CN110066225A - Double oxime ester lightlike initiating agents, preparation method, photosensitive polymer combination and application - Google Patents
Double oxime ester lightlike initiating agents, preparation method, photosensitive polymer combination and application Download PDFInfo
- Publication number
- CN110066225A CN110066225A CN201810064764.5A CN201810064764A CN110066225A CN 110066225 A CN110066225 A CN 110066225A CN 201810064764 A CN201810064764 A CN 201810064764A CN 110066225 A CN110066225 A CN 110066225A
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- China
- Prior art keywords
- group
- independently
- alkyl
- photoinitiator
- meth
- Prior art date
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- -1 oxime ester Chemical class 0.000 title abstract description 25
- 230000000977 initiatory effect Effects 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000011342 resin composition Substances 0.000 claims description 48
- 150000002148 esters Chemical class 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- 125000000962 organic group Chemical group 0.000 claims description 13
- 230000009471 action Effects 0.000 claims description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000001544 thienyl group Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 238000006146 oximation reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 230000005012 migration Effects 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 72
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003086 colorant Substances 0.000 description 13
- 239000003822 epoxy resin Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 229920000647 polyepoxide Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 238000001723 curing Methods 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical group Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 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
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-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
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-UHFFFAOYSA-N 0.000 description 1
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WLMZVBARAUTFJP-UHFFFAOYSA-N 2-(2-hydroxy-3-prop-2-enoyloxypropoxy)carbonylbenzoic acid Chemical compound C=CC(=O)OCC(O)COC(=O)C1=CC=CC=C1C(O)=O WLMZVBARAUTFJP-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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
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- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- ITMIRWIISVVMAK-UHFFFAOYSA-N 2-chloro-3-ethyloxirane Chemical compound CCC1OC1Cl ITMIRWIISVVMAK-UHFFFAOYSA-N 0.000 description 1
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- ZAWQXWZJKKICSZ-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanamide Chemical compound CC(C)(C)C(=C)C(N)=O ZAWQXWZJKKICSZ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- ZQMYEPFHTNGUQE-UHFFFAOYSA-N 6-methylheptyl nitrite Chemical compound CC(C)CCCCCON=O ZQMYEPFHTNGUQE-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
- 239000004925 Acrylic resin Substances 0.000 description 1
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- 229930185605 Bisphenol Natural products 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 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 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229960002598 fumaric acid Drugs 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 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
- 229940098895 maleic acid Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- FGPRMKMMRHMWPX-UHFFFAOYSA-N n-formylprop-2-enamide Chemical compound C=CC(=O)NC=O FGPRMKMMRHMWPX-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
- C07C255/64—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention provides a kind of double oxime ester lightlike initiating agents, preparation method, photosensitive polymer combination and applications.Double oxime ester lightlike initiating agents have structure shown in logical formula (I).Due to containing polymerizable group in above-mentioned double oxime ester lightlike initiating agents, thus in application process, the biggish macromolecular solid compound of molecular weight can be formed by polymerization reaction, so as to be effectively reduced light-initiated migration.Simultaneously because the particularity of its structure makes its efficiency of initiation with higher, thus, it is not easy to migrate and light-initiated high-efficient to have many advantages, such as that double oxime ester lightlike initiating agents of above structure have.
Description
Technical Field
The invention relates to the field of photocuring, and particularly relates to a dioxime ester photoinitiator, a preparation method, a photosensitive resin composition and application.
Background
Compared with the traditional kinescope monitor, the liquid crystal display device has the advantages of low energy consumption, small volume and no radiation, but still has the defects of small visible angle, trailing image, poor brightness and contrast. In recent years, with the increasing living standard of people, people have made higher demands on liquid crystal display devices, and demands for large size, high luminance, high contrast, wide viewing angle, and the like are mentioned, which makes higher demands on materials used in the manufacture of liquid crystal displays.
Color, black photoresist and photo spacers are important components of liquid crystal flat panel display, and are essential materials for realizing large size and high resolution of advanced flat panel display, and oxime ester initiator with high sensitivity is an important component of photoresist and spacer formula. In recent years, the research on high-sensitivity initiators is very pyro-thermal, but the migration problem of the existing photoinitiators is still not effectively solved, and the application performance of the materials is influenced to a different extent.
Disclosure of Invention
The invention mainly aims to provide a dioxime ester photoinitiator, a preparation method, a photosensitive resin composition and application thereof, so as to solve the problem that the existing photoinitiator is easy to migrate.
In order to achieve the above object, according to one aspect of the present invention, there is provided a dioxime ester type photoinitiator having a structure represented by general formula (I):
wherein R is1、R2、R3And R4Independently of one another, a monovalent organic group or a hydrogen atom; g representsOrGroup, R5And R6Independently of one another, represent a polymerizable group; j and Q represent a connecting bond or a carbonyl group; m represents a monovalent organic group or a hydrogen atom.
Further, R5And R6Independently of one another represent C2～C12Alkenyl, oxiranylalkyl or oxiranylalkyl of (A), or R5And R6Independently of one another represent C2～C12Alkenyl of (a), and C2～C12One or more-CH in the alkenyl group of (2)2Each independently of the others by-O-, -CO-, -COO-, -OCO-orSubstituted; or R5And R6Independently of one another, an ethylene oxide alkyl group or a propylene oxide alkyl group, and ethylene oxide alkyl group or propylene oxideOIn the alkyl group, one or more-CH groups in the alkyl group between the epoxy group and the host structure2May each independently be-O-, -CO-, -COO-, -OCO-or-O-CH2-CH(OH)-CH2-O-substituted.
Further, R1And R2Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C10Alkyl of (C)1～C20Alkyl substituted C3～C8At least one hydrogen atom in cycloalkyl, phenyl is replaced by C1～C4Radical obtained after alkyl substitution, C1～C4Alkoxy group of (C)1～C4A group obtained by substituting one or more hydrogen atoms in the alkoxy group with fluorine atoms, a thienyl group, or C terminated with a thienyl group1～C4An alkyl group.
Further, R3And R4Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C10Alkyl of (C)6～C20Aryl of (C)1～C5Alkyl substituted C6～C20Aryl radical, C4～C20Heteroaryl of (A), C1～C5Alkyl substituted C6～C20Heteroaryl, or C2～C20Alkenyl groups of (a).
Further, M is nitro or cyano.
Further, the dioxime ester photoinitiator is selected from
One or more of the group consisting of.
According to another aspect of the present invention, there is provided a method for preparing a dioxime ester photoinitiator, the method comprising:
s1, under the action of a first catalyst, reacting a raw material a with a raw material b to obtain an intermediate a, wherein the synthetic route is as follows:
wherein, X1Represents halogen, A represents-CH2-or-NH-, G' represents R5Or R6Group, G representsGroup, R5And R6Independently of one another, represent a polymerizable group;
s2, under the action of a second catalyst, carrying out Friedel-crafts acylation reaction on the intermediate a, the raw material c and the raw material d to obtain an intermediate b, wherein the synthetic route is as follows:
wherein, X2And X3Each independently selected from halogen;
s3, under the action of a third catalyst, carrying out oximation reaction on the intermediate b to obtain an intermediate c, wherein the synthetic route is as follows:
j and Q represent a connecting bond or a carbonyl group, R1' is R1Or R1-CH2-，R2' represents R2Or R2-CH2-，R1And R2Independently of one another, a monovalent organic group or a hydrogen atom;
s4, carrying out esterification reaction on the intermediate c and acid anhydride or acyl chloride compound to obtain the dioxime ester photoinitiator, wherein the acid anhydride is (R)3-CO)2O and/or (R)4-CO)2O, acyl chloride compound is R3-CO-Cl and/or R4-CO-Cl, the synthetic route being:
R3and R4Independently of one another, represent a monovalent organic group or a hydrogen atom.
According to another aspect of the present invention, there is provided a photosensitive resin composition comprising a resin having an ethylenically unsaturated group, a monomer having an ethylenically unsaturated group, an alkali-soluble resin, a photoinitiator including the above-mentioned dioximate photoinitiator, and an auxiliary agent.
According to another aspect of the present invention, there is provided an insulating film formed by curing the photosensitive resin composition.
According to another aspect of the present invention, there is provided a display device including the above insulating film.
By applying the technical scheme of the invention, the dioxime ester photoinitiator contains polymerizable groups, so that a high-molecular cured product with a relatively large molecular weight can be formed through a polymerization reaction in the application process, and the photoinitiation mobility can be effectively reduced. Meanwhile, due to the structural particularity, the dioxime ester photoinitiator has high initiation efficiency, so that the dioxime ester photoinitiator with the structure has the advantages of difficult migration, high photoinitiation efficiency and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background, existing photoinitiators suffer from a tendency to migrate. In order to solve the technical problem, the application provides a dioxime photoinitiator, which has a structure shown in a general formula (I):
wherein,
R1、R2、R3and R4Independently of one another, a monovalent organic group or a hydrogen atom;
g representsGroup, R5And R6Independently of one another, represent a polymerizable group; j and Q represent a connecting bond or a carbonyl group; m represents a monovalent organic group or a hydrogen atom.
The dioxime ester photoinitiator contains a polymerizable group, so that a high-molecular cured product with a relatively high molecular weight can be formed through a polymerization reaction in an application process, and the photoinitiation mobility can be effectively reduced. Meanwhile, due to the structural particularity, the dioxime ester photoinitiator has high initiation efficiency, so that the dioxime ester photoinitiator with the structure has the advantages of difficult migration, high photoinitiation efficiency and the like.
Preferably, R5And R6Independently of one another represent C2～C12Alkenyl, ethylene oxide alkyl or propylene oxide alkyl of (a); or R5And R6Independently of one another represent C2～C12Alkenyl of (a), and C2～C12One or more-CH in the alkenyl group of (2)2Each independently of the others by-O-, -CO-, -COO-, -OCO-orSubstituted; or
R5And R6Independently of one another, an ethylene oxide alkyl group or a propylene oxide alkyl group, and one or more-CH groups in the alkyl group between the epoxy group and the main structure in the ethylene oxide alkyl group or the propylene oxide alkyl group2May each independently be-O-, -CO-, -COO-, -OCO-or-O-CH2-CH(OH)-CH2-O-substituted.
The above-mentioned term "alkyl group between epoxy group and main structure" means that R is removed from the structure represented by the general formula (I)5Or R6The latter residues.
In the structure represented by the general formula (I), a substituent group And the substitution position of "M" may be substituted for any one of the hydrogen atoms on the benzene ring on which it is placed.
Preferably, R1And R2Are respectively independentIs selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C10Alkyl of (C)1～C20Alkyl substituted C3～C8At least one hydrogen atom in cycloalkyl, phenyl is replaced by C1～C4Radical obtained after alkyl substitution, C1～C4Alkoxy group of (C)1～C4Radicals obtained by substitution of one or more hydrogen atoms in alkoxy groups by fluorine atoms, thienyl radicals, or C terminated with thienyl radicals1～C4An alkyl group;
preferably, R3And R4Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C10Alkyl of (C)6～C20Aryl of (C)1～C5Alkyl substituted C6～C20Aryl radical, C4～C20Heteroaryl of (A), C1～C5Alkyl substituted C6～C20Heteroaryl, or C2～C20Alkenyl groups of (a).
Preferably, M is nitro or cyano.
In order to further reduce the migration of the above-mentioned dioxime-type photoinitiators and at the same time improve the initiation efficiency thereof, it is preferred that the dioxime-type photoinitiators are selected from
One or more of the group consisting of.
The application also provides a preparation method of the dioxime ester photoinitiator, and the preparation method comprises the following steps:
s1, under the action of a first catalyst, reacting a raw material a with a raw material b to obtain an intermediate a, wherein the synthetic route is as follows:
wherein, X1Represents halogen, A represents-CH2-or-NH-, G' represents R5Or R6Group, G representsGroup, R5And R6Independently of one another, represent a polymerizable group;
s2, under the action of a second catalyst, carrying out Friedel-crafts acylation reaction on the intermediate a, the raw material c and the raw material d to obtain an intermediate b, wherein the synthetic route is as follows:
wherein, X2And X3Each independently selected from halogen;
j and Q represent a connecting bond or a carbonyl group,
R1' is R1Or R1-CH2-，R2' represents R2Or R2-CH2-，R1And R2Independently of one another, a monovalent organic group or a hydrogen atom;
s3, under the action of a third catalyst, carrying out oximation reaction on the intermediate b to obtain an intermediate c, wherein the synthetic route is as follows:
j and Q represent a connecting bond or a carbonyl group, R1' is R1Or R1-CH2-，R2' represents R2Or R2-CH2-，R1And R2Independently of one another, a monovalent organic group or a hydrogen atom;
s4, carrying out esterification reaction on the intermediate c and acid anhydride or acyl chloride compound to obtain the dioxime ester photoinitiator, wherein the acid anhydride is (R)3-CO)2O and/or (R)4-CO)2O, acyl chloride compound is R3-CO-Cl and/or R4-CO-Cl, the synthetic route being:
R3and R4Independently of one another, represent a monovalent organic group or a hydrogen atom.
Preferably, X1、X2And X3Each independently selected from F, Cl or Br.
Preferably, the first catalyst in step S1 includes, but is not limited to, one or more of the group consisting of sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, and potassium methoxide.
Preferably, the reaction in step S1 is carried out under the action of a first organic solvent. The solvent used in the reaction is not particularly limited as long as it does not inhibit the reaction, but DMSO, THF, and DMF are preferred. The reaction temperature is usually room temperature, and the reaction time is slightly different according to the types of raw materials, and is usually 2-10 h.
Preferably, the second catalyst in step S2 includes, but is not limited to, aluminum trichloride and/or zinc chloride. Specifically, when J is a connecting bond, R1' represents R1When Q is a connecting bond, R2' represents R2When J is carbonyl, R1' represents R1-CH2-, R when Q is carbonyl2' represents R2CH2-. The raw material b and the raw material c may be the same or different, and it is preferable that the raw material b and the raw material c are the same from the viewpoint of easiness of the operation of the reaction.
Preferably, when J and Q are a connecting bond in step S3, the third catalyst is hydroxylamine hydrochloride and sodium acetate; when J and Q are carbonyl, the third catalyst is concentrated hydrochloric acid and nitrite or nitrite; step S3 is preferably performed by the action of the second organic solvent, and the type of solvent used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction. When J and Q are each a connecting bond, the solvent used may be a mixed solvent of alcohol and water, preferably a mixed solvent of ethanol and water; the reaction was carried out under heating under reflux. When J and Q are each carbonyl, the solvent used may be dichloromethane, benzene, toluene, tetrahydrofuran, etc., the nitrite may be selected from ethyl nitrite, isoamyl nitrite, isooctyl nitrite, etc., and the nitrite may be selected from sodium nitrite, potassium nitrite, etc.
Preferably, the esterification reaction in step S4 is carried out in an organic solvent, which is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene, and the like.
The application also provides a photosensitive resin composition, which comprises a resin with an ethylenic unsaturated group, a monomer with an ethylenic unsaturated group, an alkali-soluble resin, a photoinitiator and an auxiliary agent, wherein the photoinitiator comprises the dioxime ester photoinitiator.
The dioxime ester photoinitiator contains a polymerizable group, so that a high-molecular cured product with a relatively high molecular weight can be formed through a polymerization reaction in an application process, and the photoinitiation mobility can be effectively reduced. Meanwhile, due to the structural particularity of the oxime ester photoinitiator, the photoinitiator has high photoinitiation activity. Therefore, the photosensitive resin composition prepared by using the dioxime ester photoinitiator containing the polymerizable group has the advantages of high initiation efficiency, high curing speed, difficult migration and the like.
The specific composition of the photosensitive resin composition can be adjusted as necessary. The components contained therein are specifically described below.
< (A) resin having ethylenically unsaturated group
The photopolymerizable compound (a) contained in the photosensitive composition is not particularly limited, and conventionally known photopolymerizable compounds can be used. By combining the resin having an ethylenically unsaturated group and the monomer having an ethylenically unsaturated group, the curability of the photosensitive composition can be improved, so that pattern formation can be easily performed. Preferably, examples of the resin having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di, Oligomers obtained by polymerizing trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, Cardo-epoxy diacrylate (bisphenol group-epoxy diacrylate), and the like; polyester (meth) acrylates obtained by reacting (meth) acrylic acid with polyester prepolymers obtained by condensing polyhydric alcohols with monobasic acids or polybasic acids; a urethane (meth) acrylate obtained by reacting a polyol with a compound having 2 isocyanate groups and then reacting (meth) acrylic acid; epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin (linear epoxy resin or novolac type epoxy resin), resol type epoxy resin (resol type epoxy resin), trisphenol methane type epoxy resin, polyglycidyl ester of polycarboxylic acid, polyglycidyl ester of polyhydric alcohol, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin, epoxy (meth) acrylate resins obtained by reacting (meth) acrylic acid, and the like. Further, a resin obtained by reacting a polybasic acid anhydride with an epoxy (meth) acrylate resin can be preferably used.
In the present application, the term "(meth) acryl-" means "acryl-or methacryl-".
In addition, as the resin having an ethylenically unsaturated group, it is possible to suitably use: a resin obtained by further reacting a reactant of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride.
Preferably, the photosensitive resin composition includes 10 to 99.9 parts by weight of the resin having an ethylenically unsaturated group, preferably 10 to 50 parts by weight.
< (B) monomer having ethylenically unsaturated group
The monomer having an ethylenically unsaturated group includes a monofunctional monomer and a polyfunctional monomer. The monofunctional monomer and the polyfunctional monomer are explained below in order.
Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, t-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methyl (meth) acrylate, N-hydroxyhexyl (meth) acrylate, N-ethylhydroxy (meth) acrylamide, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, half-esters of phthalic acid derivatives, and the like. The above monofunctional monomers may be used alone or in combination of two or more.
Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexaacrylate, tetraethylene penta (meth) acrylate, and mixtures thereof, 2, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., a reaction product of a diisocyanate such as tolylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, or 1, 6-hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate) Methylenebis (meth) acrylamide, (meth) acrylamidomethylene ether, a condensate of a polyhydric alcohol and N-methylol (meth) acrylamide, 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine (triacrylformal), and the like. The polyfunctional monomers may be used alone or in combination of two or more.
Preferably, the photosensitive resin composition includes 10 to 99.9 parts by weight of a monomer having an ethylenically unsaturated group.
(C) photoinitiator
The photosensitive resin composition contains (C) a photoinitiator containing a compound represented by formula (I). With respect to the compound represented by the formula (I), as described above. The photosensitive resin composition has advantages such as excellent sensitivity and migration resistance because it contains the compound represented by formula (I) as a photopolymerization initiator.
The photopolymerization initiator may contain the compound represented by the formula (I) and other photopolymerization initiators. The other photopolymerization initiator can be appropriately selected from various photopolymerization initiators conventionally blended in various photosensitive resin compositions.
Preferably, the photosensitive resin composition includes 0.5 to 3 parts by weight of a photoinitiator.
< (D) colorant
Alternatively, the photosensitive resin composition may further include (D) a colorant. The photosensitive resin composition containing the colorant (D) can be preferably used for forming a color filter of a display device such as a liquid crystal display. Further, the photosensitive resin composition can be preferably used for forming a black matrix in a color filter of a display device, for example, by including a light-shielding agent as the (D) colorant.
Preferably, the photosensitive composition further comprises a colorant; preferably, the photosensitive resin composition comprises 0.5 to 5 parts by weight of a colorant.
< (E) alkali-soluble resin
The photosensitive resin composition may contain (E) an alkali-soluble resin as a resin other than the resin used as the photopolymerizable compound. By blending (E) an alkali-soluble resin in the photosensitive resin composition, alkali developability can be imparted to the photosensitive resin composition, and the alkali-soluble resin can be selectively added depending on the specific use of the photopolymerizable compound.
Preferably, the photosensitive resin composition comprises 15 to 95 parts by weight of alkali-soluble resin, preferably 35 to 85 parts by weight, and more preferably 50 to 70 parts by weight.
< (F) other component
The photosensitive resin composition may contain other components as necessary. Specifically, there may be mentioned auxiliaries such as a solvent, a surfactant, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a dispersion aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, a deflocculant, a thermal polymerization inhibitor, a defoaming agent, a surfactant, and a chain transfer agent. All the additives can be those known in the art.
Preferably, the photosensitive resin composition comprises, by weight, 10 to 50 parts of a resin having an ethylenically unsaturated group, 10 to 99.9 parts of a monomer having an ethylenically unsaturated group, 0.5 to 3 parts of a photoinitiator, 0.5 to 5 parts of a colorant, and 15 to 25 parts of an auxiliary agent.
Preferably, the photosensitive resin composition comprises, by weight, 10 to 99.9 parts of a resin having an ethylenically unsaturated group, 10 to 99.9 parts of a monomer having an ethylenically unsaturated group, 0.5 to 3 parts of a photoinitiator, 0.5 to 5 parts of a colorant, 15 to 95 parts of an alkali-soluble resin, and 1 to 30 parts of an auxiliary agent.
Preferably, the photosensitive resin composition comprises, by weight, 10 to 50 parts of a resin having an ethylenically unsaturated group, 10 to 99.9 parts of a monomer having an ethylenically unsaturated group, 0.5 to 3 parts of a photoinitiator, 0.5 to 5 parts of a colorant, 35 to 85 parts of an alkali-soluble resin, and 15 to 25 parts of an auxiliary agent.
It should be noted that the term "parts by weight" in the present application has the same dimension, for example, each represents 1g or 1kg, etc.
< preparation and application of photosensitive resin composition >
The photosensitive resin composition can be prepared by mixing all the above components with a stirrer. When the photosensitive resin composition to be produced does not contain an insoluble component such as a pigment, filtration may be performed using a filter so that the photosensitive resin composition becomes uniform.
The photosensitive resin composition described above is cured by exposure, and a cured product of the photosensitive resin composition can be used for various purposes.
Preferably, the photosensitive resin composition includes:
the application also provides an insulating film, which is formed by curing the photosensitive resin composition.
The photosensitive resin composition prepared from the polymerizable group-containing bis-oxime ester photoinitiator has the advantages of high initiation efficiency, high curing speed, difficulty in migration and the like. Therefore, when the photosensitive resin composition is used for preparing an insulating film, the curing speed is high, the curing degree is high, and the like.
When the photosensitive resin composition does not contain (D) a colorant, a transparent insulating film is formed. When the photosensitive resin composition contains (D) a colorant, a colored insulating film is formed. In particular, (D) when the coloring agent is a black light-shading agent, a light-shading black insulating film is formed as a preferable example of the light-shading black insulating film, and examples thereof include black partition walls and black columnar spacers in a black matrix included in a panel for various image display devices; when the photosensitive resin composition contains a colorant (D) having a color of RGB or the like, a colored cured film is formed in a region partitioned by the black matrix, and a color filter can be manufactured. The color filter including the black matrix and the colored cured film as a cured product can be suitably used in various display devices.
Hereinafter, a method of forming an insulating film or a cured film that can be used as a color filter using the photosensitive resin composition described above will be described. The cured film formed using the photosensitive resin composition may be patterned as necessary.
In order to form a cured film using the photosensitive resin composition of the present invention, first, a photosensitive resin composition is coated on a substrate using a contact transfer type coating apparatus such as a roll coater, a reverse coater (reverse coater), or a bar coater, or a non-contact type coating apparatus such as a spin coater or a curtain flow coater. Next, the applied photosensitive resin composition is dried to form a coating film. Next, when the coating film is selectively exposed by irradiating the coating film with an active energy ray such as an ultraviolet ray or an excimer laser beam, a pattern having a desired shape is formed by developing the exposed film with a developer.
Practical application shows that the oxime ester photoinitiator has the characteristics of high photoinitiation efficiency and no migration in application, and has good market prospect no matter the photoinitiator is applied to common photocuring fields such as coatings, printing ink and adhesives or high-end photocuring fields such as insulating films, color photoresists, black matrixes, light spacers and rib walls.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Preparation of the initiator
Example 1
(1) Synthesis of intermediate 1a
A250 mL four-necked flask was charged with 24.2g of starting material 1a, 10.8g of sodium methoxide, and 50mL of thionyl chloride (DMSO), and the mixture was stirred at room temperature for 0.5h while introducing nitrogen into the four-necked flask. Then, 1b21.3g of the raw material was slowly dropped into the above four-necked flask, and the dropping was completed within 3 hours, and the liquid phase followed until the raw material was not changed. And pouring the material obtained after the reaction into deionized water, stirring, extracting a product by using n-hexane, drying the n-hexane product solution by using anhydrous magnesium sulfate, removing the n-hexane by rotary evaporation, and recrystallizing by using methanol as a solvent to obtain 28.7g of a light yellow solid product, namely an intermediate 1a, wherein the yield is 75 wt%, and the purity is 98 wt%.
The synthetic route is as follows:
intermediate 1a was confirmed by nmr hydrogen and mass spectroscopy:
1H-NMR(CDCl3，500MHz)：4.5406-4.8647(4H，m)，7.2206-7.8906(14H，m)。
MS(m/z)：383(M+1)+。
(2) synthesis of intermediate 1 b.
19.1g of the intermediate 1a, 13.3g of aluminum trichloride and 50mL of dichloromethane are added into a 250mL four-neck flask, the temperature of a reaction system is reduced to 0 ℃ by using an ice water bath, then a mixed solution of 14.6g of the raw material 1c and 25mL of dichloromethane is dropwise added, the temperature is controlled to be below 10 ℃, the dropwise addition is completed within about 2 hours, the stirring is continued for 2 hours after the dropwise addition is completed, and the liquid phase tracking reaction is completed. Then, slowly pouring the material obtained by the reaction into dilute hydrochloric acid prepared from 200g of ice water and 25mL of concentrated hydrochloric acid (37%), and stirring while adding; then pouring into a separating funnel, separating a lower dichloromethane layer, continuously washing a water layer by using 50mL dichloromethane, combining dichloromethane layers, washing the dichloromethane layer by using 5 wt% sodium bicarbonate aqueous solution (100 mL each time, 3 times in total), and then washing the dichloromethane layer until the pH value is neutral; the dichloromethane layer was dried over 80g anhydrous magnesium sulfate, filtered, and the dichloromethane product solution was rotary evaporated, recrystallized using methanol as a solvent, and dried in an oven at 80 ℃ for 2 hours to give 25.3g of intermediate 1b in 84 wt% yield and 98 wt% purity, MS (m/z): 603(M +1)+。
The synthetic route is as follows:
(3) synthesis of intermediate 1 c.
A100 mL four-necked flask was charged with 12.0g of intermediate 1b, 2.8g of hydroxylamine hydrochloride, 3.3g of sodium acetate, 30mL of ethanol, and 10mL of water, and the mixture was refluxed at 85 ℃ while being stirred for 5 hours, whereupon the reaction was stopped. The resultant was poured into a 500mL beaker, 150mL of water was added thereto, the mixture was stirred, 30mL of methylene chloride was used for extraction, and 20g of anhydrous MgSO was added to the extract4Drying and suction filtering. The filtrate was rotary evaporated under reduced pressure to remove the solvent to give an oily viscous mass in a spinner flask. Pouring the viscous substance into 50mL petroleum ether, stirring, filtering to obtain light yellow powdery solid, and oven drying at 70 deg.C for 5 hr to obtain intermediate 1c9.1g with yield of 72 wt% and purity of 98 wt%, MS (M/z):633(M +1)+。
The synthetic route is as follows:
(4) synthesis of Compound 1
6.3g of intermediate 1c and 30mL of methylene chloride were added to a 100mL four-necked flask, and stirred at room temperature for 5min, then 1.6g of acetyl chloride was added dropwise thereto, and stirring was continued for 2h after about 30 min. Then, 5 wt% NaHCO was added to the above four-necked flask3Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 30mL water for 2 times, and 5g anhydrous MgSO4Drying, filtering and rotary evaporating solvent to obtain viscous liquid. Recrystallizing with methanol as solvent to obtain light yellow solid powder, and filtering to obtain compound 1 (5.8 g), with yield of 81 wt% and purity of 99 wt%.
The synthetic route is as follows:
the structure of compound 1 was confirmed by nmr hydrogen and mass spectroscopy:
1H-NMR(CDCl3，500MHz)：1.4056-1.4432(14H，m)，1.6037-1.6267(8H，m)，1.9976-2.0835(6H，s)，4.5645-4.8678(4H,m)，7.2786-7.2896(2H，t)，7.4987-8.1849(10H，m)。
MS(m/z)：717(M+1)+。
example 2
(1) Synthesis of intermediate 2 a.
24.3g of the raw material 2a, 10.8g of sodium methoxide and 50mL of thionyl chloride (DMSO) are added into a 250mL four-neck flask, nitrogen is introduced, stirring is carried out at room temperature for 0.5h, then 10.6g of chloroepoxy butane is slowly dripped, the dripping is controlled for 3h, and the liquid phase tracking reaction is carried out until the raw material does not change any more. And pouring the material obtained after the reaction into deionized water, stirring, extracting a product by using n-hexane, drying the n-hexane product solution by using anhydrous magnesium sulfate, removing the n-hexane by rotary evaporation, and recrystallizing by using methanol as a solvent to obtain 28.2g of a white solid product, namely an intermediate 2a, wherein the yield is 90 wt%, and the purity is 98 wt%.
The synthetic route is as follows:
the structure of the intermediate 2a is confirmed by nuclear magnetic resonance hydrogen spectrum and mass spectrum:
1H-NMR(CDCl3，500MHz)：1.8936-1.9451(2H，m)，2.4958-2.5407(3H，m)，3.8407-3.8601(2H，t)，7.1893-7.4803(12H，m)。
MS(m/z)：314(M+1)+。
(2) synthesis of intermediate 2b
Adding 15.7g of intermediate 2a, 13.6g of zinc chloride and 50mL of dichloromethane into a 250mL four-neck flask, cooling to 0 ℃ in an ice-water bath, dropwise adding a mixed solution of 14.6g of raw material 2b and 50mL of dichloromethane, controlling the temperature to be below 10 ℃, completing dropwise addition for about 2 hours, continuing stirring for 2 hours after dropwise addition, tracking the liquid phase until the reaction is completed, slowly pouring the material into dilute hydrochloric acid prepared from 200g of ice water and 30mL of concentrated hydrochloric acid (37%), stirring while adding, pouring into a separating funnel, separating a dichloromethane layer at the lower layer, continuing washing an aqueous layer with 50mL of dichloromethane, combining the dichloromethane layers, washing the dichloromethane layer with 5% sodium bicarbonate aqueous solution (50 mL each time and 3 times), washing the dichloromethane layer with water until the pH value is neutral, drying the dichloromethane layer with 20g of anhydrous magnesium sulfate, filtering, evaporating the dichloromethane product solution after filtering, recrystallizing with methanol, drying in an oven at 80 ℃ for 2 hours, 22.1g of intermediate 2b are obtained with a yield of 85% by weight and a purity of 98% by weight, MS (m/z): 520(M +1)+。
The synthetic route is as follows:
(3) synthesis of intermediate 2c
A100 mL four-necked flask was charged with 10.4g of intermediate 2b, 4.0g of 37% hydrochloric acid, 4.7g of isoamyl nitrite, and 30mL of tetrahydrofuran, and stirred at room temperature for 5 hours to stop the reaction. The mixture was poured into a 500mL beaker, 100mL of water was added, the mixture was stirred, 50mL of dichloromethane was used for extraction, and 10g of anhydrous MgSO was added to the extract4Drying, performing suction filtration, performing rotary evaporation on the filtrate under reduced pressure to remove the solvent, rotating the bottle to obtain oily sticky matter, pouring the sticky matter into 50mL of petroleum ether, stirring and separating out, performing suction filtration to obtain light yellow powdery solid, drying at 70 ℃ for 5h to obtain 8.1g of an intermediate 2c, wherein the yield is 78 wt%, the purity is 98 wt%, and the mass ratio of MS (m/z): 592(M +1)+。
The synthetic route is as follows:
(4) synthesis of Compound 2
5.9g of intermediate 2c and 20mL of dichloromethane are added into a 100mL four-neck flask, stirred at room temperature for 5min, then 2.6g of propionic anhydride is added dropwise, stirring is continued for 2h after about 30min of dropwise addition is finished, and then 5 wt% NaHCO is added3Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 20mL water for 2 times, and washing with 5g anhydrous MgSO4Drying, filtering, evaporating the solvent to obtain a viscous liquid, recrystallizing with methanol to obtain yellow solid powder, and filtering to obtain 5.8g of product with yield of 83 wt% and purity of 99 wt%.
The synthetic route is as follows:
the structure of compound 2 was confirmed by nmr hydrogen and mass spectroscopy:
1H-NMR(CDCl3，500MHz)：1.0789-1.1022(6H，t)，1.5048-1.5231(10H,m)，1.6768-1.6959(8H，m)，1.8975-1.9067(2H，m)，2.2705-2.2876(4H,m)，2.5045-2.5400(3H，m)，3.8467-3.8584(2H，d)，7.2338-7.9027(10H，m)。
MS(m/z)：704(M+1)+。
example 3
Referring to the methods of examples 1 and 2, compounds 3-13 having the structures shown were prepared from the corresponding starting materials.
TABLE 1
Preparation of photosensitive resin composition
(1) The photocurable resin compositions (parts by weight) having the following compositions were prepared, as shown in tables 2 and 3.
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| A1 | 10 | 30 | 50 | ||||
| A2 | 50 | 10 | 50 | 50 | |||
| B1 | 80 | 40 | 40 | 40 | |||
| B2 | 60 | 30 | 80 | ||||
| C1 | 3 | 3 | |||||
| C2 | 3 | 3 | 3 | ||||
| C3 | 3 | ||||||
| C4 | 3 | ||||||
| C5 | |||||||
| C6 | |||||||
| C7 | |||||||
| C8 | |||||||
| C9 | |||||||
| C11 | |||||||
| D1 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| F1 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
TABLE 3
In tables 2 and 3, A1: acrylate copolymer [ benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio 70/10/20) copolymer (Mv:10000) ]; a2 acrylate copolymer [ benzyl acrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio 80/10/10) copolymer (Mv:12000) ];
b1: 1, 6-hexanediol diacrylate; b2 dipentaerythritol hexaacrylate;
c1: compound 1; c2: a compound 2; c3: compound 4; c4: compound 5; c5: compound 6; c6: compound 11; c7: compound 13;
d: carbon black; f1: butanone (solvent).
(2) Speed of curing
Stirring the above composition under yellow light, taking out, coating on PET template, drying at 90 deg.C for 2min to obtain 2 μm film, cooling to room temperature, and exposing with high-pressure mercury lamp (model: RW-UV70201, single exposure of 30 mJ/cm)2) The coating film is exposed to light and cured to form a film.
The number of times of the belt-like exposure of the coating film cured into a cured film was evaluated, and the larger the number of times, the less desirable the curing speed was.
(3) Mobility of
Cutting the cured film, weighing 0.5g of the cured film sample, placing the cured film sample in a 50mL beaker, adding 4.5mL of methanol, ultrasonically dissolving for 30min by utilizing ultrasonic waves, transferring the obtained methanol solution to a 10mL volumetric flask, continuously washing the sample twice (2mL by 2) by using the methanol, pouring the sample into the volumetric flask, transferring 0.1mL of methylbenzene serving as an internal standard substance by using a transfer pipette, adding the methanol for dissolving, uniformly shaking and standing.
Whether or not the presence of the photoinitiator was detected was observed by Shimadzu LC-20A liquid chromatography (shim pack column, 150X 6.0nm, detector SPD-20A, detection limit 20ppm, detection wavelength 254nm) at 25 ℃ using a mobile phase (methanol/water: 90/10) at a flow rate of 1.0 mL/min. The higher the initiator content in the liquid phase, in terms of percentage of the area of the liquid phase peak to toluene, the greater the mobility.
(4) Solubility in water
The solubility of the photoinitiator in reactive diluents and oligomers is an important measure of the performance of the initiator. The solubility of the photoinitiator in PGMEA is one of the parameters that represent its solubility and measure the performance of the photoinitiator.
The solubility of the compound of the general formula (I) of the invention and the existing oxime ester photoinitiator used as a comparison were respectively tested at 25 ℃ in PGMEA. The characterization results are shown in table 4.
TABLE 4
| Speed of curing | Mobility of | Solubility in water | |
| Example 1 | 1 | Not detected | >50％ |
| Example 2 | 1 | Not detected | >50％ |
| Example 3 | 1 | Not detected | >50％ |
| Example 4 | 1 | Not detected | >50％ |
| Example 5 | 1 | Not detected | >50％ |
| Example 6 | 1 | Not detected | >50％ |
| Example 7 | 1 | Not detected | >50％ |
| Example 8 | 1 | Not detected | >50％ |
| Example 9 | 1 | Not detected | >50％ |
| Example 10 | 1 | Not detected | >50％ |
| Example 11 | 1 | Not detected | >50％ |
| Comparative example 1 | 5 | 1.94 | <20％ |
| Comparative example 2 | 2 | 1.84 | <10％ |
| Comparative example 3 | 3 | Not detected | >50％ |
As can be seen from the test results in Table 4, the dioxime photoinitiator containing polymerizable groups shown in the general formula (I) has excellent solubility, high initiator efficiency and high curing speed in photocuring application, is not easy to migrate, and has comprehensive properties obviously superior to those of the conventional oxime ester photoinitiator products.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be apparent to those skilled in the art that the photoinitiator according to the present invention may be used in combination with other photoinitiators or sensitizers, and that the monomers, resins, and auxiliaries used may be replaced, modified, or changed. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A dioxime ester photoinitiator is characterized by having a structure shown in a general formula (I):
wherein,
the R is1The R is2The R is3And said R4Independently of one another, a monovalent organic group or a hydrogen atom;
said G representsGroup R5And said R6Independently of one another, represent a polymerizable group;
said J and said Q represent a connecting bond or a carbonyl group;
the M represents a monovalent organic group or a hydrogen atom.
2. The dioxime ester photoinitiator as set forth in claim 1, wherein R is R5And said R6Independently of one another represent C2～C12Alkenyl, ethylene oxide alkyl or propylene oxide alkyl, or
The R is5And said R6Independently of one another represent C2～C12And said C is2～C12One or more-CH in the alkenyl group of (2)2Each independently of the others by-O-, -CO-, -COO-, -OCO-orSubstituted; or
The R is5And said R6Independently of one another, an ethylene oxide alkyl group or a propylene oxide alkyl group, and one or more-CH's in the alkyl group between the epoxy group and the host structure in the ethylene oxide alkyl group or the propylene oxide alkyl group2May each independently be-O-, -CO-, -COO-, -OCO-or-O-CH2-CH(OH)-CH2-O-substituted.
3. The dioxime ester photoinitiator according to claim 1 or 2, wherein R is R1And said R2Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C10Alkyl of (C)1～C20Alkyl substituted C3～C8At least one hydrogen atom in cycloalkyl, phenyl is replaced by C1～C4Radical obtained after alkyl substitution, C1～C4Alkoxy group of (C)1～C4A group obtained by substituting one or more hydrogen atoms in the alkoxy group with fluorine atoms, a thienyl group, or C terminated with a thienyl group1～C4An alkyl group.
4. The dioxime ester photoinitiator as set forth in claim 1, wherein R is R3And said R4Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C10Alkyl of (C)6～C20Aryl of (C)1～C5Alkyl substituted C6～C20Aryl radical, C4～C20Heteroaryl of (A), C1～C5Alkyl substituted C6～C20Heteroaryl, or C2～C20Alkenyl groups of (a).
5. The dioxime ester type photoinitiator as set forth in claim 1, wherein M is a nitro group or a cyano group.
6. The dioxime ester photoinitiator according to any one of claims 1 to 5, wherein the dioxime ester photoinitiator is selected from the group consisting of
One or more of the group consisting of.
7. A method for preparing the dioxime ester type photoinitiator according to any one of claims 1 to 6, comprising:
s1, under the action of a first catalyst, reacting a raw material a with a raw material b to obtain an intermediate a, wherein the synthetic route is as follows:
wherein, X is1Represents halogen, A represents-CH2-or-NH-, said G' represents R5Or R6Group, said G representsGroup R5And said R6Independently of one another, represent a polymerizable group;
s2, under the action of a second catalyst, carrying out Friedel-crafts acylation reaction on the intermediate a, the raw material c and the raw material d to obtain an intermediate b, wherein the synthetic route is as follows:
wherein, X is2And said X3Each independently selected from halogen;
s3, under the action of a third catalyst, carrying out oximation reaction on the intermediate b to obtain an intermediate c, wherein the synthetic route is as follows:
said J and said Q represent a connecting bond or a carbonyl group, said R1' is R1Or R1-CH2-, said R2' represents R2Or R2-CH2-, said R1And said R2Independently of one another, a monovalent organic group or a hydrogen atom;
s4, carrying out esterification reaction on the intermediate c and an acid anhydride or acyl chloride compound to obtain the dioxime ester photoinitiator, wherein the acid anhydride is (R)3-CO)2O and/or (R)4-CO)2O, the acyl chloride compound is R3-CO-Cl and/or R4-CO-Cl, the synthetic route being:
the R is3And said R4Independently of one another, represent a monovalent organic group or a hydrogen atom.
8. A photosensitive resin composition comprising a resin having an ethylenically unsaturated group, a monomer having an ethylenically unsaturated group, an alkali-soluble resin, a photoinitiator, and an auxiliary, wherein the photoinitiator comprises the dioxime ester photoinitiator according to any one of claims 1 to 6.
9. An insulating film obtained by curing the photosensitive resin composition according to claim 8.
10. A display device comprising the insulating film according to claim 9.
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