the supply of the rinse liquid with a paddle on the base material, and the supply of the rinse liquid to the base material by a shower.
- the method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc. there is a method of supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid with a spray nozzle is more preferable.
- the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
- the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
- a method of supplying the rinse liquid in the rinsing step a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material.
- a process of vibrating with a sound conditioner or the like and a process of combining them can be adopted.
- the production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
- the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
- the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds.
- the resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but curing of a radically polymerizable compound other than the precursor which is an unreacted specific resin is also in this step. Can be advanced with.
- the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable.
- the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
- the heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
- a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
- the temperature at the start of heating it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. °C / sec is more preferable.
- the temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C.
- the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
- the temperature of the film (layer) after drying is, for example, 30 to 200 ° C., which is higher than the boiling point of the solvent contained in the resin composition. It is preferable to gradually raise the temperature from a low temperature.
- the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
- the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.
- Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
- the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
- the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
- the pretreatment may be performed in two or more steps.
- the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
- the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
- cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
- the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
- the heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.
- the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (resin composition layer).
- metal layer existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, and copper, aluminum, and these metals are exemplified.
- the alloy containing the above is more preferable, and copper is further preferable.
- the method for forming the metal layer is not particularly limited, and an existing method can be applied.
- the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
- photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.
- the thickness of the metal layer is preferably 0.01 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m, and even more preferably 1 to 10 ⁇ m at the thickest portion.
- the production method of the present invention preferably further includes a laminating step.
- the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated resin composition layers all at once.
- the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
- the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
- An example of the surface activation treatment is plasma treatment.
- the laminating step is preferably performed 2 to 20 times, preferably 2 to 5 times, and more preferably 3 to 5 times. Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.
- a cured film (resin layer) of the resin composition so as to cover the metal layer after the metal layer is provided.
- Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided at the end or in the middle.
- the method for producing a laminate of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
- the surface activating treatment step is usually performed after the metal layer forming step, but it is also possible to perform the surface activating treatment step on the photosensitive resin composition layer after the exposure development step and then perform the metal layer forming step. good.
- the surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially.
- the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer in which the photosensitive resin composition layer is formed on the surface. ..
- the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure.
- the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF 4 / O 2 , NF 3 / O 2 , SF 6 , NF 3 , NF 3 / O 2 , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable.
- the energy is preferably 500 ⁇ 200,000J / m 2, more preferably 1000 ⁇ 100,000J / m 2, and most preferably 10,000 ⁇ 50,000J / m 2.
- the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
- the semiconductor device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
- the precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
- the total molar content of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor can be increased, and by shortening the total molar content, the total molar content can be reduced. ..
- a resin having a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor of 0.083 mmol / g was obtained.
- the produced crude polymer was filtered off and dissolved in tetrahydrofuran 403.49 g to obtain a crude polymer solution.
- the obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polyimide precursor) A-1. rice field.
- the molecular weight of the polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.
- the molar content of the benzoxazole structure in the polybenzoxazole precursor can be increased, and by shortening it, the molar content of the benzoxazole structure in the polybenzoxazole precursor can be increased.
- the molar content of the benzoxazole structure can be set to 0.373 mmol / g for 15 minutes.
- the precipitated polybenzoxazole precursor resin was filtered off and washed with 1.5 liters of water. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain A-4.
- the precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
- the total molar content of the cyclic imide structure and the cyclic isoimide structure in the polyamide-imide precursor can be increased, and by shortening the total molar content, the total molar content can be reduced. can.
- the molar content of the benzoxazole structure can be 0.104 mmol / g for 15 minutes.
- the obtained reaction solution was added to 716.21 g of ethyl alcohol to form a precipitate composed of a crude polymer.
- the produced crude polymer was filtered off and dissolved in tetrahydrofuran 403.49 g to obtain a crude polymer solution.
- the obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, the obtained precipitate was filtered off, and then vacuum dried to obtain a powdered polymer (polyamideimide precursor) A-5. Obtained.
- Examples and Comparative Examples> the components listed in the table below were mixed to obtain each curable resin composition. Further, in each comparative example, the components listed in the following table were mixed to obtain each comparative composition. Specifically, the content of each component shown in Tables 1 to 5 is the amount (parts by mass) shown in parentheses in each column of Tables 1 to 5. The obtained curable resin composition and comparative composition were pressure-filtered using a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m. Further, in Tables 1 to 5, the description of "-" indicates that the composition does not contain the corresponding component.
- the cyclic imide structure amount was specified from the ratio of the peak area around 7.15 ppm to the peak area of the aromatic ring.
- the cyclic isoimide structure in the polyimide precursor or the polyamide-imide precursor The amount of benzoxazole structure in the polybenzoxazole precursor was identified.
- the prepared curable resin composition or comparative composition was applied onto a silicon wafer by a spin coating method.
- the silicon wafer was dried on a hot plate at 100 ° C. for 5 minutes to form a curable resin composition layer having a uniform thickness of 20 ⁇ m on the silicon wafer.
- the curable resin composition layer on the silicon wafer was exposed using a stepper. The exposure was performed using light having the wavelength described in "Exposure wavelength nm" in the table, and using a photomask of a fuse box from 5 ⁇ m to 25 ⁇ m in 1 ⁇ m increments. The exposure amount was the exposure amount that minimizes the minimum line width described later.
- the exposure was performed using a direct exposure apparatus (Adtech DE-6UH III).
- the exposure was performed by laser direct imaging exposure at a wavelength of 405 nm so that the exposed portion became a line portion in a line and space pattern in 1 ⁇ m increments from 5 ⁇ m to 25 ⁇ m.
- the exposure amount was the exposure amount that minimizes the minimum line width described later.
- the exposed curable resin composition layer was developed with cyclopentanone for 60 seconds and then rinsed with PGMEA (propylene glycol monomethyl ether acetate).
- the line width of the line pattern having the smallest line width was defined as the "minimum line width" and evaluated according to the following evaluation criteria. It can be said that the smaller the line width is, the better the resolution is. For example, it means that the metal wiring width formed in the subsequent plating step can be miniaturized, which is a preferable result.
- the measurement limit is 5 ⁇ m.
- the evaluation results are described in the "Resolution" column in the table. -Evaluation criteria- A: The minimum line width was 5 ⁇ m or more and less than 8 ⁇ m. B: The minimum line width was 8 ⁇ m or more and less than 10 ⁇ m. C: The minimum line width was 10 ⁇ m or more and less than 12 ⁇ m. D: The minimum line width was 12 ⁇ m or more.
- the exposure amount was varied in 50 mJ / cm 2 increments in the range of 50 ⁇ 500mJ / cm 2.
- laser direct imaging exposure was performed using a direct exposure apparatus (Adtech DE-6UH III).
- the exposure wavelength was 405 nm, and exposure was performed so that an unexposed portion having a diameter of 15.0 ⁇ m was formed.
- the exposure amount was varied in 50 mJ / cm 2 increments in the range of 50 ⁇ 500mJ / cm 2.
- the sensitivity was evaluated according to the following evaluation criteria from the minimum exposure amount at which a hole pattern having a bottom diameter of 15.0 ⁇ m was formed.
- the minimum exposure amount was less than 100 mJ / cm 2.
- B the minimum exposure amount is less than 100 mJ / cm 2 or more 150 mJ / cm 2.
- C The minimum exposure amount was 150 mJ / cm 2 or more.
- the polyimide precursor contained in the comparative compositions according to Comparative Examples 1 to 4 has a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor of less than 0.08 mmol / g.
- the polyimide precursor contained in the comparative composition according to Comparative Example 5 has a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor exceeding 1.68 mmol / g.
- the polybenzoxazole precursor contained in the comparative composition according to Comparative Example 6 has a molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor of less than 0.22 mmol / g.
- the polybenzoxazole precursor contained in the comparative composition according to Comparative Example 7 has a molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor exceeding 3.97 mmol / g.
- the polyamide-imide precursor contained in the comparative composition according to Comparative Example 8 has a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor exceeding 1.186 mmol / g.
- the polyamide-imide precursor contained in the comparative composition according to Comparative Example 9 has a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamide-imide precursor of less than 0.062 mmol / g. It can be seen that when these comparative compositions are used, the resolution is inferior.
- Example 101 The curable resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 4 minutes. After forming a photosensitive film having a film thickness of 20 ⁇ m, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed through a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes.
- NSR1505 i6 a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m
- the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 120 minutes to form an interlayer insulating film for the rewiring layer.
- the interlayer insulating film for the rewiring layer was excellent in insulating properties. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
このような硬化性樹脂組成物を、例えば塗布等により基材に適用して感光膜を形成し、その後、必要に応じて露光、現像、加熱等を行うことにより、硬化物を基材上に形成することができる。
上記ポリイミド前駆体、ポリベンゾオキサゾール前駆体、及び、ポリアミドイミド前駆体は、例えば加熱により環化され、硬化物中でそれぞれポリイミド、ポリベンゾオキサゾール、ポリアミドイミドとなる。
硬化性樹脂組成物は、公知の塗布方法等により適用可能であるため、例えば、適用される硬化性樹脂組成物の適用時の形状、大きさ、適用位置等の設計の自由度が高いなど、製造上の適応性に優れるといえる。ポリイミド、ポリベンゾオキサゾール、ポリアミドイミド等が有する高い性能に加え、このような製造上の適応性に優れる観点から、上述の硬化性樹脂組成物の産業上の応用展開がますます期待されている。 For example, in the above-mentioned applications, resins such as polyimide, polybenzoxazole, and polyamide-imide are cured containing at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors. Used in the form of a sex resin composition.
Such a curable resin composition is applied to a base material by, for example, coating to form a photosensitive film, and then exposed, developed, heated or the like as necessary to apply the cured product onto the base material. Can be formed.
The polyimide precursor, the polybenzoxazole precursor, and the polyamide-imide precursor are cyclized by, for example, heating, and become polyimide, polybenzoxazole, and polyamide-imide in the cured product, respectively.
Since the curable resin composition can be applied by a known coating method or the like, for example, the degree of freedom in designing the shape, size, application position, etc. of the applied curable resin composition at the time of application is high. It can be said that it has excellent manufacturing adaptability. In addition to the high performance of polyimide, polybenzoxazole, polyamide-imide, etc., from the viewpoint of excellent adaptability in manufacturing, the industrial application development of the above-mentioned curable resin composition is expected more and more.
<1> 環状イミド構造及び環状イソイミド構造の少なくとも一方を含むポリイミド前駆体、ベンゾオキサゾール構造を含むポリベンゾオキサゾール前駆体、及び、環状イミド構造及び環状イソイミド構造の少なくとも一方を含むポリアミドイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂、並びに、
有機金属錯体を含み、
1gの上記ポリイミド前駆体に含まれる上記環状イミド構造及び上記環状イソイミド構造の合計含有モル量が、0.08~1.68mmol/gであり、
1gの上記ポリベンゾオキサゾール前駆体に含まれる上記ベンゾオキサゾール構造の含有モル量が、0.22~3.97mmol/gであり、
1gの上記ポリアミドイミド前駆体に含まれる上記環状イミド構造及び上記環状イソイミド構造の合計含有モル量が、0.062~1.186mmol/gである、
硬化性樹脂組成物。
<2> 光重合開始剤を更に含む、<1>に記載の硬化性樹脂組成物。
<3> 上記光重合開始剤がオキシム化合物である、<1>又は<2>に記載の硬化性樹脂組成物。
<4> 架橋剤を更に含む、<1>~<3>のいずれか1つに記載の硬化性樹脂組成物。
<5> 上記有機金属錯体が、メタロセン化合物である、<1>~<4>のいずれか1つに記載の硬化性樹脂組成物。
<6> 上記有機金属錯体に含まれる金属が、チタン、ジルコニウム及びハフニウムよりなる群から選ばれた少なくとも1種の金属である、<1>~<5>のいずれか1つに記載の硬化性樹脂組成物。
<7> 上記有機金属錯体が、光ラジカル重合開始能を有する、<1>~<6>のいずれか1つに記載の硬化性樹脂組成物。
<8> ネガ型現像に供される感光膜の形成に用いられる、<1>~<7>のいずれか1つに記載の硬化性樹脂組成物。
<9> 再配線層用層間絶縁膜の形成に用いられる、<1>~<8>のいずれか1つに記載の硬化性樹脂組成物。
<10> <1>~<9>のいずれか1つに記載の硬化性樹脂組成物を硬化してなる硬化膜。
<11> <10>に記載の硬化膜を2層以上含み、上記硬化膜同士のいずれかの間に金属層を含む積層体。
<12> <1>~<9>のいずれか1つに記載の硬化性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
<13> 上記膜を露光する露光工程及び上記膜を現像する現像工程を含む、<12>に記載の硬化膜の製造方法。
<14> 上記露光に用いられる露光光が波長405nmの光を含む、<13>に記載の硬化膜の製造方法。
<15> 上記露光がレーザーダイレクトイメージング法による露光である、<13>又は<14>に記載の硬化膜の製造方法。
<16> 上記膜を50~450℃で加熱する加熱工程を含む、<12>~<15>のいずれか1つに記載の硬化膜の製造方法。
<17> <10>に記載の硬化膜又は<11>に記載の積層体を含む、半導体デバイス。 Examples of typical embodiments of the present invention are shown below.
<1> Consists of a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor containing a benzoxazole structure, and a polyamide-imide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure. At least one resin selected from the group, as well as
Contains organometallic complexes
The total molar amount of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor is 0.08 to 1.68 mmol / g.
The molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol / g.
The total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamide-imide precursor is 0.062 to 1.186 mmol / g.
Curable resin composition.
<2> The curable resin composition according to <1>, further comprising a photopolymerization initiator.
<3> The curable resin composition according to <1> or <2>, wherein the photopolymerization initiator is an oxime compound.
<4> The curable resin composition according to any one of <1> to <3>, further comprising a cross-linking agent.
<5> The curable resin composition according to any one of <1> to <4>, wherein the organometallic complex is a metallocene compound.
<6> The curability according to any one of <1> to <5>, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium and hafnium. Resin composition.
<7> The curable resin composition according to any one of <1> to <6>, wherein the organometallic complex has a photoradical polymerization initiation ability.
<8> The curable resin composition according to any one of <1> to <7>, which is used for forming a photosensitive film to be used for negative development.
<9> The curable resin composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for a rewiring layer.
<10> A cured film obtained by curing the curable resin composition according to any one of <1> to <9>.
<11> A laminate containing two or more layers of the cured film according to <10> and containing a metal layer between any of the cured films.
<12> A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of <1> to <9> to a substrate to form a film.
<13> The method for producing a cured film according to <12>, which comprises an exposure step of exposing the film and a developing step of developing the film.
<14> The method for producing a cured film according to <13>, wherein the exposure light used for the above exposure includes light having a wavelength of 405 nm.
<15> The method for producing a cured film according to <13> or <14>, wherein the exposure is an exposure by a laser direct imaging method.
<16> The method for producing a cured film according to any one of <12> to <15>, which comprises a heating step of heating the film at 50 to 450 ° C.
<17> A semiconductor device comprising the cured film according to <10> or the laminate according to <11>.
本明細書において「~」という記号を用いて表される数値範囲は、「~」の前後に記載される数値をそれぞれ下限値及び上限値として含む範囲を意味する。
本明細書において「工程」との語は、独立した工程だけではなく、その工程の所期の作用が達成できる限りにおいて、他の工程と明確に区別できない工程も含む意味である。
本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有しない基(原子団)と共に置換基を有する基(原子団)をも包含する。例えば、「アルキル基」とは、置換基を有しないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた露光も含む。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線又は放射線が挙げられる。
本明細書において、「(メタ)アクリレート」は、「アクリレート」及び「メタクリレート」の両方、又は、いずれかを意味し、「(メタ)アクリル」は、「アクリル」及び「メタクリル」の両方、又は、いずれかを意味し、「(メタ)アクリロイル」は、「アクリロイル」及び「メタクリロイル」の両方、又は、いずれかを意味する。
本明細書において、構造式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Phはフェニル基を表す。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。また本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。
本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィ(GPC測定)に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220GPC(東ソー(株)製)を用い、カラムとしてガードカラムHZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000(東ソー(株)製)を用いることによって求めることができる。それらの分子量は特に述べない限り、溶離液としてTHF(テトラヒドロフラン)を用いて測定したものとする。また、GPC測定における検出は特に述べない限り、UV線(紫外線)の波長254nm検出器を使用したものとする。
本明細書において、積層体を構成する各層の位置関係について、「上」又は「下」と記載したときには、注目している複数の層のうち基準となる層の上側又は下側に他の層があればよい。すなわち、基準となる層と上記他の層の間に、更に第3の層や要素が介在していてもよく、基準となる層と上記他の層は接している必要はない。また、特に断らない限り、基材に対し層が積み重なっていく方向を「上」と称し、又は、感光膜がある場合には、基材から感光膜へ向かう方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。
本明細書において、特段の記載がない限り、組成物は、組成物に含まれる各成分として、その成分に該当する2種以上の化合物を含んでもよい。また、特段の記載がない限り、組成物における各成分の含有量とは、その成分に該当する全ての化合物の合計含有量を意味する。
本明細書において、特に述べない限り、温度は23℃、気圧は101,325Pa(1気圧)、相対湿度は50%RHである。
本明細書において、好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or , And "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive film, the direction from the base material to the photosensitive film is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
In the present specification, the combination of preferred embodiments is a more preferred embodiment.
本発明の硬化性樹脂組成物は、環状イミド構造及び環状イソイミド構造の少なくとも一方を含むポリイミド前駆体、ベンゾオキサゾール構造を含むポリベンゾオキサゾール前駆体、及び、環状イミド構造及び環状イソイミド構造の少なくとも一方を含むポリアミドイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂(以下、「特定樹脂」ともいう。)、並びに、有機金属錯体を含み、1gの上記ポリイミド前駆体に含まれる上記環状イミド構造及び上記環状イソイミド構造の合計含有モル量が、0.08~1.68mmol/gであり、1gの上記ポリベンゾオキサゾール前駆体に含まれる上記ベンゾオキサゾール構造の含有モル量が、0.22~3.97mmol/gであり、1gの上記ポリアミドイミド前駆体に含まれる上記環状イミド構造及び上記環状イソイミド構造の合計含有モル量が、0.062~1.186mmol/gである。 (Curable resin composition)
The curable resin composition of the present invention comprises a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor containing a benzoxazole structure, and at least one of a cyclic imide structure and a cyclic isoimide structure. The cyclic imide structure contained in 1 g of the polyimide precursor containing at least one resin (hereinafter, also referred to as “specific resin”) selected from the group consisting of polyamide imide precursors containing an organic metal complex. The total molar content of the cyclic isoimide structure is 0.08 to 1.68 mmol / g, and the molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor is 0.22 to 3 It is .97 mmol / g, and the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamideimide precursor is 0.062 to 1.186 mmol / g.
また、本発明の硬化性樹脂組成物は、ネガ型現像に供される感光膜の形成に用いられることが好ましい。
本発明において、ネガ型現像とは、露光及び現像において、現像により非露光部が除去される現像をいい、ポジ型現像とは、現像により露光部が除去される現像をいう。
上記露光の方法、上記現像液、及び、上記現像の方法としては、例えば、後述する硬化膜の製造方法の説明における露光工程において説明された露光方法、現像工程において説明された現像液及び現像方法が使用される。 The curable resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and is used for forming a film to be subjected to exposure and development using a developing solution containing an organic solvent. Is preferable.
Further, the curable resin composition of the present invention is preferably used for forming a photosensitive film to be used for negative development.
In the present invention, the negative type development means the development in which the non-exposed part is removed by the development in the exposure and the development, and the positive type development means the development in which the exposed part is removed by the development.
The exposure method, the developer, and the developing method include, for example, the exposure method described in the exposure step in the description of the method for producing a cured film described later, the developer and the developing method described in the developing step. Is used.
上記効果が得られるメカニズムは不明であるが、下記のように推測される。 The curable resin composition of the present invention is excellent in exposure sensitivity and chemical resistance of the obtained pattern.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
しかし、有機金属錯体を含む組成物を用いてパターニングした場合、有機金属錯体が膜内で凝集してしまい、解像性が低下する場合があった。
本発明においては、樹脂組成物中の樹脂として環状イミド構造、環状イソイミド構造又はベンゾオキサゾール構造を特定の含有量で含む樹脂を用いる。これらの構造と有機金属錯体とが強固に相互作用することにより、組成物に含まれる有機金属錯体が膜内で均一に近い状態で分散すると考えられる。その結果、本発明の樹脂組成物は解像性に優れると推測される。 For example, as described in Patent Document 1, in order to improve chemical resistance, an organic titanium compound or the like is added to the curable resin composition.
However, when patterning is performed using a composition containing an organometallic complex, the organometallic complex may aggregate in the film and the resolution may decrease.
In the present invention, as the resin in the resin composition, a resin containing a cyclic imide structure, a cyclic isoimide structure or a benzoxazole structure at a specific content is used. It is considered that the organometallic complex contained in the composition is dispersed in the film in a nearly uniform state by the strong interaction between these structures and the organometallic complex. As a result, it is presumed that the resin composition of the present invention has excellent resolution.
本発明の硬化性樹脂組成物は、環状イミド構造及び環状イソイミド構造の少なくとも一方を含むポリイミド前駆体、ベンゾオキサゾール構造を含むポリベンゾオキサゾール前駆体、及び、環状イミド構造及び環状イソイミド構造の少なくとも一方を含むポリアミドイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂(特定樹脂)を含む。
本発明の硬化性樹脂組成物は、特定樹脂として、環状イミド構造及び環状イソイミド構造の少なくとも一方を含むポリイミド前駆体を含むことが好ましい。
また、特定樹脂はラジカル重合性基を有することが好ましい。
特定樹脂がラジカル重合性基を有する場合、硬化性樹脂組成物は、感光剤として後述の光ラジカル重合開始剤を含むことが好ましく、感光剤として後述の光ラジカル重合開始剤を含み、かつ、後述のラジカル架橋剤を含むことがより好ましく、感光剤として後述の光ラジカル重合開始剤を含み、後述のラジカル架橋剤を含み、かつ、後述の増感剤を含むことが更に好ましい。このような硬化性樹脂組成物からは、例えば、ネガ型感光膜が形成される。
また、特定樹脂は、酸分解性基等の極性変換基を有していてもよい。
特定樹脂が酸分解性基を有する場合、硬化性樹脂組成物は、感光剤として後述の光酸発生剤を含むことが好ましい。このような硬化性樹脂組成物からは、例えば、化学増幅型であるポジ型感光膜又はネガ型感光膜が形成される。 <Specific resin>
The curable resin composition of the present invention comprises a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor containing a benzoxazole structure, and at least one of a cyclic imide structure and a cyclic isoimide structure. It contains at least one resin (specific resin) selected from the group consisting of polyamide-imide precursors containing.
The curable resin composition of the present invention preferably contains, as the specific resin, a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure.
Further, the specific resin preferably has a radically polymerizable group.
When the specific resin has a radically polymerizable group, the curable resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described below as a photosensitizer, and is described later. It is more preferable to contain the radical cross-linking agent described above, and it is further preferable to contain the photoradical polymerization initiator described below as the photosensitizer, the radical cross-linking agent described below, and the sensitizer described below. From such a curable resin composition, for example, a negative photosensitive film is formed.
Further, the specific resin may have a polarity converting group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the curable resin composition preferably contains a photoacid generator described later as a photosensitizer. From such a curable resin composition, for example, a chemically amplified positive type photosensitive film or a negative type photosensitive film is formed.
また、ポリイミド前駆体は、環状イミド構造を少なくとも含むことが好ましい。
ポリイミド前駆体は、環状イミド構造及び環状イソイミド構造の少なくとも一方を側鎖に有してもよいが、主鎖に有することが好ましい。
本明細書において、樹脂の主鎖とは、分子中で相対的に最も長い分子鎖をいう。
樹脂組成物が特定樹脂としてポリベンゾオキサゾール前駆体を含む場合、解像性の観点からは、1gの上記ポリベンゾオキサゾール前駆体におけるベンゾオキサゾール構造の含有モル量は、0.22~3.97mmol/gであり、0.25~3.00mmol/gであることが好ましく、0.28~2.50mmol/gであることがより好ましく、0.30~2.00mmol/gであることが更に好ましい。
ポリベンゾオキサゾール前駆体は、ベンゾオキサゾール構造を側鎖に有してもよいが、主鎖に有することが好ましい。
樹脂組成物が特定樹脂としてポリアミドイミド前駆体を含む場合、解像性の観点からは、1gの上記ポリアミドイミド前駆体における環状イミド構造及び環状イソイミド構造の合計含有モル量は、0.062~1.186mmol/gであり、0.070~1.000mmol/gであることが好ましく、0.080~0.800mmol/gであることがより好ましく、0.090~0.700mmol/gであることが更に好ましい。
また、ポリアミドイミド前駆体は、環状イミド構造を少なくとも含むことが好ましい。
ポリアミドイミド前駆体は、環状イミド構造及び環状イソイミド構造の少なくとも一方を側鎖に有してもよいが、主鎖に有することが好ましい。 When the resin composition contains a polyimide precursor as a specific resin, the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the polyimide precursor is 0.08 to 1.68 mmol from the viewpoint of resolution. / G, preferably 0.10 to 1.00 mmol / g, more preferably 0.12 to 0.80 mmol / g, and further preferably 0.15 to 0.60 mmol / g. preferable.
Further, the polyimide precursor preferably contains at least a cyclic imide structure.
The polyimide precursor may have at least one of a cyclic imide structure and a cyclic isoimide structure in the side chain, but preferably has at least one in the main chain.
In the present specification, the main chain of a resin means a relatively longest molecular chain in a molecule.
When the resin composition contains a polybenzoxazole precursor as a specific resin, the molar content of the benzoxazole structure in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol / from the viewpoint of resolution. It is g, preferably 0.25 to 3.00 mmol / g, more preferably 0.28 to 2.50 mmol / g, and even more preferably 0.30 to 2.00 mmol / g. ..
The polybenzoxazole precursor may have a benzoxazole structure in the side chain, but is preferably in the main chain.
When the resin composition contains a polyamide-imide precursor as a specific resin, the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the above-mentioned polyamide-imide precursor is 0.062 to 1 from the viewpoint of resolution. .186 mmol / g, preferably 0.070 to 1.000 mmol / g, more preferably 0.080 to 0.800 mmol / g, and 0.090 to 0.700 mmol / g. Is more preferable.
Further, the polyamide-imide precursor preferably contains at least a cyclic imide structure.
The polyamide-imide precursor may have at least one of a cyclic imide structure and a cyclic isoimide structure in the side chain, but preferably has at least one in the main chain.
本発明で用いるポリイミド前駆体は、その種類等特に定めるものではないが、下記式(2)で表される繰り返し単位を含むことが好ましい。
式(2)中、A1及びA2は、それぞれ独立に、酸素原子又はNHを表し、R111は、2価の有機基を表し、R115は、4価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表す。 [Polyimide precursor]
The type of the polyimide precursor used in the present invention is not particularly specified, but it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2).
In formula (2), A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and R 113. And R 114 independently represent a hydrogen atom or a monovalent organic group.
式(2)におけるR111は、2価の有機基を表す。2価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数6~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数6~20の芳香族基を含む基がより好ましい。本発明の特に好ましい実施形態として、-Ar-L-Ar-で表される基であることが例示される。但し、Arは、それぞれ独立に、芳香族基であり、Lは、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-又はNHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。 A 1 and A 2 in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
R 111 in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms. A cyclic aliphatic group of 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferable embodiment of the present invention, a group represented by -Ar-L-Ar- is exemplified. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, −CO−, —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.
具体的には、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数6~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数6~20の芳香族基からなる基を含むジアミンであることがより好ましい。芳香族基の例としては、下記が挙げられる。 R 111 is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of aromatic groups include:
式中、*は他の構造との結合部位を表す。
In the formula, * represents the binding site with other structures.
式(51)
式(51)中、R50~R57は、それぞれ独立に、水素原子、フッ素原子又は1価の有機基であり、R50~R57の少なくとも1つは、フッ素原子、メチル基又はトリフルオロメチル基である。
R50~R57の1価の有機基としては、炭素数1~10(好ましくは炭素数1~6)の無置換のアルキル基、炭素数1~10(好ましくは炭素数1~6)のフッ化アルキル基等が挙げられる。
式(61)中、R58及びR59は、それぞれ独立に、フッ素原子又はトリフルオロメチル基である。
式(51)又は(61)の構造を与えるジアミン化合物としては、2,2’-ジメチルベンジジン、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、2,2’-ビス(フルオロ)-4,4’-ジアミノビフェニル、4,4’-ジアミノオクタフルオロビフェニル等が挙げられる。これらは1種で又は2種以上を組み合わせて用いてもよい。
Further, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)
In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, methyl group or trifluoro. It is a methyl group.
The monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
In formula (61), R 58 and R 59 are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
式(5)又は式(6)中、*はそれぞれ独立に、他の構造との結合部位を表す。
式(5)中、R112は、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-、及びNHCO-、ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数1~3のアルキレン基、-O-、-CO-、-S-及びSO2-から選択される基であることがより好ましく、-CH2-、-C(CF3)2-、-C(CH3)2-、-O-、-CO-、-S-及びSO2-からなる群から選択される2価の基であることが更に好ましい。 R 115 in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or formula (6), * independently represents a binding site with another structure.
In formula (5), R 112 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —CO−, —S—, —SO. 2- , NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. More preferably, it is a group selected from-, -S- and SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2-, -O-, -CO. It is more preferably a divalent group selected from the group consisting of-, -S- and SO 2-.
テトラカルボン酸二無水物は、下記式(O)で表されることが好ましい。
式(O)中、R115は、4価の有機基を表す。R115の好ましい範囲は式(2)におけるR115と同義であり、好ましい範囲も同様である。 Specific examples of R 115 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
In formula (O), R 115 represents a tetravalent organic group. A preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
エチレン性不飽和結合を有する基としては、ビニル基、(メタ)アリル基、下記式(III)で表される基などが挙げられ、下記式(III)で表される基が好ましい。 R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and both contain a polymerizable group. preferable. The polymerizable group is a group capable of a cross-linking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group and an amino. The group is mentioned. As the radically polymerizable group contained in the polyimide precursor or the like, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
式(III)において、*は他の構造との結合部位を表す。
式(III)において、R201は、炭素数2~12のアルキレン基、-CH2CH(OH)CH2-又はポリアルキレンオキシ基を表す。
好適なR201の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基、-CH2CH(OH)CH2-、ポリアルキレンオキシ基が挙げられ、エチレン基、プロピレン基、トリメチレン基、-CH2CH(OH)CH2-、ポリアルキレンオキシ基がより好ましく、ポリアルキレンオキシ基が更に好ましい。
本発明において、ポリアルキレンオキシ基とは、アルキレンオキシ基が2以上直接結合した基をいう。ポリアルキレンオキシ基に含まれる複数のアルキレンオキシ基におけるアルキレン基は、それぞれ同一であっても異なっていてもよい。
ポリアルキレンオキシ基が、アルキレン基が異なる複数種のアルキレンオキシ基を含む場合、ポリアルキレンオキシ基におけるアルキレンオキシ基の配列は、ランダムな配列であってもよいし、ブロックを有する配列であってもよいし、交互等のパターンを有する配列であってもよい。
上記アルキレン基の炭素数(アルキレン基が置換基を有する場合、置換基の炭素数を含む)は、2以上であることが好ましく、2~10であることがより好ましく、2~6であることがより好ましく、2~5であることが更に好ましく、2~4であることが一層好ましく、2又は3であることが特に好ましく、2であることが最も好ましい。
また、上記アルキレン基は、置換基を有していてもよい。好ましい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
また、ポリアルキレンオキシ基に含まれるアルキレンオキシ基の数(ポリアルキレンオキシ基の繰り返し数)は、2~20が好ましく、2~10がより好ましく、2~6が更に好ましい。
ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰り返し数の好ましい態様は上述の通りである。 In formula (III), R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
In formula (III), * represents a binding site with another structure.
In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a polyalkyleneoxy group.
Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, and ethylene group, propylene group, trimethylene group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group are more preferable, and polyalkylene group is more preferable. An oxy group is more preferred.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group in which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
R113又はR114が、水素原子、2-ヒドロキシベンジル、3-ヒドロキシベンジル及び4-ヒドロキシベンジルであることもより好ましい。 R 113 and R 114 are independently hydrogen atoms or monovalent organic groups. Examples of the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one. Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
It is also more preferable that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.
アルキル基の炭素数は1~30が好ましい。アルキル基は直鎖、分岐、環状のいずれであってもよい。直鎖又は分岐のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基、イソプロピル基、イソブチル基、sec-ブチル基、t-ブチル基、1-エチルペンチル基、2-エチルヘキシル基2-(2-(2-メトキシエトキシ)エトキシ)エトキシ基、2-(2-(2-エトキシエトキシ)エトキシ)エトキシ)エトキシ基、2-(2-(2-(2-メトキシエトキシ)エトキシ)エトキシ)エトキシ基、及び2-(2-(2-(2-エトキシエトキシ)エトキシ)エトキシ)エトキシ基が挙げられる。環状のアルキル基は、単環の環状のアルキル基であってもよく、多環の環状のアルキル基であってもよい。単環の環状のアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基及びシクロオクチル基が挙げられる。多環の環状のアルキル基としては、例えば、アダマンチル基、ノルボルニル基、ボルニル基、カンフェニル基、デカヒドロナフチル基、トリシクロデカニル基、テトラシクロデカニル基、カンホロイル基、ジシクロヘキシル基及びピネニル基が挙げられる。中でも、高感度化との両立の観点から、シクロヘキシル基が最も好ましい。また、芳香族基で置換されたアルキル基としては、後述する芳香族基で置換された直鎖アルキル基が好ましい。
芳香族基としては、具体的には、置換又は無置換のベンゼン環、ナフタレン環、ペンタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環又はフェナジン環である。ベンゼン環が最も好ましい。 From the viewpoint of solubility in an organic solvent, R 113 or R 114 is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy group is mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a boronyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthalene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acrydin ring, phenanthrolin ring, It is a thianthracene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferred.
酸分解性基の具体例としては、tert-ブトキシカルボニル基、イソプロポキシカルボニル基、テトラヒドロピラニル基、テトラヒドロフラニル基、エトキシエチル基、メトキシエチル基、エトキシメチル基、トリメチルシリル基、tert-ブトキシカルボニルメチル基、トリメチルシリルエーテル基などが挙げられる。露光感度の観点からは、エトキシエチル基、又は、テトラヒドロフラニル基が好ましい。 At least one of R 113 and R 114 may be a polarity converting group such as an acid degradable group. The acid-degradable group is not particularly limited as long as it is decomposed by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group. , A tertiary alkyl ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl. Examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
式(2-A)
式(2-A)中、A1及びA2は、酸素原子を表し、R111及びR112は、それぞれ独立に、2価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表し、R113及びR114の少なくとも一方は、重合性基を含む基であり、両方が重合性基であることが好ましい。 The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened.
Equation (2-A)
In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group , at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.
R112は、式(5)におけるR112と同義であり、好ましい範囲も同様である。 A 1, A 2, R 111 , R 113 and R 114 each independently have the same meaning as A 1, A 2, R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same ..
R 112 has the same meaning as R 112 in formula (5), and preferred ranges are also the same.
式(2-1)~式(2-6)中、R111、R113、R114、R115、A1及びA2はそれぞれ、上述の式(2)中のR111、R113、R114、R115、A1及びA2と同義であり、好ましい態様も同様である。 The polyimide precursor is selected from the group consisting of repeating units represented by any of the following formulas (2-1) to (2-6) as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure. It is preferable to include at least one repeating unit, and the repeating unit represented by the following formula (2-1), the repeating unit represented by the following formula (2-2), and the following formula (2-3). It is more preferable to include at least one repeating unit selected from the group consisting of repeating units represented by.
In formulas (2-1) to (2-6), R 111 , R 113 , R 114 , R 115 , A 1 and A 2 are R 111 , R 113 and R in the above formula (2), respectively. It is synonymous with 114 , R 115 , A 1 and A 2 , and the preferred embodiment is also the same.
上記ポリイミド前駆体の分子量の分散度は、2.5以上が好ましく、2.7以上がより好ましく、2.8以上であることが更に好ましい。ポリイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、4.5以下が好ましく、4.0以下がより好ましく、3.8以下が更に好ましく、3.2以下が一層好ましく、3.1以下がより一層好ましく、3.0以下が更に一層好ましく、2.95以下が特に好ましい。
本明細書において、分子量の分散度とは、重量平均分子量/数平均分子量により算出される値である。 The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
本発明で用いるポリベンゾオキサゾール前駆体は、その構造等について特に定めるものではないが、好ましくは下記式(3)で表される繰り返し単位を含む。
式(3)中、R121は、2価の有機基を表し、R122は、4価の有機基を表し、R123及びR124は、それぞれ独立に、水素原子又は1価の有機基を表す。 [Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. show.
式(3)において、R121は、2価の有機基を表す。2価の有機基としては、脂肪族基及び芳香族基の少なくとも一方を含む基が好ましい。脂肪族基としては、直鎖の脂肪族基が好ましい。R121は、ジカルボン酸残基が好ましい。ジカルボン酸残基は、1種のみ用いてもよいし、2種以上用いてもよい。 In the formula (3), R 123 and R 124 are synonymous with R 113 in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
脂肪族基を含むジカルボン酸としては、直鎖又は分岐(好ましくは直鎖)の脂肪族基を含むジカルボン酸が好ましく、直鎖又は分岐(好ましくは直鎖)の脂肪族基と2つの-COOHからなるジカルボン酸がより好ましい。直鎖又は分岐(好ましくは直鎖)の脂肪族基の炭素数は、2~30であることが好ましく、2~25であることがより好ましく、3~20であることが更に好ましく、4~15であることが一層好ましく、5~10であることが特に好ましい。直鎖の脂肪族基はアルキレン基であることが好ましい。
直鎖の脂肪族基を含むジカルボン酸としては、マロン酸、ジメチルマロン酸、エチルマロン酸、イソプロピルマロン酸、ジ-n-ブチルマロン酸、スクシン酸、テトラフルオロスクシン酸、メチルスクシン酸、2,2-ジメチルスクシン酸、2,3-ジメチルスクシン酸、ジメチルメチルスクシン酸、グルタル酸、ヘキサフルオログルタル酸、2-メチルグルタル酸、3-メチルグルタル酸、2,2-ジメチルグルタル酸、3,3-ジメチルグルタル酸、3-エチル-3-メチルグルタル酸、アジピン酸、オクタフルオロアジピン酸、3-メチルアジピン酸、ピメリン酸、2,2,6,6-テトラメチルピメリン酸、スベリン酸、ドデカフルオロスベリン酸、アゼライン酸、セバシン酸、ヘキサデカフルオロセバシン酸、1,9-ノナン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、ヘンエイコサン二酸、ドコサン二酸、トリコサン二酸、テトラコサン二酸、ペンタコサン二酸、ヘキサコサン二酸、ヘプタコサン二酸、オクタコサン二酸、ノナコサン二酸、トリアコンタン二酸、ヘントリアコンタン二酸、ドトリアコンタン二酸、ジグリコール酸、更に下記式で表されるジカルボン酸等が挙げられる。 As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable. A dicarboxylic acid composed of is more preferable. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadiponic acid, 3-methyladiponic acid, pimellinic acid, 2,2,6,6-tetramethylpimelic acid, suberin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , Octadecandioic acid, Nonadecandioic acid, Eikosandioic acid, Heneikosandioic acid, Docosandioic acid, Tricosandioic acid, Tetracosandioic acid, Pentacosandioic acid, Hexacosanedioic acid, Heptakosandioic acid, Octakosandioic acid, Nonakosandioic acid, Tria Examples thereof include contandiic acid, gentria-contanic acid, dotria-contandiic acid, diglycolic acid, and dicarboxylic acid represented by the following formula.
(式中、Zは炭素数1~6の炭化水素基であり、nは1~6の整数である。)
(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
式中、Aは-CH2-、-O-、-S-、-SO2-、-CO-、-NHCO-、-C(CF3)2-、及び、-C(CH3)2-からなる群から選択される2価の基を表し、*はそれぞれ独立に、他の構造との結合部位を表す。
In the formula, A is -CH 2- , -O-, -S-, -SO 2- , -CO-, -NHCO-, -C (CF 3 ) 2- , and -C (CH 3 ) 2- Represents a divalent group selected from the group consisting of, and each independently represents a binding site with another structure.
上記構造としては、例えば、下記構造が挙げられる。下記構造中、*はそれぞれ独立に、他の構造との結合部位を表す。
Examples of the above structure include the following structures. In the following structures, * independently represents a binding site with another structure.
R122は、また、ビスアミノフェノール誘導体由来の基であることが好ましく、ビスアミノフェノール誘導体由来の基としては、例えば、3,3’-ジアミノ-4,4’-ジヒドロキシビフェニル、4,4’-ジアミノ-3,3’-ジヒドロキシビフェニル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルスルホン、ビス-(3-アミノ-4-ヒドロキシフェニル)メタン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、2,2-ビス-(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)ヘキサフルオロプロパン、ビス-(4-アミノ-3-ヒドロキシフェニル)メタン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)プロパン、4,4’-ジアミノ-3,3’-ジヒドロキシベンゾフェノン、3,3’-ジアミノ-4,4’-ジヒドロキシベンゾフェノン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルエーテル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルエーテル、1,4-ジアミノ-2,5-ジヒドロキシベンゼン、1,3-ジアミノ-2,4-ジヒドロキシベンゼン、1,3-ジアミノ-4,6-ジヒドロキシベンゼンなどが挙げられる。これらのビスアミノフェノールは、単独にて、あるいは混合して使用してもよい。 In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferable range is also the same.
R 122 is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from the bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-) 4-Hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-Amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, Examples thereof include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bis-aminophenols may be used alone or in combination.
式中、X1は、-O-、-S-、-C(CF3)2-、-CH2-、-SO2-、-NHCO-を表し、*及び#はそれぞれ、他の構造との結合部位を表す。Rは水素原子又は1価の置換基を表し、水素原子又は炭化水素基が好ましく、水素原子又はアルキル基がより好ましい。また、R122は、上記式により表される構造であることも好ましい。R122が、上記式により表される構造である場合、計4つの*及び#のうち、いずれか2つが式(3)中のR122が結合する窒素原子との結合部位であり、かつ、別の2つが式(3)中のR122が結合する酸素原子との結合部位であることが好ましく、2つの*が式(3)中のR122が結合する酸素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する窒素原子との結合部位であるか、又は、2つの*が式(3)中のR122が結合する窒素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する酸素原子との結合部位であることがより好ましく、2つの*が式(3)中のR122が結合する酸素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する窒素原子との結合部位であることが更に好ましい。
In the formula, X 1 represents -O-, -S-, -C (CF 3 ) 2- , -CH 2- , -SO 2- , -NHCO-, and * and # represent other structures, respectively. Represents the binding site of. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, it is also preferable that R 122 has a structure represented by the above formula. When R 122 has a structure represented by the above formula, any two of the four * and # in total are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, and preferably R 122 in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R 122 are attached in the formula (3) , And two # are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bound, or two * are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bound. It is more preferable that the site is a site and the two #s are the binding sites with the oxygen atom to which R 122 in the formula (3) is bonded, and the two * are the oxygen to which the R 122 in the formula (3) is bonded. It is more preferable that the binding site is a binding site with an atom and the two #s are the binding sites with a nitrogen atom to which R 122 in the formula (3) is bonded.
ポリベンゾオキサゾール前駆体は、ベンゾオキサゾール構造を有する繰返し単位として、下記式(3-1)で表される繰返し単位、下記式(3-2)で表される繰返し単位、及び、下記式(3-3)で表される繰返し単位よりなる群から選ばれた少なくとも1種の繰返し単位を含むことが好ましい。
式(3-1)~式(3-3)中、R121、R122、R123及びR124はそれぞれ、式(3)中のR121、R122、R123及びR124と同義であり、好ましい態様も同様である。 The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
The polybenzoxazole precursor is a repeating unit having a benzoxazole structure, which is a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), and the following formula (3). It is preferable to include at least one repeating unit selected from the group consisting of the repeating units represented by -3).
Equation (3-1) in to Formula (3-3), R 121, R 122, respectively R 123 and R 124 has the same meaning as R 121, R 122, R 123 and R 124 in formula (3) , The preferred embodiment is also the same.
式(SL)中、Zは、a構造とb構造を有し、R1sは、水素原子又は炭素数1~10の炭化水素基であり、R2sは炭素数1~10の炭化水素基であり、R3s、R4s、R5s、R6sのうち少なくとも1つは芳香族基で、残りは水素原子又は炭素数1~30の有機基で、それぞれ同一でも異なっていてもよい。a構造及びb構造の重合は、ブロック重合でもランダム重合でもよい。Z部分のモル%は、a構造は5~95モル%、b構造は95~5モル%であり、a+bは100モル%である。
In formula (SL), Z has an a structure and a b structure, R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 2s is a hydrocarbon group having 1 to 10 carbon atoms. Yes , at least one of R 3s, R 4s , R 5s , and R 6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.
上記ポリベンゾオキサゾール前駆体の分子量の分散度は、1.4以上であることが好ましく、1.5以上がより好ましく、1.6以上であることが更に好ましい。ポリベンゾオキサゾール前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、2.6以下が好ましく、2.5以下がより好ましく、2.4以下が更に好ましく、2.3以下が一層好ましく、2.2以下がより一層好ましい。 The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in the compositions described below. It is preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
ポリアミドイミド前駆体は、下記式(PAI-2)で表される繰返し単位を含むことが好ましい。
式(PAI-2)中、R117は3価の有機基を表し、R111は2価の有機基を表し、A2は酸素原子又は-NH-を表し、R113は水素原子又は1価の有機基を表す。 [Polyamide-imide precursor]
The polyamide-imide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, and R 113 represents a hydrogen atom or monovalent. Represents an organic group of.
上記連結基としては、-O-、-S-、-C(=O)-、-S(=O)2-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基が好ましく、-O-、-S-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基がより好ましい。
上記アルキレン基としては、炭素数1~20のアルキレン基が好ましく、炭素数1~10のアルキレン基がより好ましく、炭素数1~4のアルキレン基が更に好ましい。
上記ハロゲン化アルキレン基としては、炭素数1~20のハロゲン化アルキレン基が好ましく、炭素数1~10のハロゲン化アルキレン基がより好ましく、炭素数1~4のハロゲン化アルキレン基がより好ましい。また、上記ハロゲン化アルキレン基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。上記ハロゲン化アルキレン基は、水素原子を有していても、水素原子の全てがハロゲン原子で置換されていてもよいが、水素原子の全てがハロゲン原子で置換されていることが好ましい。好ましいハロゲン化アルキレン基の例としては、(ジトリフルオロメチル)メチレン基等が挙げられる。
上記アリーレン基としては、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましく、1,3-フェニレン基又は1,4-フェニレン基が更に好ましい。 In formula (PAI-2), R 117 is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroarophatic group, or a single bond or a linking group. Examples of the above-mentioned linked groups are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms. The aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable. A group in which two or more of the above are combined is more preferable.
The linking group includes -O-, -S-, -C (= O)-, -S (= O) 2- , an alkylene group, a halogenated alkylene group, an arylene group, or a link in which two or more of these are bonded. A group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
本発明において、カルボキシ基を3つ有する化合物をトリカルボン酸化合物という。
上記トリカルボン酸化合物の3つのカルボキシ基のうち2つのカルボキシ基は酸無水物化されていてもよい。
ポリアミドイミド前駆体の製造に用いられるハロゲン化されていてもよいトリカルボン酸化合物としては、分岐鎖状の脂肪族、環状の脂肪族又は芳香族のトリカルボン酸化合物などが挙げられる。
これらのトリカルボン酸化合物は、1種のみ用いてもよいし、2種以上用いてもよい。 Further, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound.
Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
Examples of the halogenated tricarboxylic acid compound used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.
Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.
これらの化合物は、2つのカルボキシ基が無水物化した化合物(例えば、トリメリット酸無水物)であってもよいし、少なくとも1つのカルボキシ基がハロゲン化した化合物(例えば、無水トリメリット酸クロリド)であってもよい。 Specific examples of the tricarboxylic acid compound include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid. (Or phthalic acid anhydride) and benzoic acid are single-bonded, with -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or phenylene group. Examples thereof include linked compounds.
These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (eg, trimellitic anhydride). There may be.
他の繰返し単位としては、上述の式(2)で表される繰返し単位、式(2-1)~式(2-6)のいずれかで表される繰返し単位、下記式(PAI-1)で表される繰返し単位等が挙げられる。
Other repeating units include a repeating unit represented by the above formula (2), a repeating unit represented by any of the formulas (2-1) to (2-6), and the following formula (PAI-1). Examples include the repeating unit represented by.
式(PAI-1)中、R116は、直鎖状又は分岐鎖状の脂肪族基、環状の脂肪族基、及び芳香族基、複素芳香族基、又は単結合若しくは連結基によりこれらを2以上連結した基が例示され、炭素数2~20の直鎖の脂肪族基、炭素数3~20の分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、単結合若しくは連結基によりこれらを2以上組み合わせた基が好ましく、炭素数6~20の芳香族基、又は、単結合若しくは連結基により炭素数6~20の芳香族基を2以上組み合わせた基がより好ましい。
上記連結基としては、-O-、-S-、-C(=O)-、-S(=O)2-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基が好ましく、-O-、-S-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基がより好ましい。
上記アルキレン基としては、炭素数1~20のアルキレン基が好ましく、炭素数1~10のアルキレン基がより好ましく、炭素数1~4のアルキレン基が更に好ましい。
上記ハロゲン化アルキレン基としては、炭素数1~20のハロゲン化アルキレン基が好ましく、炭素数1~10のハロゲン化アルキレン基がより好ましく、炭素数1~4のハロゲン化アルキレン基がより好ましい。また、上記ハロゲン化アルキレン基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。上記ハロゲン化アルキレン基は、水素原子を有していても、水素原子の全てがハロゲン原子で置換されていてもよいが、水素原子の全てがハロゲン原子で置換されていることが好ましい。好ましいハロゲン化アルキレン基の例としては、(ジトリフルオロメチル)メチレン基等が挙げられる。
上記アリーレン基としては、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましく、1,3-フェニレン基又は1,4-フェニレン基が更に好ましい。 In formula (PAI-1), R 116 represents a divalent organic group and R 111 represents a divalent organic group.
In formula (PAI-1), R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group. Examples of the above-mentioned linked groups are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms. The aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable. A group in which two or more of the above are combined is more preferable.
The linking group includes -O-, -S-, -C (= O)-, -S (= O) 2- , an alkylene group, a halogenated alkylene group, an arylene group, or a link in which two or more of these are bonded. A group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
本発明において、カルボキシ基を2つ有する化合物をジカルボン酸化合物、ハロゲン化されたカルボキシ基を2つ有する化合物をジカルボン酸ジハライド化合物という。
ジカルボン酸ジハライド化合物におけるカルボキシ基は、ハロゲン化されていればよいが、例えば、塩素化されていることが好ましい。すなわち、ジカルボン酸ジハライド化合物は、ジカルボン酸ジクロリド化合物であることが好ましい。
ポリアミドイミド前駆体の製造に用いられるハロゲン化されていてもよいジカルボン酸化合物又はジカルボン酸ジハライド化合物としては、直鎖状又は分岐鎖状の脂肪族、環状の脂肪族又は芳香族ジカルボン酸化合物又はジカルボン酸ジハライド化合物などが挙げられる。
これらのジカルボン酸化合物又はジカルボン酸ジハライド化合物は、1種のみ用いてもよいし、2種以上用いてもよい。 Further, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having two carboxy groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.
The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds.
Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.
ジカルボン酸ジハライド化合物の具体例としては、上記ジカルボン酸化合物の具体例における2つのカルボキシ基をハロゲン化した構造の化合物が挙げられる。 Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, glutaric acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-. Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadiponic acid, 3-methyladiponic acid, pimellinic acid, 2,2,6,6-tetramethylpimeric acid, suberic acid, Dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane Diacid, Nonadecan Diacid, Eikosan Diacid, Heneikosan Diacid, Docosan Diacid, Tricosan Diacid, Tetracosan Diacid, Pentacosan Diacid, Hexacosan Diacid, Heptakosan Diacid, Octakosan Diacid, Nonakosan Diacid, Triacanthani Acid, Hentria Contandioic Acid, DotriaContandiic Acid, Diglycolic Acid, Glutaric Acid, Isophthalic Acid, Telephthalic Acid, 4,4'-Biphenylcarboxylic Acid, 4,4'-Biphenylcarboxylic Acid, 4,4'- Examples thereof include dicarboxydiphenyl ether and benzophenone-4,4'-dicarboxylic acid.
Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups are halogenated in the specific examples of the dicarboxylic acid compound.
式(PAI-3)又は式(PAI-4)中、R111及びR117はそれぞれ、式(PAI-2)中のR111及びR117と同義であり、好ましい態様も同様である。 The polyamide-imide precursor preferably contains a repeating unit represented by any of the following formulas (PAI-3) and (PAI-4) as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure. It is more preferable to include a repeating unit represented by the following formula (PAI-3).
In formula (PAI-3) or formula (PAI-4), R 111 and R 117 are synonymous with R 111 and R 117 in formula (PAI-2), respectively, and so are preferred embodiments.
また、本発明におけるポリアミドイミド前駆体の別の一実施形態として、式(PAI-2)で表される繰返し単位、式(PAI-1)で表される繰返し単位、及び、式(PAI-3)及び(PAI-4)のいずれかで表される繰返し単位の合計含有量が、全繰り返し単位の50モル%以上である態様が挙げられる。上記合計含有量は、70モル%以上であることがより好ましく、90モル%以上であることが更に好ましく、90モル%超であることが特に好ましい。上記合計含有量の上限は、特に限定されず、末端を除くポリアミドイミド前駆体における全ての繰返し単位が、式(PAI-2)で表される繰返し単位、式(PAI-1)で表される繰返し単位、又は、式(PAI-3)及び(PAI-4)のいずれかで表される繰返し単位のいずれかであってもよい。 As one embodiment of the polyamide-imide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (PAI-3). The total of the units, the repeating unit represented by the formula (PAI-4), the repeating unit represented by the formula (2), and the repeating unit represented by any of the formulas (2-1) to (2-6). An embodiment in which the content is 50 mol% or more of all repeating units can be mentioned. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) and the formula (PAI-1). Repeating unit, repeating unit represented by any of the formulas (PAI-3) and (PAI-4), repeating unit represented by the formula (2), formulas (2-1) to (2-6). It may be any of the repeating units represented by either.
Further, as another embodiment of the polyamide-imide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a formula (PAI-3). ) And (PAI-4), the total content of the repeating units is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) and the formula (PAI-1). It may be either a repeating unit or a repeating unit represented by any of the formulas (PAI-3) and (PAI-4).
本明細書において、分子量の分散度とは、重量平均分子量を数平均分子量により除した値(重量平均分子量/数平均分子量)をいう。 The degree of dispersion of the molecular weight of the polyamide-imide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
In the present specification, the degree of dispersion of the molecular weight means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
ポリイミド前駆体等は、ジカルボン酸又はジカルボン酸誘導体とジアミンとを反応させて得られる。好ましくは、ジカルボン酸又はジカルボン酸誘導体を、ハロゲン化剤を用いてハロゲン化させた後、ジアミンと反応させて得られる。
ポリイミド前駆体等の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は1種でもよいし、2種以上でもよい。
有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドン及びN-エチルピロリドンが例示される。 [Manufacturing method of polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
ポリイミド前駆体等の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は1種でもよいし、2種以上でもよい。
有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドン及びN-エチルピロリドンが例示される。 It is also preferable to synthesize using a non-halogen catalyst without using the above halogenating agent. As the non-halogen catalyst, a known amidation catalyst containing no halogen atom can be used without particular limitation. For example, a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used. Examples include carbodiimide compounds such as salts and urea compounds. Examples of the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
ポリイミド前駆体等の製造方法に際し、保存安定性をより向上させるため、酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などの末端封止剤で、ポリイミド前駆体等の末端を封止することが好ましい。末端封止剤としては、モノアミンを用いることがより好ましく、モノアミンの好ましい化合物としては、アニリン、2-エチニルアニリン、3-エチニルアニリン、4-エチニルアニリン、5-アミノ-8-ヒドロキシキノリン、1-ヒドロキシ-7-アミノナフタレン、1-ヒドロキシ-6-アミノナフタレン、1-ヒドロキシ-5-アミノナフタレン、1-ヒドロキシ-4-アミノナフタレン、2-ヒドロキシ-7-アミノナフタレン、2-ヒドロキシ-6-アミノナフタレン、2-ヒドロキシ-5-アミノナフタレン、1-カルボキシ-7-アミノナフタレン、1-カルボキシ-6-アミノナフタレン、1-カルボキシ-5-アミノナフタレン、2-カルボキシ-7-アミノナフタレン、2-カルボキシ-6-アミノナフタレン、2-カルボキシ-5-アミノナフタレン、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、4-アミノサリチル酸、5-アミノサリチル酸、6-アミノサリチル酸、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、3-アミノ-4,6-ジヒドロキシピリミジン、2-アミノフェノール、3-アミノフェノール、4-アミノフェノール、2-アミノチオフェノール、3-アミノチオフェノール、4-アミノチオフェノールなどが挙げられる。これらを2種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。 -End sealant-
In order to further improve the storage stability in the method for producing a polyimide precursor or the like, the end of the polyimide precursor or the like is used as an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound or a monoactive ester compound. It is preferable to seal. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-. Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-Aminonaphthalene, 2-carboxy-5-Aminonaphthalene, 2-Aminobenzoic acid, 3-Aminobenzoic acid, 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-Aminothiophenol, 4-Aminothiophenol and the like. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.
ポリイミド前駆体等の製造に際し、固体を析出する工程を含んでいてもよい。具体的には、反応液中のポリイミド前駆体等を、水中に沈殿させ、テトラヒドロフラン等のポリイミド前駆体等が可溶な溶剤に溶解させることによって、固体析出することができる。
その後、ポリイミド前駆体等を乾燥して、粉末状のポリイミド前駆体等を得ることができる。 -Solid precipitation-
A step of precipitating a solid may be included in the production of the polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution can be precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
Then, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.
本発明の組成物における特定樹脂の含有量は、組成物の全固形分に対し20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、50質量%以上であることが一層好ましい。また、本発明の組成物における樹脂の含有量は、組成物の全固形分に対し、99.5質量%以下であることが好ましく、99質量%以下であることがより好ましく、98質量%以下であることが更に好ましく、97質量%以下であることが一層好ましく、95質量%以下であることがより一層好ましい。
本発明の組成物は、特定樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 〔Content〕
The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 50% by mass or more. The content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
具体的には、本発明の硬化性樹脂組成物は、特定樹脂と、後述する他の樹脂とを合計で2種以上含んでもよいし、特定樹脂を2種以上含んでいてもよいが、特定樹脂を2種以上含むことが好ましい。
本発明の硬化性樹脂組成物が特定樹脂を2種以上含む場合、例えば、ポリイミド前駆体であって、二無水物由来の構造(上述の式(2)でいうR115)が異なる2種以上のポリイミド前駆体を含むことが好ましい。
本発明の硬化性樹脂組成物がポリイミド前駆体を2種以上含む場合、少なくとも1種のポリイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量が上述の範囲内であればよく、全てのポリイミド前駆体の合計量を1gとした場合に対する、全てのポリイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量が上述の範囲であることが好ましく、硬化性樹脂組成物に含まれるポリイミド前駆体のそれぞれが、環状イミド構造及び環状イソイミド構造を上述の範囲で含むことがより好ましい。
本発明の硬化性樹脂組成物がポリベンゾオキサゾール前駆体を2種以上含む場合、少なくとも1種のポリベンゾオキサゾール前駆体に含まれるベンゾオキサゾール構造の含有モル量が上述の範囲内であればよく、全てのポリベンゾオキサゾール前駆体の合計量を1gとした場合に対する、全てのポリベンゾオキサゾール前駆体に含まれるベンゾオキサゾール構造の合計含有モル量が上述の範囲であることが好ましく、硬化性樹脂組成物に含まれるポリイミド前駆体のそれぞれが、環状イミド構造及び環状イソイミド構造の少なくとも一方を上述の範囲で含むことがより好ましい。
本発明の硬化性樹脂組成物がポリアミドイミド前駆体を2種以上含む場合、少なくとも1種のポリアミドイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量が上述の範囲内であればよく、全てのポリアミドイミド前駆体の合計量を1gとした場合に対する、全てのポリアミドイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量が上述の範囲であることが好ましく、硬化性樹脂組成物に含まれるポリアミドイミド前駆体のそれぞれが、環状イミド構造及び環状イソイミド構造の少なくとも一方を上述の範囲で含むことがより好ましい。 Further, the curable resin composition of the present invention preferably contains at least two kinds of resins.
Specifically, the curable resin composition of the present invention may contain two or more kinds of the specific resin and another resin described later in total, or may contain two or more kinds of the specific resin, but is specific. It is preferable to contain two or more kinds of resins.
When the curable resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimide precursors having different structures derived from dianhydride (R 115 in the above formula (2)). It is preferable to contain the polyimide precursor of.
When the curable resin composition of the present invention contains two or more types of polyimide precursors, the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in at least one type of polyimide precursor may be within the above range. , The total molar content of the cyclic imide structure and the cyclic isoimide structure contained in all the polyimide precursors is preferably in the above range with respect to the case where the total amount of all the polyimide precursors is 1 g, and the curable resin composition. It is more preferable that each of the polyimide precursors contained in the product contains a cyclic imide structure and a cyclic isoimide structure in the above range.
When the curable resin composition of the present invention contains two or more polybenzoxazole precursors, the molar content of the benzoxazole structure contained in at least one polybenzoxazole precursor may be within the above range. The total molar content of the benzoxazole structure contained in all the polybenzoxazole precursors is preferably in the above range with respect to the case where the total amount of all the polybenzoxazole precursors is 1 g, and the curable resin composition. It is more preferable that each of the polyimide precursors contained in the above contains at least one of a cyclic imide structure and a cyclic isoimide structure in the above range.
When the curable resin composition of the present invention contains two or more kinds of polyamide-imide precursors, the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in at least one kind of polyamide-imide precursor is within the above range. It is preferable that the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in all the polyamide-imide precursors is in the above range with respect to the case where the total amount of all the polyamide-imide precursors is 1 g. It is more preferable that each of the polyamide-imide precursors contained in the curable resin composition contains at least one of a cyclic imide structure and a cyclic isoimide structure in the above range.
本発明の硬化性樹脂組成物は、有機金属錯体を含む。
有機金属錯体とは、金属原子を含む有機錯体化合物であればよいが、金属原子及び有機基を含む錯体化合物であることが好ましく、金属原子に対して有機基が配位した化合物であることがより好ましく、メタロセン化合物であることが更に好ましい。
本発明において、メタロセン化合物とは、置換基を有してもよいシクロペンタジエニルアニオン誘導体2個をη5-配位子として有する有機金属錯体をいう。
上記有機基としては、特に限定されないが、炭化水素基、又は、炭化水素基とヘテロ原子との組み合わせからなる基が好ましい。ヘテロ原子としては、酸素原子、硫黄原子、窒素原子が好ましい。
本発明では、有機基の少なくとも1つは環状基であることが好ましく、少なくとも2つは環状基であることがより好ましい。
上記環状基は、5員環の環状基及び6員環の環状基から選択されることが好ましく、5員環の環状基であることがより好ましい。
上記環状基は、炭化水素環でも複素環でもよいが、炭化水素環が好ましい。
5員環の環状基としては、シクロペンタジエニル基が好ましい。
また、本発明で用いる有機金属錯体は、1分子中に2~4個の環状基を含むことが好ましい。 <Organometallic complex>
The curable resin composition of the present invention contains an organometallic complex.
The organic metal complex may be an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, and is a compound in which an organic group is coordinated with respect to the metal atom. More preferably, it is a metallocene compound.
In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have a substituent as η5-ligands.
The organic group is not particularly limited, but a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom is preferable. As the hetero atom, an oxygen atom, a sulfur atom and a nitrogen atom are preferable.
In the present invention, at least one of the organic groups is preferably a cyclic group, and at least two are more preferably cyclic groups.
The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
The cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferable.
As the cyclic group of the 5-membered ring, a cyclopentadienyl group is preferable.
Further, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.
本発明によれば、特定樹脂を用いることにより、有機金属錯体が膜中で均一に近い状態で分散すると考えられる。
そのため、有機金属錯体が光ラジカル重合開始能を有する場合、有機金属錯体が凝集することによる、局所的なラジカル重合開始剤の凝集が抑制されると考えられる。
ラジカル重合開始剤の凝集が抑制されることにより、特定樹脂又は架橋剤の重合度も膜内で均一に近い状態になりやすいと考えられる。そのため、現像残渣の発生、パターンの断線などが起こりにくく、解像性が向上しやすいと考えられる。
本発明において、光ラジカル重合開始能を有するとは、光の照射によりラジカル重合を開始させることのできるフリーラジカルを発生させることができることを意味する。例えば、ラジカル架橋剤と有機金属錯体とを含む組成物に対して、有機金属錯体が光を吸収する波長域であって、ラジカル架橋剤が光を吸収しない波長域の光を照射した時に、ラジカル架橋剤の消失の有無を確認することにより光ラジカル重合開始能の有無を確認することができる。消失の有無を確認するには、ラジカル架橋剤の種類に応じて適宜の方法を選択できるが、例えばIR測定(赤外分光測定)又はHPLC測定(高速液体クロマトグラフィ)により確認すればよい。
有機金属錯体が光ラジカル重合開始能を有する場合、有機金属錯体はメタロセン化合物であることが好ましく、チタノセン化合物、ジルコノセン化合物又はハフノセン化合物であることがより好ましく、チタノセン化合物、又は、ジルコノセン化合物であることが更に好ましく、チタノセン化合物であることが特に好ましい。
有機金属錯体が光ラジカル重合開始能を有しない場合、有機金属錯体は、チタノセン化合物、テトラアルコキシチタン化合物、チタンアシレート化合物、チタンキレート化合物、ジルコノセン化合物及びハフノセン化合物よりなる群から選択された少なくとも1種の化合物であることが好ましく、チタノセン化合物、ジルコノセン化合物及びハフノセン化合物よりなる群から選択された少なくとも1種の化合物であることがより好ましく、チタノセン化合物及びジルコノセン化合物よりなる群から選択された少なくとも1種の化合物であることが更に好ましく、チタノセン化合物であることが特に好ましい。 An embodiment in which the organometallic complex has an ability to initiate photoradical polymerization is also one of the preferred embodiments of the present invention.
According to the present invention, it is considered that the organometallic complex is dispersed in the film in a nearly uniform state by using the specific resin.
Therefore, when the organometallic complex has the ability to initiate photoradical polymerization, it is considered that the aggregation of the organometallic complex due to the aggregation of the organic metal complex suppresses the aggregation of the local radical polymerization initiator.
It is considered that the degree of polymerization of the specific resin or the cross-linking agent tends to be close to uniform in the film by suppressing the aggregation of the radical polymerization initiator. Therefore, it is considered that the generation of development residue and the disconnection of the pattern are unlikely to occur, and the resolution is likely to be improved.
In the present invention, having the ability to initiate photoradical polymerization means that free radicals capable of initiating radical polymerization can be generated by irradiation with light. For example, when a composition containing a radical cross-linking agent and an organic metal complex is irradiated with light in a wavelength range in which the organic metal complex absorbs light and the radical cross-linking agent does not absorb light, radicals are generated. By confirming the presence or absence of the disappearance of the cross-linking agent, the presence or absence of the photoradical polymerization initiation ability can be confirmed. In order to confirm the presence or absence of disappearance, an appropriate method can be selected depending on the type of radical cross-linking agent, and for example, it may be confirmed by IR measurement (infrared spectroscopy measurement) or HPLC measurement (high performance liquid chromatography).
When the organometallic complex has a photoradical polymerization initiating ability, the organometallic complex is preferably a metallocene compound, more preferably a titanosen compound, a zirconocene compound or a hafnosen compound, and is a titanosen compound or a zirconocene compound. Is more preferable, and a titanosen compound is particularly preferable.
When the organic metal complex does not have the ability to initiate photoradical polymerization, the organic metal complex is at least one selected from the group consisting of a titanosen compound, a tetraalkoxytitanium compound, a titanium acylate compound, a titanium chelate compound, a zirconocene compound and a hafnosen compound. It is preferably a compound of a species, more preferably at least one compound selected from the group consisting of a titanosen compound, a zirconocene compound and a hafnosen compound, and more preferably at least one selected from the group consisting of a titanosen compound and a zirconocene compound. It is more preferably a species compound, and particularly preferably a titanosen compound.
式(P)中、Mは、金属原子であり、Rはそれぞれ独立に、置換基である。
上記Rは、それぞれ独立に、芳香族基、アルキル基、ハロゲン原子及びアルキルスルホニルオキシ基から選択されることが好ましい。 As the organometallic complex, a compound represented by the following formula (P) is preferably mentioned.
In formula (P), M is a metal atom and R is an independent substituent.
The R is preferably independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.
式(P)中のRにおける芳香族基としては、炭素数6~20の芳香族基が挙げられ、炭素数6~20の芳香族炭化水素基が好ましく、フェニル基、1-ナフチル基、又は、2-ナフチル基等が挙げられる。
式(P)中のRにおけるアルキル基としては、炭素数1~20のアルキル基が好ましく、炭素数1~10のアルキル基がより好ましく、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、t-ブチル基、イソペンチル基、2-エチルヘキシル基、2-メチルヘキシル基、シクロペンチル基等が挙げられる。
上記Rにおけるハロゲン原子としては、F、Cl、Br、Iが挙げられる。
上記Rにおけるアルキルスルホニルオキシ基を構成するアルキル基としては、炭素数1~20のアルキル基が好ましく、炭素数1~10のアルキル基がより好ましく、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、t-ブチル基、イソペンチル基、2-エチルヘキシル基、2-メチルヘキシル基、シクロペンチル基等が挙げられる。
上記Rは、更に置換基を有していてもよい。置換基の例としては、ハロゲン原子(F、Cl、Br、I)、ヒドロキシ基、カルボキシ基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、モノアルキルアミノ基、ジアルキルアミノ基、モノアリールアミノ基及びジアリールアミノ基等が挙げられる。 In the formula (P), as the metal atom represented by M, an iron atom, a titanium atom, a zirconium atom or a hafnium atom is preferable, a titanium atom, a zirconium atom or a hafnium atom is more preferable, a titanium atom or a zirconium atom is further preferable, and titanium. Atoms are particularly preferred.
Examples of the aromatic group in R in the formula (P) include an aromatic group having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, a phenyl group, a 1-naphthyl group, or an aromatic group. , 2-naphthyl group and the like.
As the alkyl group in R in the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, an octyl group, and an isopropyl group. , T-Butyl group, Isopentyl group, 2-Ethylhexyl group, 2-Methylhexyl group, Cyclopentyl group and the like.
Examples of the halogen atom in R include F, Cl, Br, and I.
As the alkyl group constituting the alkylsulfonyloxy group in R, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, an octyl group, and the like. Examples thereof include an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclopentyl group and the like.
The R may further have a substituent. Examples of substituents include halogen atom (F, Cl, Br, I), hydroxy group, carboxy group, amino group, cyano group, aryl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxy. Examples thereof include a carbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group and a diarylamino group.
有機金属錯体は、1種又は2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。 The content of the organometallic complex is preferably 0.1 to 30% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.
As the organometallic complex, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
本発明の組成物は、上述した特定樹脂と、特定樹脂とは異なる、他の樹脂(以下、単に「他の樹脂」ともいう。)とを含んでもよい。
他の樹脂としては、ポリアミドイミド、ポリアミドイミド前駆体、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、アクリル樹脂等が挙げられる。
例えば、アクリル樹脂を更に加えることにより、塗布性に優れた組成物が得られ、また、耐溶剤性に優れた有機膜が得られる。
例えば、後述する架橋剤に代えて、又は、後述する架橋剤に加えて、重量平均分子量が20,000以下の重合性基価の高いアクリル系樹脂を組成物に添加することにより、組成物の塗布性、有機膜の耐溶剤性等を向上させることができる。 <Other resins>
The composition of the present invention may contain the above-mentioned specific resin and another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
Examples of other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, and acrylic resin.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
For example, the composition may be prepared by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the cross-linking agent described later or in addition to the cross-linking agent described later. It is possible to improve the coatability, the solvent resistance of the organic film, and the like.
また、本発明の組成物における、他の樹脂の含有量は、組成物の全固形分に対し、80質量%以下であることが好ましく、75質量%以下であることがより好ましく、70質量%以下であることが更に好ましく、60質量%以下であることが一層好ましく、50質量%以下であることがより一層好ましい。
また、本発明の組成物の好ましい一態様として、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、組成物の全固形分に対し、20質量%以下であることが好ましく、15質量%以下であることがより好ましく、10質量%以下であることが更に好ましく、5質量%以下であることが一層好ましく、1質量%以下であることがより一層好ましい。上記含有量の下限は特に限定されず、0質量%以上であればよい。
本発明の組成物は、他の樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 When the composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more. ..
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferable aspect of the composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
本発明の硬化性樹脂組成物は、溶剤を含有することが好ましい。溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、環式炭化水素類、スルホキシド類、アミド類、ウレア類、アルコール類などの化合物が挙げられる。 <Solvent>
The curable resin composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
本発明の組成物は、感光剤を含むことが好ましい。
感光剤には、上述の有機金属錯体であって、光ラジカル重合開始能を有する化合物は含まれないものとする。
本発明の組成物は、光重合開始剤を含むことが好ましい。 <Photosensitizer>
The composition of the present invention preferably contains a photosensitizer.
It is assumed that the photosensitizer does not contain the above-mentioned organometallic complex and a compound having a photoradical polymerization initiation ability.
The composition of the present invention preferably contains a photopolymerization initiator.
本発明の組成物は、感光剤として、光重合開始剤を含むことが好ましい。
光重合開始剤は、光ラジカル重合開始剤であることが好ましい。光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。 [Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as the photosensitizer.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
また、本発明の組成物が、ラジカル重合開始能を有する有機金属錯体を含む場合、本発明の組成物が、上記有機金属錯体と、光ラジカル重合開始剤とを含むことも好ましい。このような態様によれば、上述のように現像残渣の発生、パターンの断線などが抑制され、かつ、露光感度も向上できる。
本発明の組成物が、光ラジカル重合開始能を有しない有機金属錯体を含む場合、本発明の組成物は、光ラジカル重合開始剤を含むことが好ましい。本発明の組成物は特定樹脂を含むため、有機金属錯体の凝集が抑制されると考えられる。光ラジカル重合開始能を有しない有機金属錯体の凝集が抑制されることにより、凝集による局所的な膜の可塑性の増大が抑制され、凝集部位における局所的な重合度の増大も抑制されると推測される。その結果、膜の部位による感度のばらつきの発生が抑制され、解像度が向上すると推測される。
本発明の組成物が、有機金属錯体と光ラジカル重合開始剤とを含む場合、有機金属錯体と光ラジカル重合開始剤の合計含有量に対する有機金属錯体の含有量は、20~80質量%であることが好ましく、30~70質量%であることがより好ましい。
また、上記光ラジカル重合開始剤としては、後述のオキシム化合物が好ましい。 When the organometallic complex has a photoradical polymerization initiating ability, it is also preferable that the composition of the present invention does not substantially contain a radical polymerization initiator other than the above-mentioned organometallic complex. The fact that the composition of the present invention does not substantially contain a radical polymerization initiator other than the organometallic complex means that the content of the radical polymerization initiator other than the organometallic complex is based on the total mass of the organometallic complex. It is said that it is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass.
When the composition of the present invention contains an organometallic complex having a radical polymerization initiatoring ability, it is also preferable that the composition of the present invention contains the above-mentioned organometallic complex and a photoradical polymerization initiator. According to such an aspect, as described above, the generation of development residue, the disconnection of the pattern, and the like can be suppressed, and the exposure sensitivity can be improved.
When the composition of the present invention contains an organometallic complex having no photoradical polymerization initiator ability, the composition of the present invention preferably contains a photoradical polymerization initiator. Since the composition of the present invention contains a specific resin, it is considered that aggregation of the organometallic complex is suppressed. It is speculated that by suppressing the aggregation of organometallic complexes that do not have the ability to initiate photoradical polymerization, the local increase in plasticity of the film due to aggregation is suppressed, and the local increase in degree of polymerization at the aggregation site is also suppressed. Will be done. As a result, it is presumed that the occurrence of variation in sensitivity depending on the part of the film is suppressed and the resolution is improved.
When the composition of the present invention contains an organometallic complex and a photoradical polymerization initiator, the content of the organometallic complex with respect to the total content of the organometallic complex and the photoradical polymerization initiator is 20 to 80% by mass. It is preferably 30 to 70% by mass, and more preferably 30 to 70% by mass.
Further, as the photoradical polymerization initiator, an oxime compound described later is preferable.
市販品ではIRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04(以上、BASF社製)、アデカオプトマーN-1919((株)ADEKA製、特開2012-014052号公報に記載の光ラジカル重合開始剤2)も好適に用いられる。また、TR-PBG-304(常州強力電子新材料有限公司製)、アデカアークルズNCI-831及びアデカアークルズNCI-930((株)ADEKA製)も用いることができる。また、DFI-091(ダイトーケミックス(株)製)を用いることができる。また、下記の構造のオキシム化合物を用いることもできる。
Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used. Further, an oxime compound having the following structure can also be used.
また、本発明の組成物は、感光剤として、光酸発生剤を含むことも好ましい。
光酸発生剤を含有することで、例えば、感光膜の露光部に酸が発生して、上記露光部の現像液(例えば、アルカリ水溶液)に対する溶解性が増大し、露光部が現像液により除去されるポジ型のパターンを得ることができる。
また、組成物が、光酸発生剤と、後述するラジカル架橋剤以外の架橋剤とを含有することにより、例えば、露光部に発生した酸により上記架橋剤の架橋反応が促進され、露光部が非露光部よりも現像液により除去されにくくなる態様とすることもできる。このような態様によれば、ネガ型のパターンを得ることができる。 [Photoacid generator]
Further, the composition of the present invention preferably contains a photoacid generator as a photosensitizer.
By containing the photoacid generator, for example, acid is generated in the exposed part of the photosensitive film, the solubility of the exposed part in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed part is removed by the developing solution. A positive pattern can be obtained.
Further, when the composition contains a photoacid generator and a cross-linking agent other than the radical cross-linking agent described later, for example, the cross-linking reaction of the cross-linking agent is promoted by the acid generated in the exposed part, and the exposed part becomes It is also possible to make it more difficult to be removed by the developing solution than the non-exposed portion. According to such an aspect, a negative type pattern can be obtained.
上記ナフトキノンジアジド化合物としては、例えば、1,2-ナフトキノン-2-ジアジド-5-スルホン酸又は1,2-ナフトキノン-2-ジアジド-4-スルホン酸、これらの化合物の塩又はエステル化合物等が挙げられる。 The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.
オキシムスルホネート化合物は、オキシムスルホネート基を有していれば特に制限はないが、下記式(OS-1)、後述する式(OS-103)、式(OS-104)、又は、式(OS-105)で表されるオキシムスルホネート化合物であることが好ましい。 The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-) It is preferably an oxime sulfonate compound represented by 105).
式(OS-1)中、m3は、0~3の整数を表し、0又は1が好ましい。m3が2又は3であるとき、複数のX3は同一でも異なっていてもよい。
式(OS-1)中、R34は、アルキル基又はアリール基を表し、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基、炭素数1~5のハロゲン化アルコキシル基、Wで置換されていてもよいフェニル基、Wで置換されていてもよいナフチル基又はWで置換されていてもよいアントラニル基であることが好ましい。Wは、ハロゲン原子、シアノ基、ニトロ基、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基又は炭素数1~5のハロゲン化アルコキシル基、炭素数6~20のアリール基、炭素数6~20のハロゲン化アリール基を表す。 Wherein (OS-1), X 3 is an alkyl group, an alkoxyl group, or a halogen atom. If X 3 there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X 3 may have a substituent. The alkyl group in the above X 3, 1 to 4 carbon atoms, straight-chain or branched alkyl group is preferable. The alkoxyl group represented by X 3, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in the X 3, a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X 3 may be the same or different.
In the formula (OS-1), R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. It represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
式(OS-103)~式(OS-105)中、Rs1で表されるアルキル基(炭素数1~30が好ましい)、アリール基(炭素数6~30が好ましい)又はヘテロアリール基(炭素数4~30が好ましい)は、置換基Tを有していてもよい。 In formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group, or a heteroaryl group, and R s2 , which may be present in a plurality of groups, independently represents a hydrogen atom, an alkyl group, and an aryl. R s6 , which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. Represented, ns represents 1 or 2, ms represents an integer of 0-6.
In formulas (OS-103) to (OS-105), an alkyl group represented by R s1 (preferably having 1 to 30 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a substituent T.
式(OS-103)、式(OS-104)、又は、式(OS-105)中、XsはO又はSを表し、Oであることが好ましい。上記式(OS-103)~(OS-105)において、Xsを環員として含む環は、5員環又は6員環である。 In formulas (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable. Of the R s2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by R s2 may have a substituent T.
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
式(OS-103)~式(OS-105)中、Rs6で表されるアルキル基(炭素数1~30が好ましい)及びアルキルオキシ基(炭素数1~30が好ましい)は、置換基を有していてもよい。
式(OS-103)~式(OS-105)中、msは0~6の整数を表し、0~2の整数であることが好ましく、0又は1であることがより好ましく、0であることが特に好ましい。 In formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In formulas (OS-103) to (OS-105), the alkyl group represented by R s6 (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) have substituents. You may have.
In the formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
式(OS-106)~式(OS-111)中、Rt7は、水素原子又は臭素原子を表し、水素原子であることが好ましい。 In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, and R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R t2 represents a hydrogen atom or a methyl group.
In formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
Rt2は、水素原子又はメチル基を表し、水素原子であることが好ましい。
また、上記オキシムスルホネート化合物において、オキシムの立体構造(E,Z)については、いずれか一方であっても、混合物であってもよい。
上記式(OS-103)~式(OS-105)で表されるオキシムスルホネート化合物の具体例としては、特開2011-209692号公報の段落番号0088~0095、特開2015-194674号公報の段落番号0168~0194に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。 In formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692A and paragraphs of JP2015-194674A. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
式(OS-101)又は式(OS-102)中、Ru2aは、アルキル基又はアリール基を表す。
式(OS-101)又は式(OS-102)中、Xuは、-O-、-S-、-NH-、-NRu5-、-CH2-、-CRu6H-又はCRu6Ru7-を表し、Ru5~Ru7はそれぞれ独立に、アルキル基又はアリール基を表す。 In formula (OS-101) or formula (OS-102), Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Represents an aryl group or a heteroaryl group. The embodiment in which R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), Ru2a represents an alkyl or aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH- , -NR u5-, -CH 2- , -CR u6 H- or CR u6 R u7. Represents −, and R u5 to R u7 independently represent an alkyl group or an aryl group.
また、上記オキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造(E,Z等)についてはそれぞれ、いずれか一方であっても、混合物であってもよい。
式(OS-101)で表される化合物の具体例としては、特開2011-209692号公報の段落番号0102~0106、特開2015-194674号公報の段落番号0195~0207に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
上記化合物の中でも、下記b-9、b-16、b-31、b-33が好ましい。
The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP2011-209692 and paragraph numbers 0195 to 0207 of JP2015-194674. These contents are incorporated herein by reference.
Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferable.
より好適には、少なくとも一つのモノ、ジ、又はトリハロゲン置換メチル基がs-トリアジン環に結合したs-トリアジン誘導体、具体的には、例えば、2,4,6-トリス(モノクロロメチル)-s-トリアジン、2,4,6-トリス(ジクロロメチル)-s-トリアジン、2,4,6-トリス(トリクロロメチル)-s-トリアジン、2-メチル-4,6-ビス(トリクロロメチル)-s-トリアジン、2―n-プロピル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(α,α,β-トリクロロエチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(3,4-エポキシフェニル)-4、6-ビス(トリクロロメチル)-s-トリアジン、2-(p-クロロフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-〔1-(p-メトキシフェニル)-2,4-ブタジエニル〕-4,6-ビス(トリクロロメチル)-s-トリアジン、2-スチリル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-i-プロピルオキシスチリル)-4、6-ビス(トリクロロメチル)-s-トリアジン、2-(p-トリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-ナトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2-ベンジルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2,4,6-トリス(ジブロモメチル)-s-トリアジン、2,4,6-トリス(トリブロモメチル)-s-トリアジン、2-メチル-4,6-ビス(トリブロモメチル)-s-トリアジン、2-メトキシ-4,6-ビス(トリブロモメチル)-s-トリアジン等が挙げられる。 As the photoacid generator, an organic halogenated compound can also be applied. Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-46-4605, JP-A-A. 48-36281, JP-A-55-3270, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No. 3), (1970) and the like can be mentioned, and in particular, oxazole compounds substituted with trihalomethyl groups: S-triazine compounds can be mentioned.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example, 2,4,6-tris (monochromomethyl)-. s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- Examples thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.
式(RI-I)中、Ar11は置換基を1~6有していても良い炭素数20以下のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z11-は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオンが好ましい。式(RI-II)中、Ar21、Ar22は各々独立に置換基を1~6有していても良い炭素数20以下のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z21 -は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。式(RI-III)中、R31、R32、R33は各々独立に置換基を1~6有していても良い炭素数20以下のアリール基又はアルキル基、アルケニル基、アルキニル基を表し、好ましくは反応性、安定性の面から、アリール基であることが望ましい。好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z31-は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。 Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).
In the formula (RI-I), Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 carbon number. An alkenyl group having 12 to 12, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, and 1 to 12 carbon atoms. Alkylamino group, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, Examples thereof include a thioaryl group having 1 to 12 carbon atoms. Z11 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable. In the formula (RI-II), Ar 21 and Ar 22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms. Alkyl group, alkenyl group having 1 to 12 carbon atoms, alkynyl group having 1 to 12 carbon atoms, aryl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 1 to 12 carbon atoms, halogen atom , Alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 carbon number Examples thereof include a thioalkyl group having up to 12 and a thioaryl group having 1 to 12 carbon atoms. Z 21 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable. In formula (RI-III), R 31 , R 32 , and R 33 each represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms which may independently have 1 to 6 substituents. , Preferably an aryl group from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Allyloxy group having 1 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z31 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of properties, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
本発明の硬化性樹脂組成物は、感光剤として、光塩基発生剤を含んでもよい。
硬化性樹脂組成物が、光塩基発生剤と、後述する架橋剤とを含有することにより、例えば、露光部に発生した塩基により特定樹脂の環化が促進される、架橋剤の架橋反応が促進される等の作用により、露光部が非露光部よりも現像液により除去されにくくなる態様とすることもできる。このような態様によれば、ネガ型のレリーフパターンを得ることができる。 [Photobase generator]
The curable resin composition of the present invention may contain a photobase generator as a photosensitizer.
When the curable resin composition contains a photobase generator and a cross-linking agent described later, for example, the cyclization of the specific resin is promoted by the base generated in the exposed portion, and the cross-linking reaction of the cross-linking agent is promoted. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion due to such an action. According to such an aspect, a negative type relief pattern can be obtained.
例えば、M.Shirai,and M.Tsunooka, Prog.Polym.Sci.,21,1(1996);角岡正弘,高分子加工,46,2(1997);C.Kutal,Coord.Chem.Rev.,211,353(2001);Y.Kaneko,A.Sarker, and D.Neckers,Chem.Mater.,11,170(1999);H.Tachi,M.Shirai, and M.Tsunooka,J.Photopolym.Sci.Technol.,13,153(2000);M.Winkle, and K.Graziano,J.Photopolym.Sci.Technol.,3,419(1990);M.Tsunooka,H.Tachi, and S.Yoshitaka,J.Photopolym.Sci.Technol.,9,13(1996);K.Suyama,H.Araki,M.Shirai,J.Photopolym.Sci.Technol.,19,81(2006)に記載されているように、遷移金属化合物錯体や、アンモニウム塩などの構造を有するものや、アミジン部分がカルボン酸と塩形成することで潜在化されたもののように、塩基成分が塩を形成することにより中和されたイオン性の化合物や、カルバメート誘導体、オキシムエステル誘導体、アシル化合物などのウレタン結合やオキシム結合などにより塩基成分が潜在化された非イオン性の化合物を挙げることができる。
本発明では、光塩基発生剤として、カルバメート誘導体、アミド誘導体、イミド誘導体、αコバルト錯体類、イミダゾール誘導体、桂皮酸アミド誘導体、オキシム誘導体等がより好ましい例として挙げられる。 The photobase generator is not particularly limited as long as it generates a base by exposure, and known ones can be used.
For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A.M. Sarker, and D. Neckers, Chem. Mater. , 11, 170 (1999); Tachi, M. et al. Shirai, and M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J. et al. Photopolym. Sci. Technol. , 3,419 (1990); Tsunooka, H. et al. Tachi, and S. Yoshitaka, J.M. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H. et al. Araki, M. et al. Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as a transition metal compound complex or an ammonium salt, or those in which the amidin moiety is latent by salt formation with a carboxylic acid. Ionic compounds whose base components are neutralized by forming salts, and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. Can be mentioned.
In the present invention, as the photobase generator, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like are more preferable examples.
イミド化率の観点からは、上記塩基性物質は、共役酸のDMSO(ジメチルスルホキシド)中のpKaが大きいものであることが好ましい。上記pKaは、1以上であることが好ましく、3以上であることがより好ましい。上記pKaの上限は特に限定されないが、20以下であることが好ましい。
ここで、上記pKaとは、酸の第一解離定数の逆数の対数を表し、Determination of Organic Structures by Physical Methods(著者:Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; 編纂:Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955)や、Data for Biochemical Research(著者:Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959)に記載の値を参照することができる。これらの文献に記載の無い化合物については、ACD/pKa(ACD/Labs製)のソフトを用いて構造式より算出した値をpKaとして用いることとする。 The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
From the viewpoint of the imidization ratio, the basic substance preferably has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid. The pKa is preferably 1 or more, and more preferably 3 or more. The upper limit of the pKa is not particularly limited, but is preferably 20 or less.
Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; You can refer to the values described in Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using ACD / pKa (manufactured by ACD / Labs) software is used as pKa.
また、パターンの耐薬品性の観点からは、光塩基発生剤としては、構造中に塩を含む光塩基発生剤であることが好ましい。 From the viewpoint of storage stability of the curable resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and the nitrogen atom of the base portion generated in the photobase generator. It is preferable that there is no charge on the top. As the photobase generator, it is preferable that the generated base is latent using a covalent bond, and the mechanism of base generation is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cleaved. It is preferable that the base is generated. When the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
Further, from the viewpoint of chemical resistance of the pattern, the photobase generator is preferably a photobase generator containing a salt in the structure.
本発明に係る光塩基発生剤としては、例えば、特開2009-080452号公報及び国際公開第2009/123122号で開示されたような桂皮酸アミド構造を有する光塩基発生剤、特開2006-189591号公報及び特開2008-247747号公報で開示されたようなカルバメート構造を有する光塩基発生剤、特開2007-249013号公報及び特開2008-003581号公報で開示されたようなオキシム構造、カルバモイルオキシム構造を有する光塩基発生剤等が挙げられるが、これらに限定されず、その他にも公知の光塩基発生剤の構造を用いることができる。 Further, for the above reasons, as the photobase generator, it is preferable that the base generated as described above is latent using a covalent bond, and the generated base has an amide bond, a carbamate bond, and an oxime bond. It is preferably latent using.
Examples of the photobase generator according to the present invention include a photobase generator having a cinnamic acid amide structure as disclosed in JP-A-2009-08452 and JP-A-2009 / 123122, JP-A-2006-189591. A photobase generator having a carbamate structure as disclosed in JP-A and JP-A-2008-247747, an oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581, Carbamoyl. Examples thereof include a photobase generator having an oxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.
本発明の組成物は、熱重合開始剤を含んでもよく、特に熱ラジカル重合開始剤を含んでもよい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。熱ラジカル重合開始剤を添加することによって、後述する加熱工程において、樹脂及び架橋剤の重合反応を進行させることもできるので、より耐溶剤性を向上できる。 <Thermal polymerization initiator>
The composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the cross-linking agent can be allowed to proceed in the heating step described later, so that the solvent resistance can be further improved.
本発明の組成物は、熱酸発生剤を含んでもよい。
熱酸発生剤は、加熱により酸を発生し、ヒドロキシメチル基、アルコキシメチル基又はアシルオキシメチル基を有する化合物、エポキシ化合物、オキセタン化合物及びベンゾオキサジン化合物から選ばれる少なくとも1種の化合物の架橋反応を促進させる効果がある。 <Thermal acid generator>
The composition of the present invention may contain a thermoacid generator.
The thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
熱分解開始温度は、熱酸発生剤を耐圧カプセル中5℃/分で500℃まで加熱した場合に、最も温度が低い発熱ピークのピーク温度として求められる。
熱分解開始温度を測定する際に用いられる機器としては、Q2000(TAインスツルメント社製)等が挙げられる。 The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
本発明の硬化性樹脂組成物は、オニウム塩を更に含んでもよい。
特に、本発明の硬化性樹脂組成物が特定樹脂としてポリイミド前駆体又はポリベンゾオキサゾール前駆体を含む場合、オニウム塩を含むことが好ましい。
オニウム塩の種類等は特に定めるものではないが、アンモニウム塩、イミニウム塩、スルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましく挙げられる。
これらの中でも、熱安定性が高い観点からはアンモニウム塩又はイミニウム塩が好ましく、ポリマーとの相溶性の観点からはスルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましい。 <Onium salt>
The curable resin composition of the present invention may further contain an onium salt.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it preferably contains an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
すなわち、オニウム塩は、同一の分子構造内に、カチオン部と、アニオン部と、を有する分子内塩であってもよいし、それぞれ別分子であるカチオン分子と、アニオン分子と、がイオン結合した分子間塩であってもよいが、分子間塩であることが好ましい。また、本発明の硬化性樹脂組成物において、上記カチオン部又はカチオン分子と、上記アニオン部又はアニオン分子と、はイオン結合により結合されていてもよいし、解離していてもよい。
オニウム塩におけるカチオンとしては、アンモニウムカチオン、ピリジニウムカチオン、スルホニウムカチオン、ヨードニウムカチオン又はホスホニウムカチオンが好ましく、テトラアルキルアンモニウムカチオン、スルホニウムカチオン及びヨードニウムカチオンよりなる群から選択される少なくとも1種のカチオンがより好ましい。 The onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
熱塩基発生剤とは、加熱により塩基を発生する化合物をいい、例えば、40℃以上に加熱すると塩基を発生する化合物等が挙げられる。
オニウム塩としては、例えば、国際公開第2018/043262号の段落0122~0138に記載のオニウム塩等が挙げられる。また、その他、ポリイミド前駆体の分野で使用されるオニウム塩を、特に制限なく使用することが可能である。 The onium salt used in the present invention may be a thermobase generator described later.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.
オニウム塩は、1種又は2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
本発明の硬化性樹脂組成物は、熱塩基発生剤を更に含んでもよい。
特に、本発明の硬化性樹脂組成物が特定樹脂としてポリイミド前駆体又はポリベンゾオキサゾール前駆体を含む場合、熱塩基発生剤を含むことが好ましい。
他の熱塩基発生剤は、上述のオニウム塩に該当する化合物であってもよいし、上述のオニウム塩以外の熱塩基発生剤であってもよい。
上述のオニウム塩以外の熱塩基発生剤としては、ノニオン系熱塩基発生剤が挙げられる。
ノニオン系熱塩基発生剤としては、式(B1)又は式(B2)で表される化合物が挙げられる。
The curable resin composition of the present invention may further contain a thermosetting agent.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain a thermosetting agent.
The other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
Examples of the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
Rb13はアルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アルケニル基(炭素数2~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、本発明の効果を奏する範囲で置換基を有していてもよい。中でも、Rb13はアリールアルキル基が好ましい。 In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb 13 is preferably an arylalkyl group.
Rb15及びRb16は水素原子、アルキル基(炭素数1~12が好ましく、1~6がより好ましく、1~3が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~6がより好ましく、2~3が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~11が更に好ましい)であり、水素原子又はメチル基が好ましい。
Rb17はアルキル基(炭素数1~24が好ましく、1~12がより好ましく、3~8が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~10がより好ましく、3~8が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、中でもアリール基が好ましい。 Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in the formula (B1-1).
Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 is more preferable), and a hydrogen atom or a methyl group is preferable.
Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
本発明の硬化性樹脂組成物は、架橋剤を含むことが好ましい。
架橋剤としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。 <Crosslinking agent>
The curable resin composition of the present invention preferably contains a cross-linking agent.
Examples of the cross-linking agent include radical cross-linking agents and other cross-linking agents.
本発明の硬化性樹脂組成物は、ラジカル架橋剤を更に含むことが好ましい。
ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基などのエチレン性不飽和結合を有する基が挙げられる。
これらの中でも、上記エチレン性不飽和結合を含む基としては、(メタ)アクリロイル基が好ましく、反応性の観点からは、(メタ)アクリロキシ基がより好ましい。 <Radical cross-linking agent>
The curable resin composition of the present invention preferably further contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
Among these, the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
エチレン性不飽和結合を2個有する化合物は、上記エチレン性不飽和結合を含む基を2個有する化合物であることが好ましい。
また、得られるパターンの膜強度の観点からは、本発明の硬化性樹脂組成物は、ラジカル架橋剤として、エチレン性不飽和結合を3個以上有する化合物を含むことが好ましい。上記エチレン性不飽和結合を3個以上有する化合物としては、エチレン性不飽和結合を3~15個有する化合物が好ましく、エチレン性不飽和結合を3~10個有する化合物がより好ましく、3~6個有する化合物が更に好ましい。
また、上記エチレン性不飽和結合を3個以上有する化合物は、上記エチレン性不飽和結合を含む基を3個以上有する化合物であることが好ましく、3~15個有する化合物であることがより好ましく、3~10個有する化合物であることが更に好ましく、3~6個有する化合物であることが特に好ましい。
また、得られるパターンの膜強度の観点からは、本発明の硬化性樹脂組成物は、エチレン性不飽和結合を2個有する化合物と、上記エチレン性不飽和結合を3個以上有する化合物とを含むことも好ましい。 The radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but a compound having two or more ethylenically unsaturated bonds is more preferable.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
Further, from the viewpoint of the film strength of the obtained pattern, the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent. As the compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable. The compound having is more preferable.
The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds. A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
Further, from the viewpoint of the film strength of the obtained pattern, the curable resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable.
また、パターンの弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、n-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、グリシジル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等の(メタ)アクリル酸誘導体、N-ビニルピロリドン、N-ビニルカプロラクタム等のN-ビニル化合物類、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で100℃以上の沸点を持つ化合物も好ましい。 For the curable resin composition of the present invention, it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene. Glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives Dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. can. If necessary, two or more of these can be mixed and used. For example, the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
Further, from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern, a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent. Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
本発明の硬化性樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことが好ましい。
本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の感光剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
上記酸又は塩基は、露光工程において、感光剤である光酸発生剤又は光塩基発生剤から発生する酸又は塩基であることが好ましい。
他の架橋剤としては、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基を有する化合物が好ましく、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも1種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をメチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
これらの中でも、本発明の硬化性樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことがより好ましい。 <Other cross-linking agents>
The curable resin composition of the present invention preferably contains another cross-linking agent different from the radical cross-linking agent described above.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer. It is preferable that the compound has a plurality of groups in the molecule for which the reaction to be formed is promoted, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of an acid or a base. A compound having a plurality of groups promoted by the above in the molecule is preferable.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator which is a photosensitizer in the exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable. A compound having a structure directly bonded to a nitrogen atom is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to a methylol group or an alkoxymethyl group. Examples thereof include compounds having a substituted structure. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and preferably contains a glycoluril-based cross-linking agent and melamine, which will be described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.
ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、
モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、
モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノジエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、
1,3-ジ(メトキシメチル)4,5-ジヒドロキシ-2-イミダゾリジノン、1,3-ジ(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリジノンなどが挙げられる。 Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl. , Trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, di Propoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl, etc. Glycoluryl-based cross-linking agent;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneureated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy A propylene urea-based cross-linking agent such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.
このような化合物の具体例としては、ベンゼンジメタノール、ビス(ヒドロキシメチル)クレゾール、ビス(ヒドロキシメチル)ジメトキシベンゼン、ビス(ヒドロキシメチル)ジフェニルエーテル、ビス(ヒドロキシメチル)ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス(ヒドロキシメチル)ビフェニル、ジメチルビス(ヒドロキシメチル)ビフェニル、ビス(メトキシメチル)ベンゼン、ビス(メトキシメチル)クレゾール、ビス(メトキシメチル)ジメトキシベンゼン、ビス(メトキシメチル)ジフェニルエーテル、ビス(メトキシメチル)ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス(メトキシメチル)ビフェニル、ジメチルビス(メトキシメチル)ビフェニル、4,4’,4’’-エチリデントリス[2,6-ビス(メトキシメチル)フェノール]、5,5’-[2,2,2‐トリフルオロ‐1‐(トリフルオロメチル)エチリデン]ビス[2‐ヒドロキシ‐1,3‐ベンゼンジメタノール]、3,3’,5,5’-テトラキス(メトキシメチル)-1,1’-ビフェニル-4,4’-ジオール等が挙げられる。 In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which the seed groups are directly attached are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like can be mentioned.
エポキシ化合物としては、一分子中にエポキシ基を2以上有する化合物であることが好ましい。エポキシ基は、200℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、硬化性樹脂組成物の低温硬化及び反りの抑制に効果的である。 [Epoxy compound (compound having an epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.
オキセタン化合物としては、一分子中にオキセタン環を2つ以上有する化合物、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン、3-エチル-3-(2-エチルヘキシルメチル)オキセタン、1,4-ベンゼンジカルボン酸-ビス[(3-エチル-3-オキセタニル)メチル]エステル等を挙げることができる。具体的な例としては、東亞合成(株)製のアロンオキセタンシリーズ(例えば、OXT-121、OXT-221、OXT-191、OXT-223)が好適に使用することができ、これらは単独で、又は2種以上混合してもよい。 [Oxetane compound (compound having an oxetanyl group)]
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、更に熱収縮を小さくして反りの発生が抑えられることから好ましい。 [Benzoxazine compound (compound having a benzoxazolyl group)]
Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
得られるパターンの基材への密着性を向上する観点からは、本発明の硬化性樹脂組成物は、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物よりなる群から選ばれた少なくとも1種の化合物を更に含むことが好ましい。 <Compounds having a sulfonamide structure, compounds having a thiourea structure>
From the viewpoint of improving the adhesion of the obtained pattern to the substrate, the curable resin composition of the present invention is at least one selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. It is preferable to further contain a compound.
スルホンアミド構造とは、下記式(S-1)で表される構造である。
式(S-1)中、Rは水素原子又は有機基を表し、Rは他の構造と結合して環構造を形成してもよく、*はそれぞれ独立に、他の構造との結合部位を表す。
上記Rは、下記式(S-2)におけるR2と同様の基であることが好ましい。
スルホンアミド構造を有する化合物は、スルホンアミド構造を2以上有する化合物であってもよいが、スルホンアミド構造を1つ有する化合物であることが好ましい。 [Compound having a sulfonamide structure]
The sulfonamide structure is a structure represented by the following formula (S-1).
In the formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to another structure to form a ring structure, and * may independently form a binding site with another structure. show.
The R is preferably the same group as R 2 in the following formula (S-2).
The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but a compound having one sulfonamide structure is preferable.
式(S-2)中、R1、R2及びR3はそれぞれ独立に、水素原子又は1価の有機基を表し、R1、R2及びR3のうち2つ以上が互いに結合して環構造を形成していてもよい。
R1、R2及びR3はそれぞれ独立に、1価の有機基であることが好ましい。
R1、R2及びR3の例としては、水素原子、又は、アルキル基、シクロアルキル基、アルコキシ基、アルキルエーテル基、アルキルシリル基、アルコキシシリル基、アリール基、アリールエーテル基、カルボキシ基、カルボニル基、アリル基、ビニル基、複素環基、若しくはこれらを2以上組み合わせた基などが挙げられる。
上記アルキル基としては、炭素数1~10のアルキル基が好ましく、炭素数1~6のアルキル基がより好ましい。上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、2-エチルへキシル基等が挙げられる。
上記シクロアルキル基としては、炭素数5~10のシクロアルキル基が好ましく、炭素数6~10のシクロアルキル基がより好ましい。上記シクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基及びシクロヘキシル基等が挙げられる。
上記アルコキシ基としては、炭素数1~10のアルコキシ基が好ましく、炭素数1~5のアルコキシ基がより好ましい。上記アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基及びペントキシ基等が挙げられる。
上記アルコキシシリル基としては、炭素数1~10のアルコキシシリル基が好ましく、炭素数1~4のアルコキシシリル基がより好ましい。上記アルコキシシリル基としては、メトキシシリル基、エトキシシリル基、プロポキシシリル基及びブトキシシリル基等が挙げられる。
上記アリール基としては、炭素数6~20のアリール基が好ましく、炭素数6~12のアリール基がより好ましい。上記アリール基は、アルキル基等の置換基を有していてもよい。上記アリール基としては、フェニル基、トリル基、キシリル基及びナフチル基等が挙げられる。
上記複素環基としては、トリアゾール環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジジン環、ピラジン環、ピペリジン環、ピペリジン、ピペラジン環、モルホリン環、ジヒドロピラン環、テトラヒドロピラン基、トリアジン環等の複素環構造から水素原子を1つ除いた基などが挙げられる。 The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
In formula (S-2), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of R 1 , R 2 and R 3 are bonded to each other. It may form a ring structure.
It is preferable that R 1 , R 2 and R 3 are independently monovalent organic groups.
Examples of R 1 , R 2 and R 3 include a hydrogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, and a carboxy group. Examples thereof include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, and a pyrimididine ring. , Pyrazole ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring and other heterocyclic structures from which one hydrogen atom has been removed.
チオウレア構造とは、下記式(T-1)で表される構造である。
式(T-1)中、R4及びR5はそれぞれ独立に、水素原子又は1価の有機基を表し、R4及びR5は結合して環構造を形成してもよく、R4は*が結合する他の構造と結合して環構造を形成してもよく、R5は*が結合する他の構造と結合して環構造を形成してもよく、*はそれぞれ独立に、他の構造との結合部位を表す。 [Compound with thiourea structure]
The thiourea structure is a structure represented by the following formula (T-1).
In formula (T-1), R 4 and R 5 each independently represent a hydrogen atom or a monovalent organic group, and R 4 and R 5 may be combined to form a ring structure, where R 4 is. The ring structure may be formed by combining with other structures to which * is bonded, R 5 may be combined with other structures to which * is bonded to form a ring structure, and * may be independently and others. Represents the site of connection with the structure of.
R4及びR5の例としては、水素原子、又は、アルキル基、シクロアルキル基、アルコキシ基、アルキルエーテル基、アルキルシリル基、アルコキシシリル基、アリール基、アリールエーテル基、カルボキシ基、カルボニル基、アリル基、ビニル基、複素環基、若しくは、これらを2以上組み合わせた基などが挙げられる。
上記アルキル基としては、炭素数1~10のアルキル基が好ましく、炭素数1~6のアルキル基がより好ましい。上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、2-エチルへキシル基等が挙げられる。
上記シクロアルキル基としては、炭素数5~10のシクロアルキル基が好ましく、炭素数6~10のシクロアルキル基がより好ましい。上記シクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基及びシクロヘキシル基等が挙げられる。
上記アルコキシ基としては、炭素数1~10のアルコキシ基が好ましく、炭素数1~5のアルコキシ基がより好ましい。上記アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基及びペントキシ基等が挙げられる。
上記アルコキシシリル基としては、炭素数1~10のアルコキシシリル基が好ましく、炭素数1~4のアルコキシシリル基がより好ましい。上記アルコキシシリル基としては、メトキシシリル基、エトキシシリル基、プロポキシシリル基及びブトキシシリル基等が挙げられる。
上記アリール基としては、炭素数6~20のアリール基が好ましく、炭素数6~12のアリール基がより好ましい。上記アリール基は、アルキル基等の置換基を有していてもよい。上記アリール基としては、フェニル基、トリル基、キシリル基及びナフチル基等が挙げられる。
上記複素環基としては、トリアゾール環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジジン環、ピラジン環、ピペリジン環、ピペリジン、ピペラジン環、モルホリン環、ジヒドロピラン環、テトラヒドロピラン基、トリアジン環等の複素環構造から水素原子を1つ除いた基などが挙げられる。
チオウレア構造を有する化合物は、チオウレア構造を2以上有する化合物であってもよいが、チオウレア構造を1つ有する化合物であることが好ましい。 It is preferable that R 4 and R 5 are independently hydrogen atoms.
Examples of R 4 and R 5 include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, and a carbonyl group. Examples thereof include an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, and a pyrimididine ring. , Pyrazole ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring and other heterocyclic structures from which one hydrogen atom has been removed.
The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferable.
式(T-2)中、R4~R7はそれぞれ独立に、水素原子又は1価の有機基を表し、R4~R7のうち少なくとも2つは互いに結合して環構造を形成していてもよい。 The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
In formula (T-2), R 4 to R 7 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R 4 to R 7 are bonded to each other to form a ring structure. You may.
式(T-2)中、R6及びR7はそれぞれ独立に、1価の有機基であることが好ましい。
式(T-2)中、R6及びR7における1価の有機基の好ましい態様は、式(T-1)中のR4及びR5における1価の有機基の好ましい態様と同様である。 Wherein (T-2), R 4 and R 5 have the same meanings as R 4 and R 5 in formula (T-1), a preferable embodiment thereof is also the same.
In the formula (T-2), it is preferable that R 6 and R 7 are independently monovalent organic groups.
In the formula (T-2), the preferred embodiment of the monovalent organic group in R 6 and R 7 is the same as the preferred embodiment of the monovalent organic group in R 4 and R 5 in the formula (T-1). ..
本発明の硬化性樹脂組成物の全質量に対する、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物の合計含有量は、0.05~10質量%であることが好ましく、0.1~5質量%であることがより好ましく、0.2~3質量%であることが更に好ましい。
本発明の硬化性樹脂組成物は、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物よりなる群から選ばれる化合物を、1種のみ含んでもよいし、2種以上を含んでもよい。1種のみ含む場合にはその化合物の含有量が、2種以上を含む場合にはその合計量が、上記の範囲となることが好ましい。 〔Content〕
The total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, preferably 0.1 to 5% by mass, based on the total mass of the curable resin composition of the present invention. It is more preferably%, and further preferably 0.2 to 3% by mass.
The curable resin composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more compounds. When only one type is contained, the content of the compound is preferably within the above range, and when two or more types are contained, the total amount thereof is preferably within the above range.
本発明の硬化性樹脂組成物は、更にマイグレーション抑制剤を含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層(金属配線)由来の金属イオンが感光膜内へ移動することを効果的に抑制可能となる。 <Migration inhibitor>
The curable resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the photosensitive film.
本発明の硬化性樹脂組成物は、重合禁止剤を含むことが好ましい。 <Polymerization inhibitor>
The curable resin composition of the present invention preferably contains a polymerization inhibitor.
本発明の硬化性樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、シランカップリング剤、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物等などが挙げられる。 <Metal adhesion improver>
The curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds and the like. And so on.
アルミニウム系接着助剤としては、例えば、アルミニウムトリス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。 [Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetone), ethyl acetoacetate aluminum diisopropirate, and the like.
本発明の硬化性樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、特開2014-186186号公報の段落0046~0049に記載の化合物、特開2013-072935号公報の段落0032~0043に記載のスルフィド系化合物を用いることもできる。 <Metal adhesion improver>
The curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. As the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.
本発明の硬化性樹脂組成物は、本発明の効果が得られる範囲で、必要に応じて、各種の添加物、例えば、増感剤、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は硬化性樹脂組成物の固形分の3質量%以下とすることが好ましい。 <Other additives>
The curable resin composition of the present invention contains various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and an inorganic particle, if necessary, as long as the effects of the present invention can be obtained. , Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, anti-aggregation agent and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
本発明の硬化性樹脂組成物は、増感剤を含んでいてもよい。増感剤は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸又は塩基を生成する。
増感剤としては、例えば、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2,5-ビス(4’-ジエチルアミノベンザル)シクロペンタン、2,6-ビス(4’-ジエチルアミノベンザル)シクロヘキサノン、2,6-ビス(4’-ジエチルアミノベンザル)-4-メチルシクロヘキサノン、4,4’-ビス(ジメチルアミノ)カルコン、4,4’-ビス(ジエチルアミノ)カルコン、p-ジメチルアミノシンナミリデンインダノン、p-ジメチルアミノベンジリデンインダノン、2-(p-ジメチルアミノフェニルビフェニレン)-ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3-ビス(4’-ジメチルアミノベンザル)アセトン、1,3-ビス(4’-ジエチルアミノベンザル)アセトン、3,3’-カルボニル-ビス(7-ジエチルアミノクマリン)、3-アセチル-7-ジメチルアミノクマリン、3-エトキシカルボニル-7-ジメチルアミノクマリン、3-ベンジロキシカルボニル-7-ジメチルアミノクマリン、3-メトキシカルボニル-7-ジエチルアミノクマリン、3-エトキシカルボニル-7-ジエチルアミノクマリン、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、N-フェニルエタノールアミン、4-モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2-メルカプトベンズイミダゾール、1-フェニル-5-メルカプトテトラゾール、2-メルカプトベンゾチアゾール、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンズチアゾール、2-(p-ジメチルアミノスチリル)ナフト(1,2-d)チアゾール、2-(p-ジメチルアミノベンゾイル)スチレン、ジフェニルアセトアミド、ベンズアニリド、N-メチルアセトアニリド、3’,4’-ジメチルアセトアニリド等が挙げられる。
増感剤としては、増感色素を用いてもよい。
増感色素の詳細については、特開2016-027357号公報の段落0161~0163の記載を参酌でき、この内容は本明細書に組み込まれる。 [Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electron-excited state. The sensitizer in the electron-excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminosinnamiri Denindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) iso Naftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3 -Acetyl-7-dimethylaminocumine, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocumine, 3-methoxycarbonyl-7-diethylaminocumine, 3-ethoxycarbonyl-7-diethylamino Kumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) ) Naft (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4'-dimethylacetanilide and the like.
As the sensitizer, a sensitizing dye may be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.
本発明の硬化性樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版(高分子学会編、2005年)683-684頁に定義されている。連鎖移動剤としては、例えば、分子内にSH、PH、SiH、及びGeHを有する化合物群が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、若しくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物を好ましく用いることができる。 [Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, a thiol compound can be preferably used.
本発明の硬化性樹脂組成物には、塗布性をより向上させる観点から、界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。また、下記界面活性剤も好ましい。下記式中、主鎖の繰返し単位を示す括弧は各繰返し単位の含有量(モル%)を、側鎖の繰返し単位を示す括弧は各繰返し単位の繰り返し数をそれぞれ表す。
また、界面活性剤は、国際公開第2015/199219号の段落0159~0165に記載の化合物を用いることもできる。
フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報の段落0050~0090および段落0289~0295に記載された化合物、例えばDIC(株)製のメガファックRS-101、RS-102、RS-718K等が挙げられる。 [Surfactant]
A surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.
本発明の硬化性樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で硬化性樹脂組成物の表面に偏在させてもよい。 [Higher fatty acid derivative]
The curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.
本発明の樹脂組成物は、無機粒子を含んでもよい。無機粒子として、具体的には、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン、ガラス等を含むことができる。 [Inorganic particles]
The resin composition of the present invention may contain inorganic particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
上記無機粒子の平均粒子径を多量に含有させることによって、上記硬化膜の機械特性が劣化することがある。また、上記無機粒子の平均粒子径が2.0μmを超えると、露光光の散乱によって解像度が低下することがある。 The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
By containing a large amount of the average particle size of the inorganic particles, the mechanical properties of the cured film may deteriorate. Further, if the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.
本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、p-オクチルフェニルサリシレート、p-t-ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-アミル-5’-イソブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-プロピルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-[2’-ヒドロキシ-5’-(1,1,3,3-テトラメチル)フェニル]ベンゾトリアゾールなどが挙げられる。 [UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxy-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.
本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、0.001質量%以上1質量%以下であることが好ましく、0.01質量%以上0.1質量%以下であることがより好ましい。 In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。 [Organic titanium compound]
The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
有機チタン化合物の具体例を、以下のI)~VII)に示す:
I)チタンキレート化合物:中でも、ネガ型感光性樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を2個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
II)テトラアルコキシチタン化合物:例えば、チタニウムテトラ(n-ブトキサイド)、チタニウムテトラエトキサイド、チタニウムテトラ(2-エチルヘキソキサイド)、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ(n-ノニロキサイド)、チタニウムテトラ(n-プロポキサイド)、チタニウムテトラステアリロキサイド、チタニウムテトラキス[ビス{2,2-(アリロキシメチル)ブトキサイド}]等である。
III)チタノセン化合物:例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロフェニル)チタニウム、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム等である。
IV)モノアルコキシチタン化合物:例えば、チタニウムトリス(ジオクチルホスフェート)イソプロポキサイド、チタニウムトリス(ドデシルベンゼンスルホネート)イソプロポキサイド等である。
V)チタニウムオキサイド化合物:例えば、チタニウムオキサイドビス(ペンタンジオネート)、チタニウムオキサイドビス(テトラメチルヘプタンジオネート)、フタロシアニンチタニウムオキサイド等である。
VI)チタニウムテトラアセチルアセトネート化合物:例えば、チタニウムテトラアセチルアセトネート等である。
VII)チタネートカップリング剤:例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。 Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide. , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titanium tris (dioctyl phosphate) isopropoxyside, titanium tris (dodecylbenzene sulfonate) isopropoxide, and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetone compound: For example, titanium tetraacetylacetone.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。前述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物を使用することもできる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。好ましい酸化防止剤の例としては、2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノールおよび一般式(3)で表される化合物が挙げられる。 〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material. Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).
本発明の硬化性樹脂組成物の水分含有量は、塗布面性状の観点から、5質量%未満が好ましく、1質量%未満がより好ましく、0.6質量%未満が更に好ましい。水分の含有量を維持する方法としては、保管条件における湿度の調整、収容容器の空隙率低減などが挙げられる。 <Restrictions on other contained substances>
The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.
ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。 Considering the use as a semiconductor material, the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.
本発明の硬化性樹脂組成物は、再配線層用層間絶縁膜の形成に用いられることが好ましい。
また、その他、半導体デバイスの絶縁膜の形成、又は、ストレスバッファ膜の形成等にも用いることができる。 <Use of curable resin composition>
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
本発明の硬化性樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。 <Preparation of curable resin composition>
The curable resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.
フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。 Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is further preferable. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
次に、硬化膜、積層体、半導体デバイス、及びそれらの製造方法について説明する。 (Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.
本発明の硬化膜の製造方法は、上記膜形成工程、並びに、上記膜を露光する露光工程及び上記膜を現像する現像工程を含むことが好ましい。上記露光工程及び現像工程により、硬化膜のパターンが得られる。
また、本発明の硬化膜の製造方法は、上記膜形成工程、及び、必要に応じて上記現像工程を含み、かつ、上記膜を50~450℃で加熱する加熱工程を含むことがより好ましい。
具体的には、以下の(a)~(d)の工程を含むことも好ましい。
(a)樹脂組成物を基材に適用して膜(樹脂組成物層)を形成する膜形成工程
(b)膜形成工程の後、膜を露光する露光工程
(c)露光された上記膜を現像する現像工程
(d)現像された上記膜を50~450℃で加熱する加熱工程
上記加熱工程において加熱することにより、露光で硬化した樹脂層を更に硬化させることができる。この加熱工程で、例えば上述の熱塩基発生剤が分解し、十分な硬化性が得られる。 The method for producing a cured film of the present invention (hereinafter, also simply referred to as “the method for producing the present invention”) is a film forming step of applying the resin composition of the present invention to a substrate to form a film (resin film). It is preferable to include it.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film. By the above exposure step and development step, a pattern of a cured film can be obtained.
Further, the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C.
Specifically, it is also preferable to include the following steps (a) to (d).
(A) Film forming step of applying the resin composition to a substrate to form a film (resin composition layer) (b) Exposure step of exposing the film after the film forming step (c) The exposed film Development step for developing (d) Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.
本発明の好ましい実施形態に係る製造方法は、樹脂組成物を基材に適用して膜(層状)にする、膜形成工程(層形成工程)を含む。 <Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the resin composition is applied to a substrate to form a film (layered).
また、これらの基材にはヘキサメチルジシラザン(HMDS)等による密着層や酸化層などの層が表面に設けられていてもよい。
また、基材としては、例えば板状の基材(基板)が用いられる。
基材の形状は特に限定されず、円形状であっても矩形状であってもよいが、矩形状であることが好ましい。
基材のサイズとしては、円形状であれば、例えば直径が100~450mmであり、好ましくは200~450mmである。矩形状であれば、例えば短辺の長さが100~1000mmであり、好ましくは200~700mmである。 The type of the base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin film, There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, and electrode plates of plasma display panels (PDPs). Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a mold base material are more preferable.
Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
Further, as the base material, for example, a plate-shaped base material (board) is used.
The shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
また感光性樹脂組成物の粘度や設定する膜厚によっては、300~3,500rpmの回転数で、10~180秒適用することも好ましい。また膜厚の均一性を得るために、複数の回転数を組み合わせて塗布することもできる。
また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
転写方法に関しては特開2006-023696号公報の段落0023、0036~0051や、特開2006-047592号公報の段落0096~0108に記載の作製方法を本発明においても好適に用いることができる。
また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス(EBR)、エアナイフ、バックリンスなどが挙げられる。
また樹脂組成物を基材に塗布する前に基材を種々の溶剤を塗布し、基材の濡れ性を向上させた後に樹脂組成物を塗布するプリウェット工程を採用しても良い。 Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the base material. For a circular base material such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Further, depending on the viscosity of the photosensitive resin composition and the film thickness to be set, it is preferable to apply the photosensitive resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Further, in order to obtain the uniformity of the film thickness, a plurality of rotation speeds can be combined and applied.
Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
Further, a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like.
Further, a pre-wetting step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
本発明の製造方法は、膜形成工程(層形成工程)の後に、溶剤を除去するために乾燥する工程を含んでいてもよい。好ましい乾燥温度は50~150℃で、70℃~130℃がより好ましく、90℃~110℃が更に好ましい。乾燥時間としては、30秒~20分が例示され、1分~10分が好ましく、3分~7分がより好ましい。 <Drying process>
The production method of the present invention may include a step of drying to remove the solvent after the film forming step (layer forming step). The preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
本発明の製造方法は、上記膜(樹脂組成物層)を露光する露光工程を含んでもよい。露光量は、樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長365nmでの露光エネルギー換算で100~10,000mJ/cm2照射することが好ましく、200~8,000mJ/cm2照射することがより好ましい。 <Exposure process>
The production method of the present invention may include an exposure step of exposing the film (resin composition layer). The exposure amount is not particularly specified as long as the resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 It is more preferable to irradiate.
また、露光光が波長365nm又は波長405nmの光を含むことが好ましく、波長405nmの光を含むことがより好ましい。 The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
Further, the exposure light preferably contains light having a wavelength of 365 nm or 405 nm, and more preferably contains light having a wavelength of 405 nm.
また取り扱いと生産性の観点では、高圧水銀灯のブロード(g,h,i線の3波長)光源や半導体レーザー405nmも好適である。 In relation to the light source, the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. The resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
本発明において、露光工程における露光がレーザーダイレクトイメージング法による露光である態様も、好ましい態様の1つである。 The exposure method is not particularly limited as long as it exposes at least a part of the film (photosensitive film) made of the curable resin composition, but an exposure using a photomask or a laser direct imaging method is used. Exposure and the like can be mentioned.
In the present invention, an embodiment in which the exposure in the exposure step is an exposure by a laser direct imaging method is also one of the preferred embodiments.
本発明の製造方法は、露光された膜(樹脂組成物層)に対して、現像を行う(上記膜を現像する)現像工程を含んでもよい。現像を行うことにより、露光されていない部分(非露光部)が除去される。現像方法は、所望のパターンを形成できれば特に制限は無く、例えばノズルからの現像液の吐出、スプレー噴霧、基材の現像液浸漬などが挙げられ、ノズルからの吐出が好ましく利用される。現像工程には、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、現像液を超音波等で振動させる工程およびそれらを組み合わせた工程などが採用可能である。 <Development process>
The production method of the present invention may include a developing step of developing (developing the above-mentioned film) the exposed film (resin composition layer). By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used. The developing steps include a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, a step in which the developer is vibrated by ultrasonic waves or the like, and a combination thereof. Processes can be adopted.
現像液としては、有機溶剤を含む現像液、又は、アルカリ水溶液を用いることができる。 Development is performed using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
As the developing solution, a developing solution containing an organic solvent or an alkaline aqueous solution can be used.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The developer may further contain other components.
Examples of other components include known surfactants and known defoamers.
現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材を現像液に浸漬する方法、基材上にノズルを用いて現像液を供給しパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [How to supply developer]
The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the developer, the method of supplying the developer on the base material using a nozzle, paddle development, or continuous development. There is a way to supply. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable, and the developing solution to the image area is supplied. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
Further, after the developing solution is continuously supplied by the straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, the developing solution is continuously supplied by the straight nozzle again, and then the base material is spun to use the developing solution as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times.
Further, as a method of supplying the developer in the developing process, a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, and a step in which the developer is superposed on the base material. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
現像液が有機溶剤を含む現像液である場合、リンス液としては、PGMEA(プロピレングリコールモノエチルエーテルアセテート)、IPA(イソプロパノール)などが挙げられ、好ましくはPGMEAである。また、アルカリ水溶液を含む現像液による現像に対するリンス液としては、水が好ましい。
リンス時間は、10秒~10分間が好ましく、20秒~5分間がより好ましく、5秒~1分が更に好ましい。
リンス時のリンス液の温度は、特に定めるものではないが、好ましくは、10~45℃、より好ましくは、18℃~30℃で行うことができる。 After the treatment with the developing solution, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with the solvent contained in the resin composition.
When the developer is a developer containing an organic solvent, examples of the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA. Further, water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, still more preferably 5 seconds to 1 minute.
The temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The rinse solution may further contain other components.
Examples of other components include known surfactants and known defoamers.
リンス液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材をリンス液に浸漬する方法、基材上でのパドルによるリンス液の供給、基材にリンス液をシャワーで供給する方法、基材上にストレートノズル等の手段によりリンス液を連続供給する方法がある。
リンス液の浸透性、非画像部の除去性、製造上の効率の観点から、リンス液をシャワーノズル、ストレートノズル、スプレーノズルなどで供給する方法があり、スプレーノズルにて連続供給する方法が好ましく、画像部へのリンス液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
すなわち、リンス工程は、リンス液を上記露光後の膜に対してストレートノズルにより供給、又は、連続供給する工程であることが好ましく、リンス液をスプレーノズルにより供給する工程であることがより好ましい。
またリンス工程におけるリンス液の供給方法としては、リンス液が連続的に基材に供給され続ける工程、基材上でリンス液が略静止状態で保たれる工程、基材上でリンス液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Supplying method of rinse liquid]
The method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinse liquid, the supply of the rinse liquid with a paddle on the base material, and the supply of the rinse liquid to the base material by a shower. There is a method, a method of continuously supplying a rinse liquid onto a base material by means such as a straight nozzle.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
That is, the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
Further, as a method of supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material. A process of vibrating with a sound conditioner or the like and a process of combining them can be adopted.
本発明の製造方法は、現像された上記膜を50~450℃で加熱する工程(加熱工程)を含むことが好ましい。
加熱工程は、膜形成工程(層形成工程)、乾燥工程、及び現像工程の後に含まれることが好ましい。加熱工程では、例えば上述の熱塩基発生剤が分解することにより塩基が発生し、特定樹脂である前駆体の環化反応が進行する。また、本発明の樹脂組成物は特定樹脂である前駆体以外のラジカル重合性化合物を含んでいてもよいが、未反応の特定樹脂である前駆体以外のラジカル重合性化合物の硬化などもこの工程で進行させることができる。加熱工程における層の加熱温度(最高加熱温度)としては、50℃以上であることが好ましく、80℃以上であることがより好ましく、140℃以上であることが更に好ましく、150℃以上であることが一層好ましく、160℃以上であることがより一層好ましく、170℃以上であることが更に一層好ましい。上限としては、500℃以下であることが好ましく、450℃以下であることがより好ましく、350℃以下であることが更に好ましく、250℃以下であることが一層好ましく、220℃以下であることがより一層好ましい。 <Heating process>
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds. Further, the resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but curing of a radically polymerizable compound other than the precursor which is an unreacted specific resin is also in this step. Can be advanced with. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブンなどが挙げられる。 The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.
本発明の製造方法は、現像後の膜(樹脂組成物層)の表面に金属層を形成する金属層形成工程を含むことが好ましい。 <Metal layer forming process>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (resin composition layer).
本発明の製造方法は、更に、積層工程を含むことが好ましい。 <Laminating process>
The production method of the present invention preferably further includes a laminating step.
また、積層工程における各層は、組成、形状、膜厚等が同一の層であってもよいし、異なる層であってもよい。 The laminating step is preferably performed 2 to 20 times, preferably 2 to 5 times, and more preferably 3 to 5 times.
Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.
本発明の積層体の製造方法は、上記金属層および感光性樹脂組成物層の少なくとも一部を表面活性化処理する、表面活性化処理工程を含んでもよい。
表面活性化処理工程は、通常、金属層形成工程の後に行うが、上記露光現像工程の後、感光性樹脂組成物層に表面活性化処理工程を行ってから、金属層形成工程を行ってもよい。
表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、露光後の感光性樹脂組成物層の少なくとも一部のみに行ってもよいし、金属層および露光後の感光性樹脂組成物層の両方について、それぞれ、少なくとも一部に行ってもよい。表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、表面に感光性樹脂組成物層を形成する領域の一部または全部に表面活性化処理を行うことが好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる樹脂層との密着性を向上させることができる。
また、表面活性化処理は、露光後の感光性樹脂組成物層(樹脂層)の一部または全部についても行うことが好ましい。このように、感光性樹脂組成物層の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や樹脂層との密着性を向上させることができる。
表面活性化処理としては、具体的には、各種原料ガス(酸素、水素、アルゴン、窒素、窒素/水素混合ガス、アルゴン/酸素混合ガスなど)のプラズマ処理、コロナ放電処理、CF4/O2、NF3/O2、SF6、NF3、NF3/O2によるエッチング処理、紫外線(UV)オゾン法による表面処理、塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種有する化合物を含む有機表面処理剤への浸漬処理、ブラシを用いた機械的な粗面化処理から選択され、プラズマ処理が好ましく、特に原料ガスに酸素を用いた酸素プラズマ処理が好ましい。コロナ放電処理の場合、エネルギーは、500~200,000J/m2が好ましく、1000~100,000J/m2がより好ましく、10,000~50,000J/m2が最も好ましい。 (Surface activation treatment process)
The method for producing a laminate of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
The surface activating treatment step is usually performed after the metal layer forming step, but it is also possible to perform the surface activating treatment step on the photosensitive resin composition layer after the exposure development step and then perform the metal layer forming step. good.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer in which the photosensitive resin composition layer is formed on the surface. .. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin layer provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure. By performing the surface activation treatment on the surface of the photosensitive resin composition layer in this way, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment.
Specifically, the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF 4 / O 2 , NF 3 / O 2 , SF 6 , NF 3 , NF 3 / O 2 , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500 ~ 200,000J / m 2, more preferably 1000 ~ 100,000J / m 2, and most preferably 10,000 ~ 50,000J / m 2.
4,4’-オキシジフタル酸二無水物(ODPA) 23.48gと4,4’-ビフタル酸二無水物(BPDA) 22.27gをセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA) 39.69gとγ-ブチロラクトン136.83gを入れて室温下で撹拌し、撹拌しながらピリジン 24.66gを加えて反応混合物を得た。反応による発熱の終了後に室温まで放冷し、16時間室温で放置した。
次に、氷冷下において、ジシクロヘキシルカルボジイミド(DCC) 62.46gをγ-ブチロラクトン61.57gに溶解した溶液を撹拌しながら40分かけて反応混合物に加え、続いて4,4’-ジアミノジフェニルエーテル(DADPE)27.42gをγ-ブチロラクトン119.73gに懸濁したものを撹拌しながら60分かけて加えた。更に室温で一定の時間において撹拌した後、エチルアルコール7.17gを加えて1時間撹拌し、次に、γ-ブチロラクトン136.83gを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。
上記一定の時間を長くすることで、ポリイミド前駆体中の環状イミド構造及び環状イソイミド構造の合計含有モル量を多くすることができ、短くすることで、上記合計含有モル量を少なくすることができる。例えば、上記時間を30分間とすることにより、1gの上記ポリイミド前駆体に含まれる上記環状イミド構造及び上記環状イソイミド構造の合計含有モル量が、0.083mmol/gである樹脂が得られた。
本実施例及び比較例においては、上記一定の時間を適宜調整することにより、ポリイミド前駆体中の環状イミド構造及び環状イソイミド構造の合計含有モル量を変化させた複数のポリイミド前駆体を用いて実験を行った。各実施例及び比較例において、環状イミド構造及び環状イソイミド構造の合計含有モル量がどの程度であるかは、表中の「特定構造 mmol/g」の欄に記載した。
得られた反応液を716.21gのエチルアルコールに加えて粗ポリマーから成る沈殿物を生成した。生成した粗ポリマーを濾別し、テトラヒドロフラン403.49gに溶解して粗ポリマー溶液を得た。得られた粗ポリマー溶液を8470.26gの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾別した後、真空乾燥して粉末状のポリマー(ポリイミド前駆体)A-1を得た。ポリマーA-1の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は20,000であった。 <Synthesis Example 1: Synthesis of Polymer A-1>
23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of 4,4'-biphthalic dianhydride (BPDA) were placed in a separable flask and 2-hydroxyethyl methacrylate (HEMA) 39. 69 g and 136.83 g of γ-butyrolactone were added and stirred at room temperature, and 24.66 g of pyridine was added with stirring to obtain a reaction mixture. After the exothermic reaction was completed, the mixture was allowed to cool to room temperature and left at room temperature for 16 hours.
Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether ( 27.42 g of DADPE) suspended in 119.73 g of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for a certain period of time, 7.17 g of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
By lengthening the fixed time, the total molar content of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor can be increased, and by shortening the total molar content, the total molar content can be reduced. .. For example, by setting the time to 30 minutes, a resin having a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor of 0.083 mmol / g was obtained.
In this example and the comparative example, experiments were carried out using a plurality of polyimide precursors in which the total molar amount of the cyclic imide structure and the cyclic isoimide structure in the polyimide precursor was changed by appropriately adjusting the above-mentioned fixed time. Was done. In each Example and Comparative Example, the total molar content of the cyclic imide structure and the cyclic isoimide structure is described in the column of "Specific structure mmol / g" in the table.
The obtained reaction solution was added to 716.21 g of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in tetrahydrofuran 403.49 g to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polyimide precursor) A-1. rice field. When the molecular weight of the polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.
ODPA 23.48gとBPDA 22.27gを、ODPA 46.96gに変更した以外は、合成例1と同様の方法により、ポリマーA-2を合成した。実施例において、環状イミド構造及び環状イソイミド構造の合計含有モル量がどの程度であるかは、表中の「特定構造 mmol/g」の欄に記載した。 <Synthesis Example 2: Synthesis of Polymer A-2>
Polymer A-2 was synthesized by the same method as in Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA. In the examples, the total molar content of the cyclic imide structure and the cyclic isoimide structure is described in the column of “specific structure mmol / g” in the table.
ODPA 23.48gとBPDA 22.27gを、ODPA 46.96gに変更し、HEMA 39.69gを、HEMA 19.85g及びジエチレングリコールモノメチルエーテル 18.32gに変更した以外は、合成例1と同様の方法により、ポリマーA-3を合成した。実施例において、環状イミド構造及び環状イソイミド構造の合計含有モル量がどの程度であるかは、表中の「特定構造 mmol/g」の欄に記載した。 <Synthesis Example 3: Synthesis of Polymer A-3>
By the same method as in Synthesis Example 1, except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA and 39.69 g of HEMA was changed to 19.85 g of HEMA and 18.32 g of diethylene glycol monomethyl ether. , Polymer A-3 was synthesized. In the examples, the total molar content of the cyclic imide structure and the cyclic isoimide structure is described in the column of “specific structure mmol / g” in the table.
撹拌機、コンデンサー及び内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、4,6-ジヒドロキシ-1,3-フェニレンジアミン二塩酸塩 10.65g(50ミリモル)をN-メチルピロリドン(NMP) 85.8g中に溶解させた。次に、テレフタル酸クロリド 9.74g(48ミリモル)をNMP 55.0gに溶解したものを、1時間かけて滴下し、25℃で一定の時間撹拌した。
上記一定の時間を長くすることで、ポリベンゾオキサゾール前駆体中のベンゾオキサゾール構造の含有モル量を多くすることができ、短くすることで、ポリベンゾオキサゾール前駆体中のベンゾオキサゾール構造の含有モル量を少なくすることができる。例えば、15分間とすることで、ベンゾオキサゾール構造の含有モル量を0.373mmol/gとすることができる。
撹拌後、2リットルの水/メタノール=75/25(体積比)中で沈殿させ、2,000rpmの速度で30分間撹拌した。析出したポリベンゾオキサゾール前駆体樹脂を濾過して除き、1.5リットルの水でかけ洗いした。得られた樹脂を減圧下で、40℃で1日間乾燥し、A-4を得た。 <Synthesis Example 4: Synthesis of Polymer A-4>
10.65 g (50 mmol) of 4,6-dihydroxy-1,3-phenylenediamine dihydrochloride while removing water in a drying reactor with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. It was dissolved in 85.8 g of N-methylpyrrolidone (NMP). Next, 9.74 g (48 mmol) of terephthalic acid chloride dissolved in 55.0 g of NMP was added dropwise over 1 hour, and the mixture was stirred at 25 ° C. for a certain period of time.
By lengthening the above fixed time, the molar content of the benzoxazole structure in the polybenzoxazole precursor can be increased, and by shortening it, the molar content of the benzoxazole structure in the polybenzoxazole precursor can be increased. Can be reduced. For example, the molar content of the benzoxazole structure can be set to 0.373 mmol / g for 15 minutes.
After stirring, the mixture was precipitated in 2 liters of water / methanol = 75/25 (volume ratio) and stirred at a rate of 2,000 rpm for 30 minutes. The precipitated polybenzoxazole precursor resin was filtered off and washed with 1.5 liters of water. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain A-4.
トリメリット酸無水物 29.08gをセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA) 19.85gとγ-ブチロラクトン136.83gを入れて室温下で撹拌し、撹拌しながらピリジン 24.66gを加えて反応混合物を得た。反応による発熱の終了後に室温まで放冷し、16時間室温で放置した。
次に、氷冷下において、ジシクロヘキシルカルボジイミド(DCC) 62.46gをγ-ブチロラクトン61.57gに溶解した溶液を撹拌しながら40分かけて反応混合物に加え、続いて4,4’-ジアミノジフェニルエーテル(DADPE)27.42gをγ-ブチロラクトン119.73gに懸濁したものを撹拌しながら60分かけて加えた。更に室温で一定の時間において撹拌した後、エチルアルコール7.17gを加えて1時間撹拌し、次に、γ-ブチロラクトン136.83gを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。
上記一定の時間を長くすることで、ポリアミドイミド前駆体中の環状イミド構造及び環状イソイミド構造の合計含有モル量を多くすることができ、短くすることで、上記合計含有モル量を少なくすることができる。例えば、15分間とすることで、ベンゾオキサゾール構造の含有モル量を0.104mmol/gとすることができる。
得られた反応液を716.21gのエチルアルコールに加えて粗ポリマーから成る沈殿物を生成した。生成した粗ポリマーを濾別し、テトラヒドロフラン403.49gに溶解して粗ポリマー溶液を得た。得られた粗ポリマー溶液を8470.26gの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾別した後、真空乾燥して粉末状のポリマー(ポリアミドイミド前駆体)A-5を得た。 <Synthesis Example 5: Synthesis of Polymer A-5>
Put 29.08 g of trimellitic acid anhydride in a separable flask, add 19.85 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone, and stir at room temperature to add 24.66 g of pyridine while stirring. In addition, a reaction mixture was obtained. After the exothermic reaction was completed, the mixture was allowed to cool to room temperature and left at room temperature for 16 hours.
Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether ( 27.42 g of DADPE) suspended in 119.73 g of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for a certain period of time, 7.17 g of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
By lengthening the fixed time, the total molar content of the cyclic imide structure and the cyclic isoimide structure in the polyamide-imide precursor can be increased, and by shortening the total molar content, the total molar content can be reduced. can. For example, the molar content of the benzoxazole structure can be 0.104 mmol / g for 15 minutes.
The obtained reaction solution was added to 716.21 g of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in tetrahydrofuran 403.49 g to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, the obtained precipitate was filtered off, and then vacuum dried to obtain a powdered polymer (polyamideimide precursor) A-5. Obtained.
ODPA 23.48gとBPDA 22.27gを、BPDA 44.54gに変更した以外は、合成例1と同様の方法により、ポリマーA-6を合成した。実施例において、環状イミド構造及び環状イソイミド構造の合計の含有モル量がどの程度であるかは、表中の「特定構造 mmol/g」の欄に記載した。 <Synthesis Example 6: Synthesis of Polymer A-6>
Polymer A-6 was synthesized by the same method as in Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 44.54 g of BPDA. In the examples, the total molar content of the cyclic imide structure and the cyclic isoimide structure is described in the column of “specific structure mmol / g” in the table.
ODPA 23.48gとBPDA 22.27gを、ODPA 46.96gに変更し、HEMA 39.69gを、下記式(7-1)で表される化合物 52.52gに変更した以外は、合成例1と同様の方法により、ポリマーA-7を合成した。実施例において、環状イミド構造及び記環状イソイミド構造の合計含有モル量がどの程度であるかは、表中の「特定構造 mmol/g」の欄に記載した。
Synthetic Example 1 and Synthetic Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA and 39.69 g of HEMA was changed to 52.52 g of the compound represented by the following formula (7-1). Polymer A-7 was synthesized by the same method. In the examples, the total molar content of the cyclic imide structure and the cyclic isoimide structure is described in the column of “specific structure mmol / g” in the table.
各実施例において、それぞれ、下記表に記載の成分を混合し、各硬化性樹脂組成物を得た。また、各比較例において、それぞれ、下記表に記載の成分を混合し、各比較用組成物を得た。
具体的には、表1~表5に記載の各成分の含有量は、表1~表5の各欄の括弧内に記載の量(質量部)とした。
得られた硬化性樹脂組成物及び比較用組成物を、細孔の幅が0.8μmのポリテトラフルオロエチレン製フィルターを用いて加圧ろ過した。
また、表1~表5中、「-」の記載は該当する成分を組成物が含有していないことを示している。 <Examples and Comparative Examples>
In each example, the components listed in the table below were mixed to obtain each curable resin composition. Further, in each comparative example, the components listed in the following table were mixed to obtain each comparative composition.
Specifically, the content of each component shown in Tables 1 to 5 is the amount (parts by mass) shown in parentheses in each column of Tables 1 to 5.
The obtained curable resin composition and comparative composition were pressure-filtered using a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in Tables 1 to 5, the description of "-" indicates that the composition does not contain the corresponding component.
・A-1~A-7:上記合成例により得られたポリマーA-1~A-7 〔resin〕
-A-1 to A-7: Polymers A-1 to A-7 obtained by the above synthetic example.
・B-1~B-3:下記構造の化合物
-B-1 to B-3: Compounds having the following structure
・X-1:ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム
・X-2:ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド
・X-3:ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロフェニル)チタニウム
・X-4:テトライソプロポキシチタン(マツモトファインケミカル社製)
・X-5:ジイソプロポキシビス(アセチルアセトナト)チタン(マツモトファインケミカル社製)
・X-6~X-8:下記構造の化合物。
上記X-1及びX-3は光ラジカル重合開始能を有する化合物である。 [Organometallic complex]
-X-1: Bis (η5-2,4-cyclopentadiene-1-yl) Bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) Titanium-X-2: Pentamethylcyclo Pentazienyl Titanium Trimethoxide ・ X-3: Bis (η5-2,4-Cyclopentadiene-1-yl) Bis (2,6-difluorophenyl) Titanium ・ X-4: Tetraisopropoxytitanium (Matsumoto Fine Chemicals) Made)
・ X-5: Diisopropoxybis (acetylacetonato) titanium (manufactured by Matsumoto Fine Chemical Co., Ltd.)
-X-6 to X-8: Compounds having the following structures.
The above X-1 and X-3 are compounds having an ability to initiate photoradical polymerization.
・C-1~C-2:下記構造の化合物
-C-1 to C-2: Compounds with the following structure
・D-1~D-7:下記構造の化合物
-D-1 to D-7: Compounds having the following structure
・F-1~F-6:下記構造の化合物
上記構造式中、Meはメチル基を、Etはエチル基をそれぞれ表す。 [Metal adhesion improver]
-F-1 to F-6: Compounds with the following structure
In the above structural formula, Me represents a methyl group and Et represents an ethyl group.
・NMP:N-メチル-2-ピロリドン
・EL:乳酸エチル
・DMSO:ジメチルスルホキシド [Solvent (solvent)]
-NMP: N-methyl-2-pyrrolidone-EL: Ethyl lactate-DMSO: Dimethyl sulfoxide
〔環状構造の含有モル量の測定〕
各実施例で使用した樹脂について、1gのポリイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量、1gのポリベンゾオキサゾール前駆体に含まれるベンゾオキサゾール構造の含有モル量、1gのポリアミドイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量をそれぞれ測定した。測定結果は、表中の「特定構造 mmol/g」の欄に記載した。
具体的には、NMRを用い,ポリマー0.1gを重DMSO 0.9gに溶解して測定した。ポリイミド前駆体又はポリアミドイミド前駆体に関しては,7.15ppm付近のピーク面積と芳香環のピーク面積の比率から環状イミド構造量を特定した
同様に、ポリイミド前駆体又はポリアミドイミド前駆体における環状イソイミド構造、ポリベンゾオキサゾール前駆体におけるベンゾオキサゾール構造の量を特定した。 <Evaluation>
[Measurement of molar content of cyclic structure]
For the resin used in each example, the total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor, and the molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor, 1 g. The total molar content of the cyclic imide structure and the cyclic isoimide structure contained in the polyamide-imide precursor was measured. The measurement results are described in the column of "Specific structure mmol / g" in the table.
Specifically, using NMR, 0.1 g of the polymer was dissolved in 0.9 g of heavy DMSO for measurement. Regarding the polyimide precursor or the polyamide-imide precursor, the cyclic imide structure amount was specified from the ratio of the peak area around 7.15 ppm to the peak area of the aromatic ring. Similarly, the cyclic isoimide structure in the polyimide precursor or the polyamide-imide precursor, The amount of benzoxazole structure in the polybenzoxazole precursor was identified.
各実施例又は比較例において、調製した硬化性樹脂組成物又は比較用組成物を、シリコンウエハ上にスピンコート法により塗布した。上記シリコンウエハをホットプレート上で、100℃で5分間乾燥し、シリコンウエハ上に20μmの均一な厚さの硬化性樹脂組成物層を形成した。
露光条件に「M」と記載した例においては、シリコンウエハ上の硬化性樹脂組成物層を、ステッパーを用いて露光した。露光は表中の「露光波長 nm」に記載した波長の光を用い、5μm~25μmまで1μm刻みのヒューズボックスのフォトマスクを使用して、露光を行った。露光量は後述の最小線幅を最小とする露光量とした。
露光条件に「D」と記載した例においては、ダイレクト露光装置(アドテック DE-6UH III)を用いて露光した。露光は波長405nmにおいて、露光部が5μmから25μmまで1μm刻みのラインアンドスペースパターンにおけるライン部となるようなレーザーダイレクトイメージング露光を行った。露光量は後述の最小線幅を最小とする露光量とした。
露光した硬化性樹脂組成物層を、シクロペンタノンで60秒間現像した後に、PGMEA(プロピレングリコールモノメチルエーテルアセテート)でリンスした。
現像後に得られたパターンにおいて、ラインパターンの間にシリコンウエハが露出しているラインパターンのうち線幅が最小であるものの線幅を「最小線幅」として、下記評価基準に従って評価した。線幅が小さければ小さいほど解像性に優れるといえ、例えば、その後のめっき工程で形成される金属配線幅を微細化できることを表すため、好ましい結果となる。測定限界は5μmである。評価結果は、表中の「解像性」の欄に記載した。
-評価基準-
A:最小線幅が5μm以上8μm未満であった。
B:最小線幅が8μm以上10μm未満であった。
C:最小線幅が10μm以上12μm未満であった。
D:最小線幅が12μm以上であった。 [Resolution evaluation]
In each Example or Comparative Example, the prepared curable resin composition or comparative composition was applied onto a silicon wafer by a spin coating method. The silicon wafer was dried on a hot plate at 100 ° C. for 5 minutes to form a curable resin composition layer having a uniform thickness of 20 μm on the silicon wafer.
In the example described as "M" in the exposure conditions, the curable resin composition layer on the silicon wafer was exposed using a stepper. The exposure was performed using light having the wavelength described in "Exposure wavelength nm" in the table, and using a photomask of a fuse box from 5 μm to 25 μm in 1 μm increments. The exposure amount was the exposure amount that minimizes the minimum line width described later.
In the example described as "D" in the exposure condition, the exposure was performed using a direct exposure apparatus (Adtech DE-6UH III). The exposure was performed by laser direct imaging exposure at a wavelength of 405 nm so that the exposed portion became a line portion in a line and space pattern in 1 μm increments from 5 μm to 25 μm. The exposure amount was the exposure amount that minimizes the minimum line width described later.
The exposed curable resin composition layer was developed with cyclopentanone for 60 seconds and then rinsed with PGMEA (propylene glycol monomethyl ether acetate).
In the pattern obtained after development, among the line patterns in which the silicon wafer was exposed between the line patterns, the line width of the line pattern having the smallest line width was defined as the "minimum line width" and evaluated according to the following evaluation criteria. It can be said that the smaller the line width is, the better the resolution is. For example, it means that the metal wiring width formed in the subsequent plating step can be miniaturized, which is a preferable result. The measurement limit is 5 μm. The evaluation results are described in the "Resolution" column in the table.
-Evaluation criteria-
A: The minimum line width was 5 μm or more and less than 8 μm.
B: The minimum line width was 8 μm or more and less than 10 μm.
C: The minimum line width was 10 μm or more and less than 12 μm.
D: The minimum line width was 12 μm or more.
上記解像性評価と同様の方法によりシリコンウエハ上に20μmの均一な厚さの硬化性樹脂組成物層を形成した。
露光条件に「M」と記載した例においては、シリコンウエハ上の硬化性樹脂組成物層を、ステッパーにより、直径15.0μmのマスク部(表中の現像条件の欄に「ネガ」と記載されている例)又は非マスク部(表中の現状条件の欄に「ポジ」と記載されている例)を有するフォトマスクを用いて露光した。露光波長は表中の「露光波長 nm」に記載した。露光量は50~500mJ/cm2の範囲で50mJ/cm2刻みで変化させた。
露光条件に「D」と記載した例においては、ダイレクト露光装置(アドテック DE-6UH III)を用いてレーザーダイレクトイメージング露光を行った。露光波長は405nmとし、直径15.0μmの非露光部が形成されるよう露光した。露光量は50~500mJ/cm2の範囲で50mJ/cm2刻みで変化させた。
下底の径が15.0μmのホールパターンが形成される最小の露光量をから、下記評価基準に従い、感度を評価した。上記最小の露光量が小さいほど(高感度であるほど)好ましく、露光感度に優れるといえる。評価結果は、表中の「感度」の欄に記載した。
-評価基準-
A:上記最小の露光量が100mJ/cm2未満であった。
B:上記最小の露光量が100mJ/cm2以上150mJ/cm2未満であった。
C:上記最小の露光量が150mJ/cm2以上であった。 [Exposure sensitivity evaluation]
A curable resin composition layer having a uniform thickness of 20 μm was formed on the silicon wafer by the same method as in the above resolution evaluation.
In the example in which "M" is described in the exposure condition, the curable resin composition layer on the silicon wafer is described as "negative" in the mask portion having a diameter of 15.0 μm by a stepper (in the column of development conditions in the table). (Example) or a photomask having a non-masked portion (an example in which "Positive" is described in the column of current conditions in the table) was used for exposure. The exposure wavelength is described in "Exposure wavelength nm" in the table. The exposure amount was varied in 50 mJ / cm 2 increments in the range of 50 ~ 500mJ / cm 2.
In the example described as "D" in the exposure condition, laser direct imaging exposure was performed using a direct exposure apparatus (Adtech DE-6UH III). The exposure wavelength was 405 nm, and exposure was performed so that an unexposed portion having a diameter of 15.0 μm was formed. The exposure amount was varied in 50 mJ / cm 2 increments in the range of 50 ~ 500mJ / cm 2.
The sensitivity was evaluated according to the following evaluation criteria from the minimum exposure amount at which a hole pattern having a bottom diameter of 15.0 μm was formed. It can be said that the smaller the minimum exposure amount (the higher the sensitivity), the more preferable, and the better the exposure sensitivity. The evaluation results are described in the "Sensitivity" column in the table.
-Evaluation criteria-
A: The minimum exposure amount was less than 100 mJ / cm 2.
B: the minimum exposure amount is less than 100 mJ / cm 2 or more 150 mJ / cm 2.
C: The minimum exposure amount was 150 mJ / cm 2 or more.
比較例1~4に係る比較用組成物に含まれるポリイミド前駆体は、1gのポリイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量が0.08mmol/g未満である。
比較例5に係る比較用組成物に含まれるポリイミド前駆体は、1gのポリイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量が1.68mmol/gを超える。
比較例6に係る比較用組成物に含まれるポリベンゾオキサゾール前駆体は、1gのポリベンゾオキサゾール前駆体に含まれる上記ベンゾオキサゾール構造の含有モル量が0.22mmol/g未満である。
比較例7に係る比較用組成物に含まれるポリベンゾオキサゾール前駆体は、1gのポリベンゾオキサゾール前駆体に含まれる上記ベンゾオキサゾール構造の含有モル量が3.97mmol/gを超える。
比較例8に係る比較用組成物に含まれるポリアミドイミド前駆体は、1gのポリイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量が1.186mmol/gを超える。
比較例9に係る比較用組成物に含まれるポリアミドイミド前駆体は、1gのポリアミドイミド前駆体に含まれる環状イミド構造及び環状イソイミド構造の合計含有モル量が0.062mmol/g未満である。
これらの比較用組成物を用いた場合、解像性に劣ることがわかる。 From the above results, it can be seen that the curable resin composition of the present invention is excellent in resolution.
The polyimide precursor contained in the comparative compositions according to Comparative Examples 1 to 4 has a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor of less than 0.08 mmol / g.
The polyimide precursor contained in the comparative composition according to Comparative Example 5 has a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor exceeding 1.68 mmol / g.
The polybenzoxazole precursor contained in the comparative composition according to Comparative Example 6 has a molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor of less than 0.22 mmol / g.
The polybenzoxazole precursor contained in the comparative composition according to Comparative Example 7 has a molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor exceeding 3.97 mmol / g.
The polyamide-imide precursor contained in the comparative composition according to Comparative Example 8 has a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor exceeding 1.186 mmol / g.
The polyamide-imide precursor contained in the comparative composition according to Comparative Example 9 has a total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamide-imide precursor of less than 0.062 mmol / g.
It can be seen that when these comparative compositions are used, the resolution is inferior.
実施例1において使用した硬化性樹脂組成物を、表面に銅薄層が形成された樹脂基材の銅薄層の表面にスピンコート法により層状に適用して、100℃で4分間乾燥し、膜厚20μmの感光膜を形成した後、ステッパー((株)ニコン製、NSR1505 i6)を用いて露光した。露光はマスク(パターンが1:1ラインアンドスペースであり、線幅が10μmであるバイナリマスク)を介して、波長365nmで行った。露光後、100℃で4分間加熱した。上記加熱後、シクロヘキサノンで2分間現像し、PGMEAで30秒間リンスし、層のパターンを得た。
次いで、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、230℃で120分間維持して、再配線層用層間絶縁膜を形成した。この再配線層用層間絶縁膜は、絶縁性に優れていた。
また、これらの再配線層用層間絶縁膜を使用して半導体デバイスを製造したところ、問題なく動作することを確認した。 <Example 101>
The curable resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 4 minutes. After forming a photosensitive film having a film thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed through a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes. After the above heating, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 120 minutes to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating properties.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.
Claims (17)
- 環状イミド構造及び環状イソイミド構造の少なくとも一方を含むポリイミド前駆体、ベンゾオキサゾール構造を含むポリベンゾオキサゾール前駆体、及び、環状イミド構造及び環状イソイミド構造の少なくとも一方を含むポリアミドイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂、並びに、
有機金属錯体を含み、
1gの前記ポリイミド前駆体に含まれる前記環状イミド構造及び前記環状イソイミド構造の合計含有モル量が、0.08~1.68mmol/gであり、
1gの前記ポリベンゾオキサゾール前駆体に含まれる前記ベンゾオキサゾール構造の含有モル量が、0.22~3.97mmol/gであり、
1gの前記ポリアミドイミド前駆体に含まれる前記環状イミド構造及び前記環状イソイミド構造の合計含有モル量が、0.062~1.186mmol/gである、
硬化性樹脂組成物。 Selected from the group consisting of a polyimide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure, a polybenzoxazole precursor containing a benzoxazole structure, and a polyamide-imide precursor containing at least one of a cyclic imide structure and a cyclic isoimide structure. At least one resin, as well as
Contains organometallic complexes
The total molar amount of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyimide precursor is 0.08 to 1.68 mmol / g.
The molar content of the benzoxazole structure contained in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol / g.
The total molar content of the cyclic imide structure and the cyclic isoimide structure contained in 1 g of the polyamide-imide precursor is 0.062 to 1.186 mmol / g.
Curable resin composition. - 光重合開始剤を更に含む、請求項1に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, further comprising a photopolymerization initiator.
- 前記光重合開始剤がオキシム化合物である、請求項1又は2に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1 or 2, wherein the photopolymerization initiator is an oxime compound.
- 架橋剤を更に含む、請求項1~3のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 3, further comprising a cross-linking agent.
- 前記有機金属錯体が、メタロセン化合物である、請求項1~4のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 4, wherein the organometallic complex is a metallocene compound.
- 前記有機金属錯体に含まれる金属が、チタン、ジルコニウム及びハフニウムよりなる群から選ばれた少なくとも1種の金属である、請求項1~5のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 5, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium and hafnium.
- 前記有機金属錯体が、光ラジカル重合開始能を有する、請求項1~6のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 6, wherein the organometallic complex has an ability to initiate photoradical polymerization.
- ネガ型現像に供される感光膜の形成に用いられる、請求項1~7のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 7, which is used for forming a photosensitive film to be used for negative development.
- 再配線層用層間絶縁膜の形成に用いられる、請求項1~8のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 8, which is used for forming an interlayer insulating film for a rewiring layer.
- 請求項1~9のいずれか1項に記載の硬化性樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the curable resin composition according to any one of claims 1 to 9.
- 請求項10に記載の硬化膜を2層以上含み、前記硬化膜同士のいずれかの間に金属層を含む積層体。 A laminate containing two or more layers of the cured film according to claim 10 and containing a metal layer between any of the cured films.
- 請求項1~9のいずれか1項に記載の硬化性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。 A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of claims 1 to 9 to a substrate to form a film.
- 前記膜を露光する露光工程及び前記膜を現像する現像工程を含む、請求項12に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 12, further comprising an exposure step of exposing the film and a developing step of developing the film.
- 前記露光に用いられる露光光が波長405nmの光を含む、請求項13に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 13, wherein the exposure light used for the exposure includes light having a wavelength of 405 nm.
- 前記露光がレーザーダイレクトイメージング法による露光である、請求項13又は14に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 13 or 14, wherein the exposure is an exposure by a laser direct imaging method.
- 前記膜を50~450℃で加熱する加熱工程を含む、請求項12~15のいずれか1項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 12 to 15, which comprises a heating step of heating the film at 50 to 450 ° C.
- 請求項10に記載の硬化膜又は請求項11に記載の積層体を含む、半導体デバイス。 A semiconductor device including the cured film according to claim 10 or the laminate according to claim 11.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202180016937.6A CN115190891B (en) | 2020-02-28 | 2021-02-25 | Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device |
JP2022503684A JPWO2021172420A1 (en) | 2020-02-28 | 2021-02-25 | |
KR1020227029396A KR20220134583A (en) | 2020-02-28 | 2021-02-25 | A curable resin composition, a cured film, a laminated body, the manufacturing method of a cured film, and a semiconductor device |
JP2024038234A JP2024083351A (en) | 2020-02-28 | 2024-03-12 | Curable resin composition, cured film, laminate, method for producing cured film and semiconductor device |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-033667 | 2020-02-28 | ||
JP2020033667 | 2020-02-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021172420A1 true WO2021172420A1 (en) | 2021-09-02 |
Family
ID=77491521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/007075 WO2021172420A1 (en) | 2020-02-28 | 2021-02-25 | Curable resin composition, cured film, laminate, cured film production method and semiconductor device |
Country Status (5)
Country | Link |
---|---|
JP (2) | JPWO2021172420A1 (en) |
KR (1) | KR20220134583A (en) |
CN (1) | CN115190891B (en) |
TW (1) | TW202200671A (en) |
WO (1) | WO2021172420A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2022044998A1 (en) * | 2020-08-25 | 2022-03-03 | ||
WO2022044999A1 (en) * | 2020-08-25 | 2022-03-03 | 富士フイルム株式会社 | Curable resin composition, cured article, laminated body, method for producing cured article, semiconductor device, polyimide precursor, and method for producing same |
WO2023157911A1 (en) * | 2022-02-21 | 2023-08-24 | 富士フイルム株式会社 | Resin composition, cured product, multilayer body, method for producing cured product, method for producing multilayer body, method for producing semiconductor device, and semiconductor device |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11100517A (en) * | 1997-09-29 | 1999-04-13 | Hitachi Chem Co Ltd | Resin paste, film forming method, electronic part and semi-conductor device |
JP2002296767A (en) * | 2001-03-29 | 2002-10-09 | Toray Ind Inc | Photosensitive polyimide precursor composition |
JP2016027357A (en) * | 2014-03-27 | 2016-02-18 | 富士フイルム株式会社 | Photosensitive resin composition, cured film, method for producing cured film, and semiconductor device |
WO2017002858A1 (en) * | 2015-06-30 | 2017-01-05 | 富士フイルム株式会社 | Precursor composition, photosensitive resin composition, method for producing precursor composition, cured film, method for producing cured film, and semiconductor device |
WO2017081922A1 (en) * | 2015-11-11 | 2017-05-18 | 東レ株式会社 | Semiconductor device, and manufacturing method for same |
WO2017146152A1 (en) * | 2016-02-26 | 2017-08-31 | 富士フイルム株式会社 | Laminate, method for manufacturing laminate, semiconductor device, and method for manufacturing semiconductor device |
WO2018025738A1 (en) * | 2016-08-01 | 2018-02-08 | 富士フイルム株式会社 | Photosensitive resin composition, cured film, laminate, method for producing cured film, method for producing laminate, and semiconductor device |
US20190309131A1 (en) * | 2018-04-04 | 2019-10-10 | Samsung Electronics Co., Ltd. | Composition comprising polymer and inorganic particles, polyimide-inorganic particles composite, article including the composite, and optical device including the article |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI413860B (en) | 2010-02-16 | 2013-11-01 | Asahi Kasei E Materials Corp | A negative photosensitive resin composition, a method for manufacturing a hardened embossed pattern, and a semiconductor device |
-
2021
- 2021-02-24 TW TW110106531A patent/TW202200671A/en unknown
- 2021-02-25 CN CN202180016937.6A patent/CN115190891B/en active Active
- 2021-02-25 JP JP2022503684A patent/JPWO2021172420A1/ja active Pending
- 2021-02-25 KR KR1020227029396A patent/KR20220134583A/en not_active Application Discontinuation
- 2021-02-25 WO PCT/JP2021/007075 patent/WO2021172420A1/en active Application Filing
-
2024
- 2024-03-12 JP JP2024038234A patent/JP2024083351A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11100517A (en) * | 1997-09-29 | 1999-04-13 | Hitachi Chem Co Ltd | Resin paste, film forming method, electronic part and semi-conductor device |
JP2002296767A (en) * | 2001-03-29 | 2002-10-09 | Toray Ind Inc | Photosensitive polyimide precursor composition |
JP2016027357A (en) * | 2014-03-27 | 2016-02-18 | 富士フイルム株式会社 | Photosensitive resin composition, cured film, method for producing cured film, and semiconductor device |
WO2017002858A1 (en) * | 2015-06-30 | 2017-01-05 | 富士フイルム株式会社 | Precursor composition, photosensitive resin composition, method for producing precursor composition, cured film, method for producing cured film, and semiconductor device |
WO2017081922A1 (en) * | 2015-11-11 | 2017-05-18 | 東レ株式会社 | Semiconductor device, and manufacturing method for same |
WO2017146152A1 (en) * | 2016-02-26 | 2017-08-31 | 富士フイルム株式会社 | Laminate, method for manufacturing laminate, semiconductor device, and method for manufacturing semiconductor device |
WO2018025738A1 (en) * | 2016-08-01 | 2018-02-08 | 富士フイルム株式会社 | Photosensitive resin composition, cured film, laminate, method for producing cured film, method for producing laminate, and semiconductor device |
US20190309131A1 (en) * | 2018-04-04 | 2019-10-10 | Samsung Electronics Co., Ltd. | Composition comprising polymer and inorganic particles, polyimide-inorganic particles composite, article including the composite, and optical device including the article |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2022044998A1 (en) * | 2020-08-25 | 2022-03-03 | ||
WO2022044999A1 (en) * | 2020-08-25 | 2022-03-03 | 富士フイルム株式会社 | Curable resin composition, cured article, laminated body, method for producing cured article, semiconductor device, polyimide precursor, and method for producing same |
WO2022044998A1 (en) * | 2020-08-25 | 2022-03-03 | 富士フイルム株式会社 | Curable resin composition, cured object, layered product, method for producing cured object, semiconductor device, and polyimide precursor and production method therefor |
JP7530430B2 (en) | 2020-08-25 | 2024-08-07 | 富士フイルム株式会社 | CURABLE RESIN COMPOSITION, CURED PRODUCT, LAMINATE, METHOD FOR PRODUCING CURED PRODUCT, SEMICONDUCTOR DEVICE, POLYIMIDE PRECURSOR AND METHOD FOR PRODUCING SAME |
WO2023157911A1 (en) * | 2022-02-21 | 2023-08-24 | 富士フイルム株式会社 | Resin composition, cured product, multilayer body, method for producing cured product, method for producing multilayer body, method for producing semiconductor device, and semiconductor device |
Also Published As
Publication number | Publication date |
---|---|
CN115190891B (en) | 2024-10-15 |
JPWO2021172420A1 (en) | 2021-09-02 |
CN115190891A (en) | 2022-10-14 |
TW202200671A (en) | 2022-01-01 |
JP2024083351A (en) | 2024-06-21 |
KR20220134583A (en) | 2022-10-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7412530B2 (en) | Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device | |
JP7300511B2 (en) | Method for producing cured film, photocurable resin composition, method for producing laminate, and method for producing semiconductor device | |
JP7492003B2 (en) | CURABLE RESIN COMPOSITION, CURED FILM, LAMINATE, METHOD FOR PRODUCING CURED FILM, AND SEMICONDUCTOR DEVICE | |
JP7470790B2 (en) | Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device | |
JP7334268B2 (en) | Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device | |
WO2021172420A1 (en) | Curable resin composition, cured film, laminate, cured film production method and semiconductor device | |
JP7504213B2 (en) | Method for producing cured product, method for producing laminate, and method for producing semiconductor device | |
JP7425088B2 (en) | Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and resin | |
WO2022138606A1 (en) | Resin composition, cured product, laminate, method for producing cured product, and semiconductor device | |
JP2023159205A (en) | Resin composition, cured film, laminate, manufacturing method of cured film, and semiconductor device | |
JP7498281B2 (en) | CURABLE RESIN COMPOSITION, CURED PRODUCT, LAMINATE, PROCESS FOR PRODUCING CURED PRODUCT, AND SEMICONDUCTOR DEVICE | |
JP7576617B2 (en) | CURABLE RESIN COMPOSITION, CURED FILM, LAMINATE, METHOD FOR PRODUCING CURED FILM, AND SEMICONDUCTOR DEVICE | |
WO2022059622A1 (en) | Resin composition, cured object, layered product, method for producing cured object, and semiconductor device | |
WO2022045120A1 (en) | Photosensitive resin composition, cured product, laminate, method for manufacturing cured product, and semiconductor device | |
JP7454672B2 (en) | Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and thermosetting resin | |
JP7558988B2 (en) | Resin composition, cured film, laminate, method for producing cured film, and semiconductor device | |
JP7526272B2 (en) | Method for producing polyimide precursor and method for producing curable resin composition | |
JP7453260B2 (en) | Curable resin composition, resin film, cured film, laminate, method for producing cured film, and semiconductor device | |
JP7367049B2 (en) | Pattern forming method, photosensitive resin composition, laminate manufacturing method, and semiconductor device manufacturing method | |
WO2022050278A1 (en) | Curable resin composition, cured object, layered product, method for producing cured object, semiconductor device, and photobase generator | |
JP7573026B2 (en) | CURABLE RESIN COMPOSITION, CURED FILM, LAMINATE, METHOD FOR PRODUCING CURED FILM, AND SEMICONDUCTOR DEVICE | |
JP7506735B2 (en) | Photosensitive resin composition, pattern manufacturing method, photosensitive film, cured product, laminate, and device | |
JP7451681B2 (en) | Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device | |
KR102727376B1 (en) | Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device | |
WO2022176869A1 (en) | Method for producing permanent film, method for producing multilayer body, and method for producing semiconductor device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21761334 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022503684 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20227029396 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21761334 Country of ref document: EP Kind code of ref document: A1 |