JP2021178962A - Polyhydroxyamide composition for manufacturing substrates for electronic devices, and polybenzoxazole resin film - Google Patents
Polyhydroxyamide composition for manufacturing substrates for electronic devices, and polybenzoxazole resin film Download PDFInfo
- Publication number
- JP2021178962A JP2021178962A JP2021101262A JP2021101262A JP2021178962A JP 2021178962 A JP2021178962 A JP 2021178962A JP 2021101262 A JP2021101262 A JP 2021101262A JP 2021101262 A JP2021101262 A JP 2021101262A JP 2021178962 A JP2021178962 A JP 2021178962A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- polyhydroxyamide
- following formula
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 title claims abstract description 38
- 229920002577 polybenzoxazole Polymers 0.000 title claims abstract description 29
- -1 biphenyldiyl group Chemical group 0.000 claims abstract description 97
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 85
- 125000003118 aryl group Chemical group 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000000304 alkynyl group Chemical group 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 150000001721 carbon Chemical group 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 150000001408 amides Chemical class 0.000 claims description 9
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000004580 weight loss Effects 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims description 2
- ZXKINMCYCKHYFR-UHFFFAOYSA-N aminooxidanide Chemical compound [O-]N ZXKINMCYCKHYFR-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 41
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- XULIXFLCVXWHRF-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidine Chemical compound CN1C(C)(C)CCCC1(C)C XULIXFLCVXWHRF-UHFFFAOYSA-N 0.000 description 1
- MDEIZAFOJJIXIS-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-1-ol Chemical compound C(C)OC(COC(CC)O)C MDEIZAFOJJIXIS-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-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
- 125000006433 1-ethyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006019 1-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006018 1-methyl-ethenyl group Chemical group 0.000 description 1
- 125000006439 1-n-propyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 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
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- DZLUPKIRNOCKJB-UHFFFAOYSA-N 2-methoxy-n,n-dimethylacetamide Chemical compound COCC(=O)N(C)C DZLUPKIRNOCKJB-UHFFFAOYSA-N 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 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
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- VZQSBJKDSWXLKX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C=C(O)C=CC=2)=C1 VZQSBJKDSWXLKX-UHFFFAOYSA-N 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
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- CRORGGSWAKIXSA-UHFFFAOYSA-N 3-methylbutyl 2-hydroxypropanoate Chemical compound CC(C)CCOC(=O)C(C)O CRORGGSWAKIXSA-UHFFFAOYSA-N 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 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
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- OZNFSVCWVQJTHE-UHFFFAOYSA-N Cc(c(O)c1)ccc1-c1cc(O)c(C)cc1 Chemical compound Cc(c(O)c1)ccc1-c1cc(O)c(C)cc1 OZNFSVCWVQJTHE-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 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
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940057867 methyl lactate Drugs 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
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyamides (AREA)
- Liquid Crystal (AREA)
Abstract
Description
本発明は、電子デバイス用基板製造用ポリヒドロキシアミド組成物、及び該組成物から得られるポリベンゾオキサゾール樹脂フィルムに関する。 The present invention relates to a polyhydroxyamide composition for manufacturing a substrate for an electronic device, and a polybenzoxazole resin film obtained from the composition.
近年、電子機器の小型化、高性能化が進むなか、電子機器に用いる部材にも、軽さ、耐熱性等の特性が求められている。特に、有機エレクトロルミネッセンス(EL)ディスプレイ等の分野では、ガラス部材がその機器の重量の大半を占める場合があるだけでなく、市場においてフレキシブルディスプレイに対する期待がますます高まってきていることから、ガラスに代わる、柔軟性を備えた新材料を求める要望は大きい。 In recent years, with the progress of miniaturization and high performance of electronic devices, the members used for electronic devices are also required to have characteristics such as lightness and heat resistance. Especially in the field of organic electroluminescence (EL) displays, glass members may occupy most of the weight of the equipment, and the market is expecting more and more flexible displays. There is a great demand for new materials with flexibility to replace them.
ガラスは、優れた耐熱性と低い線膨張係数を有するため、電子機器の部材として用いられる。それゆえに、ガラスに代わる新材料にも、優れた耐熱性と低い線膨張係数が必要となる。とりわけ、高精細なディスプレイ等の製造プロセスにおいては、高い寸法精度を維持したまま、200℃以上、場合によっては400℃以上もの高温で処理をする必要があることから、基板等の部材は、これらの特性面で優れていることが必須となる。 Glass is used as a member of electronic devices because of its excellent heat resistance and low coefficient of linear expansion. Therefore, new materials to replace glass also require excellent heat resistance and a low coefficient of linear expansion. In particular, in the manufacturing process of high-definition displays and the like, it is necessary to process at a high temperature of 200 ° C. or higher, and in some cases 400 ° C. or higher while maintaining high dimensional accuracy. It is essential that the characteristics of the product are excellent.
この観点から、ポリイミド樹脂は、耐熱性が高く難燃性で電気絶縁性に優れるため、新材料の候補として注目を集めている。しかしながら、一般的に用いられるポリイミド樹脂は、高温処理下でも高い寸法精度を維持できる程度まで十分に低い線膨張係数を有しておらず、そのため、ディスプレイの製造プロセスでは、樹脂が縮小(又は膨張)してしまうほどの高温での処理ができない場合があった。このような事情に鑑み、ポリイミド樹脂が縮小(又は膨張)する温度での熱処理を含まない表示素子の製造方法に関する技術や、特徴的な酸二水物を用いた、低線膨張係数を有するポリイミド樹脂に関する技術が提案されている(特許文献1、2)。 From this point of view, polyimide resin is attracting attention as a candidate for a new material because it has high heat resistance, flame retardancy, and excellent electrical insulation. However, commonly used polyimide resins do not have a sufficiently low coefficient of linear expansion to the extent that high dimensional accuracy can be maintained even under high temperature treatment, and therefore the resin shrinks (or expands) in the display manufacturing process. ) In some cases, it could not be processed at such a high temperature. In view of these circumstances, a technique for manufacturing a display element that does not include heat treatment at a temperature at which the polyimide resin shrinks (or expands), and a polyimide having a low coefficient of linear expansion using a characteristic acid dihydrate. Techniques related to resins have been proposed (Patent Documents 1 and 2).
しかし、このような技術を用いた場合であっても、製造プロセスが複雑になる、汎用性に乏しい高価な酸二水物を用いなければならない等の問題があるだけでなく、フレキシブルディスプレイ等の用途に用いるのに十分な柔軟性を実現することが困難である。このため、従来のポリイミド樹脂では、これらの点を解決することは困難であり、代替材料が必要であった。 However, even if such a technique is used, there are problems such as complicated manufacturing process and the need to use an expensive acid dihydrate having poor versatility, as well as flexible displays and the like. It is difficult to achieve sufficient flexibility for use in applications. Therefore, it is difficult to solve these problems with the conventional polyimide resin, and an alternative material is required.
一方、ポリイミドと同様以上の耐熱性と低線膨張係数を有する材料として、ポリベンゾオキサゾール樹脂がある(非特許文献1)。しかし、ポリベンゾオキサゾールの前駆体であるポリヒドロキシアミドは、ポリイミドの前駆体であるポリアミック酸より溶解性が乏しく、合成中に析出する、又は精製後の再溶解が困難であるといった問題がある。このため、溶解性を付与するため、側鎖ヒドロキシ基をシリル基で保護する、溶媒にヘキサメチルリン酸トリアミドを用いる、又はポリアミック酸との共重合を行う技術が報告されている(非特許文献1〜3、特許文献3)。しかし、シリル化剤は高価であり、ヘキサメチルリン酸トリアミドは高い毒性を有するため産業上の利用性に乏しい。また、ポリアミック酸との共重合では、耐熱性に劣るといった欠点があった。 On the other hand, there is a polybenzoxazole resin as a material having heat resistance equal to or higher than that of polyimide and a low coefficient of linear expansion (Non-Patent Document 1). However, polyhydroxyamide, which is a precursor of polybenzoxazole, has a problem that it is less soluble than polyamic acid, which is a precursor of polyimide, and it is difficult to precipitate during synthesis or to be redissolved after purification. Therefore, in order to impart solubility, a technique of protecting a side chain hydroxy group with a silyl group, using a hexamethylphosphoric acid triamide as a solvent, or copolymerizing with a polyamic acid has been reported (Non-Patent Documents). 1-3, Patent Document 3). However, the silylating agent is expensive, and hexamethylphosphoric acid triamide is highly toxic and therefore has poor industrial utility. Further, the copolymerization with the polyamic acid has a drawback that the heat resistance is inferior.
本発明は、前記事情に鑑みてなされたものであり、耐熱性が高いポリベンゾオキサゾール樹脂フィルムを与え得るポリヒドロキシアミド組成物、及び該組成物から得られるポリベンゾオキサゾール樹脂フィルムを提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a polyhydroxyamide composition capable of providing a polybenzoxazole resin film having high heat resistance, and a polybenzoxazole resin film obtained from the composition. The purpose.
本発明者らは、前記目的を達成するため鋭意検討を重ねた結果、後述する式(1)で表される単位及び下記式(2)で表される単位を含むポリヒドロキシアミド、及び(B)有機溶媒を含む組成物から得られるポリベンゾオキサゾール樹脂フィルムが、耐熱性が高く、線膨張係数が小さいことを見出し、本発明を完成させた。 As a result of diligent studies to achieve the above object, the present inventors have made a polyhydroxyamide containing a unit represented by the formula (1) described later and a unit represented by the following formula (2), and (B). ) The present invention was completed by finding that a polybenzoxazole resin film obtained from a composition containing an organic solvent has high heat resistance and a small coefficient of linear expansion.
したがって、本発明は、下記電子デバイス用基板製造用ポリヒドロキシアミド組成物、及びポリベンゾオキサゾール樹脂フィルムを提供する。
1.(A)下記式(1)で表される単位及び下記式(2)で表される単位を含むポリヒドロキシアミド、及び(B)有機溶媒を含む電子デバイス用基板製造用ポリヒドロキシアミド組成物。
2.X1が、下記式(4)で表される基である1の電子デバイス用基板製造用ポリヒドロキシアミド組成物。
3.X1が、下記式(4')で表される基である2の電子デバイス用基板製造用ポリヒドロキシアミド組成物。
4.Y1が下記式(5)で表される基であり、Y2が下記式(6)で表される基である1〜3のいずれかの電子デバイス用基板製造用ポリヒドロキシアミド組成物。
5.R7〜R18が、水素原子である4の電子デバイス用基板製造用ポリヒドロキシアミド組成物。
6.Y2が、下記式(7)、(8)又は(9)で表される基である1〜5のいずれかの電子デバイス用基板製造用ポリヒドロキシアミド組成物。
7.n及びmが、5≦n≦25、75≦m≦95、及び80≦n+m≦100を満たす正数である1〜6のいずれかの電子デバイス用基板製造用ポリヒドロキシアミド組成物。
8.(B)有機溶媒が、下記式(S1)で表されるアミド類、下記式(S2)で表されるアミド類及び下記式(S3)で表されるアミド類から選ばれる少なくとも1つを含む1〜7のいずれかの電子デバイス用基板用ポリヒドロキシアミド組成物。
9.1〜8のいずれかの電子デバイス用基板製造用ポリヒドロキシアミド組成物を基材上に塗布する工程、及び加熱して溶媒を蒸発させ、ポリヒドロキシアミドを閉環させる工程を含む電子デバイス用基板用ポリベンゾオキサゾール樹脂フィルムの製造方法。
10.1〜8のいずれかのポリヒドロキシアミド組成物から得られる電子デバイス用基板用ポリベンゾオキサゾール樹脂フィルム。
11.5%重量減少温度が600℃以上であり、50〜400℃の線膨張係数が8ppm/℃以下である10の電子デバイス用基板用ポリベンゾオキサゾール樹脂フィルム。
12.10又は11の電子デバイス用基板用ポリベンゾオキサゾール樹脂フィルムを基板として備える電子デバイス。
13.下記式(10)で表される単位及び下記式(11)で表される単位を含むポリヒドロキシアミド。
14.X1が、下記式(4)で表される基である13のポリヒドロキシアミド。
15.X1が、下記式(4')で表される基である14のポリヒドロキシアミド。
16.Y1が下記式(5)で表される基であり、Y2が下記式(6)で表される基である13〜15のいずれかのポリヒドロキシアミド。
17.R7〜R18が、水素原子である16のポリヒドロキシアミド。
18.Y2が、下記式(7)、(8)又は(9)で表される基である13〜17のいずれかのポリヒドロキシアミド。
19.下記式(12)で表されるジアミン化合物、前記ジアミン化合物1モルに対して0.05〜0.25モルとなる量の下記式(13)で表されるジカルボン酸誘導体、及び前記ジアミン化合物1モルに対して0.75〜0.95モルとなる量の下記式(14)で表されるジカルボン酸誘導体を、溶媒中、触媒の存在下で縮合重合させる、ポリヒドロキシアミドの製造方法。
20.X1が、下記式(4)で表される基である19のポリヒドロキシアミドの製造方法。
21.X1が、下記式(4')で表される基である20のポリヒドロキシアミドの製造方法。
22.Y1が下記式(5)で表される基であり、Y2が下記式(6)で表される基である19〜21のいずれかのポリヒドロキシアミドの製造方法。
23.R7〜R18が、水素原子である22のポリヒドロキシアミドの製造方法。
24.Y2が、下記式(7)、(8)又は(9)で表される基である19〜23のいずれかのポリヒドロキシアミドの製造方法。
1. 1. (A) A polyhydroxyamide composition containing a unit represented by the following formula (1) and a unit represented by the following formula (2), and (B) a polyhydroxyamide composition for manufacturing a substrate for an electronic device containing an organic solvent.
2. 2. The polyhydroxyamide composition for manufacturing a substrate for an electronic device in which X 1 is a group represented by the following formula (4).
3. 3. A polyhydroxyamide composition for manufacturing a substrate for an electronic device in which X 1 is a group represented by the following formula (4').
4. A polyhydroxyamide composition for manufacturing a substrate for an electronic device according to any one of 1 to 3, wherein Y 1 is a group represented by the following formula (5) and Y 2 is a group represented by the following formula (6).
5. Polyhydroxyamide compositions for manufacturing substrates for electronic devices in which R 7 to R 18 are hydrogen atoms 4.
6. A polyhydroxyamide composition for manufacturing a substrate for an electronic device according to any one of 1 to 5, wherein Y 2 is a group represented by the following formula (7), (8) or (9).
7. The polyhydroxyamide composition for manufacturing a substrate for an electronic device according to any one of 1 to 6, wherein n and m are positive numbers satisfying 5 ≦ n ≦ 25, 75 ≦ m ≦ 95, and 80 ≦ n + m ≦ 100.
8. (B) The organic solvent contains at least one selected from amides represented by the following formula (S1), amides represented by the following formula (S2) and amides represented by the following formula (S3). The polyhydroxyamide composition for a substrate for any of 1 to 7 electronic devices.
9. For electronic devices, which comprises a step of applying the polyhydroxyamide composition for manufacturing a substrate for an electronic device according to any one of 9 to 8 onto a substrate, and a step of heating to evaporate the solvent to close the polyhydroxyamide. A method for producing a polybenzoxazole resin film for a substrate.
A polybenzoxazole resin film for a substrate for an electronic device obtained from any one of 10.1 to 8 polyhydroxyamide compositions.
A polybenzoxazole resin film for a substrate for an electronic device having a 11.5% weight loss temperature of 600 ° C. or higher and a linear expansion coefficient of 50 to 400 ° C. of 8 ppm / ° C. or lower.
12. An electronic device comprising a polybenzoxazole resin film for a substrate for an electronic device of 10 or 11 as a substrate.
13. A polyhydroxyamide containing a unit represented by the following formula (10) and a unit represented by the following formula (11).
14. X 1 is a polyhydroxyamide of 13 which is a group represented by the following formula (4).
15. 14 polyhydroxyamides in which X 1 is a group represented by the following formula (4').
16. The polyhydroxyamide according to any one of 13 to 15, wherein Y 1 is a group represented by the following formula (5) and Y 2 is a group represented by the following formula (6).
17. 16 polyhydroxyamides in which R 7 to R 18 are hydrogen atoms.
18. Y 2 is a polyhydroxyamide according to any one of 13 to 17, which is a group represented by the following formula (7), (8) or (9).
19. The diamine compound represented by the following formula (12), the dicarboxylic acid derivative represented by the following formula (13) in an amount of 0.05 to 0.25 mol with respect to 1 mol of the diamine compound, and the diamine compound 1 A method for producing a polyhydroxyamide, wherein a dicarboxylic acid derivative represented by the following formula (14) in an amount of 0.75 to 0.95 mol with respect to a molar is condensed and polymerized in a solvent in the presence of a catalyst.
20. A method for producing 19 polyhydroxyamides, wherein X 1 is a group represented by the following formula (4).
21. A method for producing 20 polyhydroxyamides, wherein X 1 is a group represented by the following formula (4').
22. A method for producing a polyhydroxyamide according to any one of 19 to 21, wherein Y 1 is a group represented by the following formula (5) and Y 2 is a group represented by the following formula (6).
23. A method for producing a polyhydroxyamide of 22 in which R 7 to R 18 are hydrogen atoms.
24. A method for producing a polyhydroxyamide according to any one of 19 to 23, wherein Y 2 is a group represented by the following formula (7), (8) or (9).
本発明のポリヒドロキシアミド組成物から得られるポリベンゾオキサゾール樹脂フィルムは、耐熱性が高く、線膨張係数が小さい。そのため、前記ポリベンゾオキサゾール樹脂フィルムは、電子デバイス用基板として有用である。 The polybenzoxazole resin film obtained from the polyhydroxyamide composition of the present invention has high heat resistance and a small coefficient of linear expansion. Therefore, the polybenzoxazole resin film is useful as a substrate for an electronic device.
[電子デバイス用基板製造用ポリヒドロキシアミド組成物]
本発明の電子デバイス用基板製造用ポリヒドロキシアミド組成物は、(A)所定の構造のポリヒドロキシアミド、及び(B)有機溶媒を含むものである。
[Polyhydroxyamide composition for manufacturing substrates for electronic devices]
The polyhydroxyamide composition for producing a substrate for an electronic device of the present invention contains (A) a polyhydroxyamide having a predetermined structure and (B) an organic solvent.
[(A)ポリヒドロキシアミド]
(A)成分であるポリヒドロキシアミドは、下記式(1)で表される単位及び下記式(2)で表される単位を含むものである。
The polyhydroxyamide as a component (A) contains a unit represented by the following formula (1) and a unit represented by the following formula (2).
式中、X1は、窒素原子と結合する炭素原子に隣接する炭素原子上にヒドロキシ基を有するビフェニルジイル基である。 In the formula, X 1 is a biphenyldiyl group having a hydroxy group on a carbon atom adjacent to the carbon atom bonded to the nitrogen atom.
X1として具体的には、下記式(4)で表される基が好ましい。
式中、R1〜R6は、互いに独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、又はハロゲン原子で置換されていてもよい、炭素数1〜20のアルキル基、炭素数2〜20のアルケニル基、炭素数2〜20のアルキニル基、炭素数6〜20のアリール基若しくは炭素数2〜20のヘテロアリール基を表す。破線は、結合手を表す。 In the formula, R 1 to R 6 may be substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a halogen atom independently of each other, an alkyl group having 1 to 20 carbon atoms, and 2 carbon atoms. It represents an alkenyl group of ~ 20, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms. The dashed line represents the bond.
前記アルキル基は、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、メチル基、エチル基、n−プロピル基、イソプロピル基、シクロプロピル基、n−ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基、シクロブチル基、1−メチル−シクロプロピル基、2−メチル−シクロプロピル基、n−ペンチル基、1−メチル−n−ブチル基、2−メチル−n−ブチル基、3−メチル−n−ブチル基、1,1−ジメチル−n−プロピル基、1,2−ジメチル−n−プロピル基、2,2−ジメチル−n−プロピル基、1−エチル−n−プロピル基、シクロペンチル基、1−メチル−シクロブチル基、2−メチル−シクロブチル基、3−メチル−シクロブチル基、1,2−ジメチル−シクロプロピル基、2,3−ジメチル−シクロプロピル基、1−エチル−シクロプロピル基、2−エチル−シクロプロピル基、n−ヘキシル基、1−メチル−n−ペンチル基、2−メチル−n−ペンチル基、3−メチル−n−ペンチル基、4−メチル−n−ペンチル基、1,1−ジメチル−n−ブチル基、1,2−ジメチル−n−ブチル基、1,3−ジメチル−n−ブチル基、2,2−ジメチル−n−ブチル基、2,3−ジメチル−n−ブチル基、3,3−ジメチル−n−ブチル基、1−エチル−n−ブチル基、2−エチル−n−ブチル基、1,1,2−トリメチル−n−プロピル基、1,2,2−トリメチル−n−プロピル基、1−エチル−1−メチル−n−プロピル基、1−エチル−2−メチル−n−プロピル基、シクロヘキシル基、1−メチル−シクロペンチル基、2−メチル−シクロペンチル基、3−メチル−シクロペンチル基、1−エチル−シクロブチル基、2−エチル−シクロブチル基、3−エチル−シクロブチル基、1,2−ジメチル−シクロブチル基、1,3−ジメチル−シクロブチル基、2,2−ジメチル−シクロブチル基、2,3−ジメチル−シクロブチル基、2,4−ジメチル−シクロブチル基、3,3−ジメチル−シクロブチル基、1−n−プロピル−シクロプロピル基、2−n−プロピル−シクロプロピル基、1−イソプロピル−シクロプロピル基、2−イソプロピル−シクロプロピル基、1,2,2−トリメチル−シクロプロピル基、1,2,3−トリメチル−シクロプロピル基、2,2,3−トリメチル−シクロプロピル基、1−エチル−2−メチル−シクロプロピル基、2−エチル−1−メチル−シクロプロピル基、2−エチル−2−メチル−シクロプロピル基、2−エチル−3−メチル−シクロプロピル基等が挙げられる。 The alkyl group may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group and an isobutyl group. sec-butyl group, tert-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl Group, 3-Methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n- Propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl -Cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n -Pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2, 3-Dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-Methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl- Cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2 -N-propyl-cyclopropyl group, 1-isopropyl-cyclopropyl group, 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2 , 2,3-trimethyl-Cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1 -Methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group and the like can be mentioned.
前記アルケニル基は、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、エテニル基、n−1−プロペニル基、n−2−プロペニル基、1−メチルエテニル基、n−1−ブテニル基、n−2−ブテニル基、n−3−ブテニル基、2−メチル−1−プロペニル基、2−メチル−2−プロペニル基、1−エチルエテニル基、1−メチル−1−プロペニル基、1−メチル−2−プロペニル基、n−1−ペンテニル基、n−1−デセニル基、n−1−エイコセニル基等が挙げられる。 The alkenyl group may be linear, branched or cyclic, and specific examples thereof include an ethenyl group, an n-1-propenyl group, an n-2-propenyl group, a 1-methylethenyl group and an n-1- Butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1 -Methyl-2-propenyl group, n-1-pentenyl group, n-1-decenyl group, n-1-eicosenyl group and the like can be mentioned.
前記アルキニル基は、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、エチニル基、n−1−プロピニル基、n−2−プロピニル基、n−1−ブチニル基、n−2−ブチニル基、n−3−ブチニル基、1−メチル−2−プロピニル基、n−1−ペンチニル基、n−2−ペンチニル基、n−3−ペンチニル基、n−4−ペンチニル基、1−メチル−n−ブチニル基、2−メチル−n−ブチニル基、3−メチル−n−ブチニル基、1,1−ジメチル−n−プロピニル基、n−1−ヘキシニル基、n−1−デシニル基、n−1−ペンタデシニル基、n−1−エイコシニル基等が挙げられる。 The alkynyl group may be linear, branched or cyclic, and specific examples thereof include an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, an n-1-butynyl group and an n-. 2-butynyl group, n-3-butynyl group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1 -Methyl-n-butynyl group, 2-methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decynyl group , N-1-pentadecynyl group, n-1-eicosynyl group and the like.
前記アリール基の具体例としては、フェニル基、1−ナフチル基、2−ナフチル基、1−アントリル基、2−アントリル基、9−アントリル基、1−フェナントリル基、2−フェナントリル基、3−フェナントリル基、4−フェナントリル基、9−フェナントリル基等が挙げられる。 Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, and a 3-phenanthryl group. Examples include a group, a 4-phenanthryl group, a 9-phenanthryl group and the like.
前記ヘテロアリール基の具体例としては、2−チエニル基、3−チエニル基、2−フラニル基、3−フラニル基、2−オキサゾリル基、4−オキサゾリル基、5−オキサゾリル基、3−イソオキサゾリル基、4−イソオキサゾリル基、5−イソオキサゾリル基、2−チアゾリル基、4−チアゾリル基、5−チアゾリル基、3−イソチアゾリル基、4−イソチアゾリル基、5−イソチアゾリル基、2−イミダゾリル基、4−イミダゾリル基、2−ピリジル基、3−ピリジル基、4−ピリジル基等が挙げられる。 Specific examples of the heteroaryl group include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group and 3-isoxazolyl group. 4-isooxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4-imidazolyl group, Examples thereof include 2-pyridyl group, 3-pyridyl group and 4-pyridyl group.
これらのうち、R1〜R6としては、水素原子、メチル基、ハロゲン原子、フェニル基が好ましく、水素原子、メチル基、ハロゲン原子がより好ましく、水素原子が最も好ましい。 Of these, as R 1 to R 6 , a hydrogen atom, a methyl group, a halogen atom and a phenyl group are preferable, a hydrogen atom, a methyl group and a halogen atom are more preferable, and a hydrogen atom is the most preferable.
X1としては、下記式(4')で表される基が最も好ましい。
式(1)中、Y1は、炭素数6〜14の2価の芳香族基を表す。式(2)中、Y2は、下記式(3)で表される基を表す。
式(3)中、Z1は、−O−、−NH−又は−N(R)−を表し、Rは、炭素数1〜10のアルキル基を表す。Rで表されるアルキル基として具体的には、前述したものと同様のものが挙げられる。Z1としては、−O−、−NH−が好ましい。 In formula (3), Z 1 represents −O−, −NH− or −N (R) −, and R represents an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group represented by R include the same as those described above. As Z 1 , -O- and -NH- are preferable.
式(3)中、Ar1及びAr2は、互いに独立して、炭素数6〜14の2価の芳香族基を表す。 In formula (3), Ar 1 and Ar 2 represent divalent aromatic groups having 6 to 14 carbon atoms independently of each other.
Y1、Ar1及びAr2で表される2価の芳香族基としては、フェニレン基、ナフチレン基、アントラセンジイル基、フェナントレンジイル基、ビフェニルジイル基等が挙げられ、これらの基の水素原子の一部又は全部が、置換基で置換されていてもよい。 Examples of the divalent aromatic group represented by Y 1 , Ar 1 and Ar 2 include a phenylene group, a naphthylene group, an anthracendyl group, a phenanthrangeyl group, a biphenyldiyl group and the like, and the hydrogen atom of these groups Part or all may be substituted with a substituent.
Y1としては、下記式(5)で表される基が好ましく、Y2としては下記式(6)で表される基が好ましい。
式中、Z1は、前記と同じである。R7〜R18は、互いに独立して、水素原子、ヒドロキシ基、ハロゲン原子、ニトロ基、シアノ基、又はハロゲン原子で置換されていてもよい、炭素数1〜20のアルキル基、炭素数2〜20のアルケニル基、炭素数2〜20のアルキニル基、炭素数6〜20のアリール基若しくは炭素数2〜20のヘテロアリール基を表す。破線は、結合手を表す。前記アルキル基、アルケニル基、アルキニル基、アリール基及びヘテロアリール基としては、前述したものと同様のものが挙げられる。 In the formula, Z 1 is the same as described above. R 7 to R 18 may be substituted with a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, or a halogen atom independently of each other, an alkyl group having 1 to 20 carbon atoms, and 2 carbon atoms. Represents an alkenyl group of ~ 20, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms. The dashed line represents the bond. Examples of the alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group include those similar to those described above.
R7〜R18としては、水素原子、炭素数1〜20のアルキル基、ハロゲン原子、フェニル基が好ましく、水素原子、炭素数1〜20のアルキル基、ハロゲン原子がより好ましく、水素原子、メチル基、ハロゲン原子がより一層好ましく、水素原子が最も好ましい。 As R 7 to R 18 , a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom and a phenyl group are preferable, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and a halogen atom are more preferable, and a hydrogen atom and a methyl are used. A group and a halogen atom are more preferable, and a hydrogen atom is most preferable.
Y2としては、下記式(7)、(8)又は(9)で表される基が最も好ましい。
式(1)及び(2)中、n及びmは、0<n<100、0<m<100、及び0<n+m≦100を満たす正数を表す。n及びmは、溶解性と耐熱性の点から、5≦n≦25、75≦m≦95、及び80≦n+m≦100を満たす正数が好ましく、10≦n≦25、75≦m≦90、及び85≦n+m≦100を満たす正数がより好ましく、20≦n≦25、75≦m≦80、及び95≦n+m≦100を満たす正数がより一層好ましい。 In the formulas (1) and (2), n and m represent positive numbers satisfying 0 <n <100, 0 <m <100, and 0 <n + m ≦ 100. From the viewpoint of solubility and heat resistance, n and m are preferably positive numbers satisfying 5 ≦ n ≦ 25, 75 ≦ m ≦ 95, and 80 ≦ n + m ≦ 100, and 10 ≦ n ≦ 25, 75 ≦ m ≦ 90. , And a positive number satisfying 85 ≦ n + m ≦ 100 is more preferable, and a positive number satisfying 20 ≦ n ≦ 25, 75 ≦ m ≦ 80, and 95 ≦ n + m ≦ 100 is even more preferable.
前記ポリヒドロキシアミドは、式(1)で表される単位及び式(2)で表される単位以外の単位(以下、その他の単位ともいう。)を含んでもよい。 The polyhydroxyamide may contain a unit represented by the formula (1) and a unit other than the unit represented by the formula (2) (hereinafter, also referred to as another unit).
前記ポリヒドロキシアミドの重量平均分子量(Mw)は、5,000〜1,000,000が好ましく、10,000〜100,000がより好ましく、20,000〜100,000がより一層好ましい。なお、本発明においてMwは、ゲルパーミエーションクロマトグラフィー(GPC)分析による標準ポリスチレン換算で得られる平均分子量である。 The weight average molecular weight (Mw) of the polyhydroxyamide is preferably 5,000 to 1,000,000, more preferably 10,000 to 100,000, and even more preferably 20,000 to 100,000. In the present invention, Mw is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (GPC) analysis.
[ポリヒドロキシアミドの製造方法]
前記ポリヒドロキシアミドは、下記式(12)で表されるジアミン化合物、下記式(13)で表されるジカルボン酸誘導体、及び下記式(14)で表されるジカルボン酸誘導体を、溶媒中で、必要に応じて塩基の存在下で縮合重合させることによって製造することができる。
The polyhydroxyamide contains a diamine compound represented by the following formula (12), a dicarboxylic acid derivative represented by the following formula (13), and a dicarboxylic acid derivative represented by the following formula (14) in a solvent. If necessary, it can be produced by condensation polymerization in the presence of a base.
このとき、式(13)で表されるジカルボン酸誘導体の使用量は、式(12)で表されるジアミン化合物1モルに対して、0.05〜0.25モルが好ましく、0.10〜0.25モルがより好ましく、0.20〜0.25モルがより一層好ましい。また、式(14)で表されるジカルボン酸誘導体の使用量は、式(12)で表されるジアミン化合物1モルに対して、0.75〜0.95モルが好ましく、0.75〜0.90モルがより好ましく、0.75〜0.80モルがより一層好ましい。 At this time, the amount of the dicarboxylic acid derivative represented by the formula (13) is preferably 0.05 to 0.25 mol, preferably 0.1 to 10 mol, with respect to 1 mol of the diamine compound represented by the formula (12). 0.25 mol is more preferable, and 0.20 to 0.25 mol is even more preferable. The amount of the dicarboxylic acid derivative represented by the formula (14) is preferably 0.75 to 0.95 mol, preferably 0.75 to 0, based on 1 mol of the diamine compound represented by the formula (12). .90 mol is more preferred, and 0.75 to 0.80 mol is even more preferred.
前記縮合重合反応に用いる溶媒としては、N−メチル−2−ピロリドン(NMP)、N−エチル−2−ピロリドン、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、ヘキサメチルリン酸トリアミド、3−メトキシ−N,N−ジメチルプロパンアミド、3−ブトキシ−N,N−ジメチルプロパンアミド等が挙げられる。 Examples of the solvent used for the condensation polymerization reaction include N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and hexamethylphosphoric acid triamide, 3. Examples thereof include −methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.
前記塩基としては、炭酸カリウム、水酸化カリウム、炭酸ナトリウム、水酸化ナトリウム、炭酸水素ナトリウム、ナトリウムエトキシド、酢酸ナトリウム、炭酸リチウム、水酸化リチウム、酸化リチウム、酢酸カリウム、酸化マグネシウム、酸化カルシウム、水酸化バリウム、リン酸三リチウム、リン酸三ナトリウム、リン酸三カリウム、フッ化セシウム、酸化アルミニウム、アンモニア、n−プロピルアミン、トリメチルアミン、トリエチルアミン、ジイソプロピルアミン、ジイソプロピルエチルアミン、N−メチルピペリジン、2,2,6,6−テトラメチル−N−メチルピペリジン、ピリジン、4−ジメチルアミノピリジン、N−メチルモルホリン等が挙げられる。塩基の添加量は、ジアミン化合物1モルに対して、0.5〜3.0モルが好ましく、0.8〜2.0モルがより好ましい。 Examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, sodium ethoxydo, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, and water. Barium oxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2 , 6,6-Tetramethyl-N-methylpiperidin, pyridine, 4-dimethylaminopyridine, N-methylmorpholin and the like. The amount of the base added is preferably 0.5 to 3.0 mol, more preferably 0.8 to 2.0 mol, relative to 1 mol of the diamine compound.
反応温度は、用いる溶媒の融点から溶媒の沸点までの範囲で適宜設定すればよく、通常−20〜100℃程度であり、好ましくは−10〜100℃程度である。また、重合の反応時間は、通常1〜48時間程度であり、好ましくは1〜24時間程度である。反応終了後は、定法に従って後処理をし、必要に応じて再沈殿等の精製を施して目的物を得ることができる。 The reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, and is usually about -20 to 100 ° C, preferably about -10 to 100 ° C. The reaction time of the polymerization is usually about 1 to 48 hours, preferably about 1 to 24 hours. After completion of the reaction, post-treatment is carried out according to a conventional method, and if necessary, purification such as reprecipitation can be performed to obtain the desired product.
[(B)有機溶媒]
(B)成分の有機溶媒としては、前記ポリヒドロキシアミドを溶解できるものである限り特に限定されないが、平坦性の高いポリベンゾオキサゾール樹脂フィルムを再現性よく得ることを考慮すると、下記式(S1)で表されるアミド類、下記式(S2)で表されるアミド類及び下記式(S3)で表されるアミド類から選ばれる少なくとも1種を含むものが好ましい。
The organic solvent of the component (B) is not particularly limited as long as it can dissolve the polyhydroxyamide, but in consideration of obtaining a highly flat polybenzoxazole resin film with good reproducibility, the following formula (S1) It is preferable that the amides represented by the following formula (S2) and at least one selected from the amides represented by the following formula (S2) and the amides represented by the following formula (S3) are contained.
式中、R21及びR22は、互いに独立して、炭素数1〜10のアルキル基を表す。R23は、水素原子、又は炭素数1〜10のアルキル基を表す。前記アルキル基としては、直鎖状、分岐状、環状のいずれでもよく、具体的には、メチル基、エチル基、n−プロピル基、イソプロピル基、シクロプロピル基、n−ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基等が挙げられる。 In the formula, R 21 and R 22 independently represent an alkyl group having 1 to 10 carbon atoms. R 23 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group or an isobutyl group. Examples thereof include sec-butyl group and tert-butyl group.
また、式(S1)中、aは、自然数を表すが、1〜3の自然数が好ましく、1又は2がより好ましい。 Further, in the formula (S1), a represents a natural number, but a natural number of 1 to 3 is preferable, and 1 or 2 is more preferable.
式(S1)で表される有機溶媒としては、2−メトキシ−N,N−ジメチルアセトアミド、3−メトキシ−N,N−ジメチルプロピルアミド、3−エトキシ−N,N−ジメチルプロピルアミド、3−プロポキシ−N,N−ジメチルプロピルアミド、3−イソプロポキシ−N,N−ジメチルプロピルアミド、3−ブトキシ−N,N−ジメチルプロピルアミド、3−sec−ブトキシ−N,N−ジメチルプロピルアミド、3−tert−ブトキシ−N,N−ジメチルプロピルアミド等が挙げられる。 Examples of the organic solvent represented by the formula (S1) include 2-methoxy-N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide and 3-. Propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3 -Tart-butoxy-N, N-dimethylpropylamide and the like can be mentioned.
式(S2)で表される有機溶媒としては、N−メチル−2−ピロリドン(NMP)、N−エチル−2−ピロリドン、N−プロピル−2−ピロリドン、N−ブチル−2−ピロリドン等が挙げられる。 Examples of the organic solvent represented by the formula (S2) include N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone and the like. Be done.
式(S3)で表される有機溶媒としては、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N,N−ジメチルプロピオンアミド、N,N−ジメチルイソブチルアミド等が挙げられる。 Examples of the organic solvent represented by the formula (S3) include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, N, N-dimethylisobutyramide and the like.
また、単独では前記ポリヒドロキシアミドを溶解しない溶媒であっても、溶解性を損なわない範囲であれば前記溶媒に加えて使用することができる。その具体例としては、エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、ブチルカルビトール、エチルカルビトールアセテート、エチレングリコール、1−メトキシ−2−プロパノール、1−エトキシ−2−プロパノール、1−ブトキシ−2−プロパノール、1−フェノキシ−2−プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール−1−モノメチルエーテル−2−アセテート、プロピレングリコール−1−モノエチルエーテル−2−アセテート、ジプロピレングリコール、2−(2−エトキシプロポキシ)プロパノール、乳酸メチル、乳酸エチル、乳酸n−プロピル、乳酸n−ブチル、乳酸イソアミル等が挙げられる。 Further, even if the solvent does not dissolve the polyhydroxyamide alone, it can be used in addition to the solvent as long as the solubility is not impaired. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-butoxy-2-propanol. , 1-Phenoxy-2-propanol, Propylene Glycol Monoacetate, Propylene Glycol Diacetate, Propylene Glycol-1-monomethyl Ether-2-acetate, Propylene Glycol-1-monoethyl Ether-2-acetate, Dipropylene Glycol, 2- Examples thereof include (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and the like.
前記ポリヒドロキシアミド組成物中、ポリヒドロキシアミドの濃度は、作製する樹脂フィルムの厚み、組成物の粘度等を勘案して適宜設定するものではあるが、通常1〜30質量%程度、好ましくは1〜20質量%程度である。 In the polyhydroxyamide composition, the concentration of the polyhydroxyamide is appropriately set in consideration of the thickness of the resin film to be produced, the viscosity of the composition, etc., but is usually about 1 to 30% by mass, preferably 1. It is about 20% by mass.
[ポリベンゾオキサゾール樹脂フィルム]
本発明のポリベンゾオキサゾール樹脂フィルムは、前記ポリヒドロキシアミド組成物から得られるものである。前記ポリベンゾオキサゾール樹脂フィルムの製造方法は、前記ポリヒドロキシアミド組成物を基材上に塗布する工程、及び加熱して溶媒を蒸発させ、ポリヒドロキシアミドを閉環させる工程を含むものである。
[Polybenzoxazole resin film]
The polybenzoxazole resin film of the present invention is obtained from the polyhydroxyamide composition. The method for producing the polybenzoxazole resin film includes a step of applying the polyhydroxyamide composition onto a substrate and a step of heating to evaporate the solvent to close the polyhydroxyamide.
前記基材としては、ガラス、プラスチック(ポリカーボネート、ポリメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース、ABS、AS、ノルボルネン系樹脂等)、金属(シリコンウエハ等)、SiNやSiO膜等の蒸着膜付ガラス基板、木材、紙、スレート等が挙げられるが、特に、生産性の観点から、ガラス、金属(シリコンウエハ等)等が好ましい。なお、基材表面は、単一の材料で構成されていてもよく、2以上の材料で構成されていてもよい。 Examples of the base material include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.), SiN, and the like. Examples thereof include a glass substrate with a vapor-deposited film such as a SiO film, wood, paper, slate, etc., and in particular, glass, metal (silicon wafer, etc.) and the like are preferable from the viewpoint of productivity. The surface of the base material may be made of a single material or may be made of two or more materials.
前記ポリヒドロキシアミド組成物を塗布する方法としては、特に限定されないが、例えば、キャストコート法、スピンコート法、ブレードコート法、ディップコート法、ロールコート法、バーコート法、ダイコート法、インクジェット法、印刷法(凸版、凹版、平版、スクリーン印刷等)等が挙げられる。 The method for applying the polyhydroxyamide composition is not particularly limited, and for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, and the like. Printing methods (letter plate, intaglio plate, lithographic plate, screen printing, etc.) and the like can be mentioned.
前記有機溶媒を蒸発させるときの加熱温度は、50〜200℃が好ましく、50〜150℃がより好ましい。また、そのときの加熱時間は、5分間〜5時間が好ましく、5分間〜3時間がより好ましい。 The heating temperature for evaporating the organic solvent is preferably 50 to 200 ° C, more preferably 50 to 150 ° C. The heating time at that time is preferably 5 minutes to 5 hours, more preferably 5 minutes to 3 hours.
このとき、閉環するための加熱温度は、通常50〜550℃の範囲内で適宜決定されるが、好ましくは200℃以上、また、好ましくは500℃以下である。加熱温度をこのようにすることで、得られる膜の脆弱化を防ぎつつ、オキサゾール化反応を十分に進行させることが可能となる。加熱時間は、加熱温度によって異なるため一概に規定できないが、通常5分〜5時間である。また、閉環率は、50〜100%の範囲であればよい。 At this time, the heating temperature for ring closure is usually appropriately determined within the range of 50 to 550 ° C, but is preferably 200 ° C or higher, and preferably 500 ° C or lower. By setting the heating temperature in this way, it becomes possible to sufficiently proceed the oxazoleization reaction while preventing the resulting film from becoming fragile. The heating time cannot be unconditionally specified because it varies depending on the heating temperature, but it is usually 5 minutes to 5 hours. The ring closure rate may be in the range of 50 to 100%.
加熱態様の好ましい一例としては、50〜100℃で5分間〜2時間加熱した後に、そのまま段階的に加熱温度を上昇させて最終的に375℃超〜450℃で30分〜4時間加熱する手法が挙げられる。特に、50〜100℃で5分間〜2時間加熱した後に、100℃超〜375℃で5分間〜2時間、最後に375℃超〜450℃で30分〜4時間加熱することが好ましい。 As a preferable example of the heating mode, a method of heating at 50 to 100 ° C. for 5 minutes to 2 hours, then gradually increasing the heating temperature and finally heating at 375 ° C. to 450 ° C. for 30 minutes to 4 hours. Can be mentioned. In particular, it is preferable to heat at 50 to 100 ° C. for 5 minutes to 2 hours, then at 100 ° C. to 375 ° C. for 5 minutes to 2 hours, and finally at 375 ° C. to 450 ° C. for 30 minutes to 4 hours.
前記樹脂フィルムの厚さは、特に限定されないが、後述する電子デバイスの基板として使用する場合、通常1〜100μm程度、十分な自己支持性と柔軟性の観点から、好ましくは5〜75μm程度、より好ましくは5〜50μm程度である。 The thickness of the resin film is not particularly limited, but when used as a substrate for an electronic device described later, it is usually about 1 to 100 μm, preferably about 5 to 75 μm from the viewpoint of sufficient self-support and flexibility. It is preferably about 5 to 50 μm.
前記樹脂フィルム形成後、該樹脂フィルムを基材から剥離して回収することができる。フィルムの剥離は、水への浸漬、波長308nmの紫外光を用いたレーザーリフトオフ法等によって行うことができる。 After forming the resin film, the resin film can be peeled off from the substrate and recovered. The film can be peeled off by immersion in water, a laser lift-off method using ultraviolet light having a wavelength of 308 nm, or the like.
このようにして得られた本発明のポリベンゾオキサゾール樹脂フィルムは、耐熱性が高く、線膨張係数が小さいものである。具体的には、本発明のポリベンゾオキサゾール樹脂フィルムは、5%重量減少温度が600℃以上であり、50〜400℃の線膨張係数が8ppm/℃以下であることが好ましい。 The polybenzoxazole resin film of the present invention thus obtained has high heat resistance and a small coefficient of linear expansion. Specifically, the polybenzoxazole resin film of the present invention preferably has a 5% weight loss temperature of 600 ° C. or higher and a linear expansion coefficient of 50 to 400 ° C. of 8 ppm / ° C. or lower.
[電子デバイス]
本発明の電子デバイスは、前述したポリベンゾオキサゾール樹脂フィルムを基板として備えるものである。前記電子デバイスとしては、有機EL素子、液晶ディスプレイ、有機ELディスプレイ、光半導体(LED)素子、電子ペーパー、固体撮像素子、有機薄膜太陽電池、色素増感太陽電池、有機薄膜トランジスタ(TFT)、3Dディスプレイ、タッチパネル等が挙げられる。
[Electronic device]
The electronic device of the present invention comprises the above-mentioned polybenzoxazole resin film as a substrate. Examples of the electronic device include an organic EL element, a liquid crystal display, an organic EL display, an optical semiconductor (LED) element, an electronic paper, a solid image pickup element, an organic thin film solar cell, a dye sensitized solar cell, an organic thin film transistor (TFT), and a 3D display. , Touch panel and the like.
本発明の電子デバイスの製造方法の一例について説明する。前述の方法によって、基材上に前記ポリヒドロキシアミド組成物を塗布し、加熱して、基材に固定されたポリベンゾオキサゾール樹脂フィルムを形成する。次に、前記樹脂フィルムの上に、所望の回路を形成し、その後、前記樹脂フィルムをカットし、この回路が形成された樹脂フィルムを前記基材から剥離して、回路が形成された樹脂フィルムと基材とを分離することで、電子デバイスを製造することができる。 An example of the method for manufacturing the electronic device of the present invention will be described. By the above-mentioned method, the polyhydroxyamide composition is applied onto a substrate and heated to form a polybenzoxazole resin film immobilized on the substrate. Next, a desired circuit is formed on the resin film, then the resin film is cut, and the resin film on which the circuit is formed is peeled off from the base material to form the circuit. By separating the base material from the base material, an electronic device can be manufactured.
以下、実施例及び比較例を示して本発明を具体的に説明するが、本発明は下記実施例に限定されない。なお、下記例において使用した化合物、並びに重量平均分子量及び分子量分布の測定方法は、以下のとおりである。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The compounds used in the following examples, and the methods for measuring the weight average molecular weight and the molecular weight distribution are as follows.
NMP:N−メチルピロリドン
HAB:4,4'−ジアミノ−3,3'−ジヒドロキシビフェニル
4BP:3,3'−ジアミノ−4,4'−ジヒドロキシビフェニル
TPC:テレフタル酸クロリド
IPC:イソフタル酸クロリド
DEDC:4,4'−ジフェニルエーテルジカルボン酸クロリド
NMP: N-methylpyrrolidone HAB: 4,4'-diamino-3,3'-dihydroxybiphenyl 4BP: 3,3'-dihydroxybiphenyl TPC: terephthalic acid chloride IPC: isophthalic acid chloride DEDC: 4,4'-Diphenyl ether dicarboxylic acid chloride
[重量平均分子量(Mw)及び分子量分布(Mw/Mn)の測定]
ポリマーのMwとMw/Mnは、日本分光(株)製GPC装置(カラム:昭和電工(株)製Shodex(登録商標)カラムKF803L及びKF805L、溶出溶媒:ジメチルホルムアミド、流量:1.0mL/分、カラム温度:50℃、Mw:標準ポリスチレン換算値)を用いて測定した。
[Measurement of weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The polymers Mw and Mw / Mn are GPC equipment manufactured by JASCO Corporation (column: Shodex® columns KF803L and KF805L manufactured by Showa Denko Corporation, elution solvent: dimethylformamide, flow rate: 1.0 mL / min, Column temperature: 50 ° C., Mw: standard polystyrene conversion value) was used for measurement.
[1]ポリマーの合成
[実施例1]ポリヒドロキシアミドP1の合成
HAB1.052g(4.87mmol)をNMP27.6gに溶かし、ピリジン0.963g(12.18mmol)を添加した後、DEDC1.149g(3.90mmol)とTPC0.198g(0.97mmol)とを添加し、室温にて24時間攪拌した。その後、得られた溶液を純水500mLへ投入した。得られた沈殿物を濾別後、70℃で24時間減圧乾燥し、目的のポリヒドロキシアミドP1を得た。GPC測定によるポリヒドロキシアミドP1のMwは60,300、Mw/Mnは2.8であった。
[1] Polymer Synthesis [Example 1] Polyhydroxyamide P1 synthesis HAB 1.052 g (4.87 mmol) was dissolved in NMP 27.6 g, pyridine 0.963 g (12.18 mmol) was added, and then DEDC 1.149 g (DEDC 1.149 g). 3.90 mmol) and TPC 0.198 g (0.97 mmol) were added, and the mixture was stirred at room temperature for 24 hours. Then, the obtained solution was put into 500 mL of pure water. The obtained precipitate was filtered off and then dried under reduced pressure at 70 ° C. for 24 hours to obtain the desired polyhydroxyamide P1. The Mw of the polyhydroxyamide P1 was 60,300 and the Mw / Mn was 2.8 as measured by GPC.
[実施例2、比較例1〜5]ポリヒドロキシアミドP2、ポリヒドロキシアミドCP1〜CP5の合成
実施例1と同様の方法で、ポリヒドロキシアミドP2、ポリヒドロキシアミドCP1〜CP5を合成した。使用したジカルボン酸塩化物の種類と使用量、ジアミンの種類と使用量、NMPの使用量、Mw、及びMw/Mnを表1に示す。
[Example 2, Comparative Examples 1 to 5] Synthesis of polyhydroxyamide P2 and polyhydroxyamide CP1 to CP5 Polyhydroxyamide P2 and polyhydroxyamide CP1 to CP5 were synthesized in the same manner as in Example 1. Table 1 shows the types and amounts of dicarboxylic acid chlorides used, the types and amounts of diamines used, the amounts of NMP used, Mw, and Mw / Mn.
[2]ポリヒドロキシアミドの溶解性の評価
作製したポリヒドロキシアミド1gをNMP20gに入れ、室温で48時間攪拌し、再溶解させた。
結果を表1に併記する。なお、溶解性の評価基準は、以下のとおりである。
○:重合中溶解し、精製後も再溶解する。
△:重合中溶解するが、精製後は再溶解しない。
×:重合中析出する。
[2] Evaluation of Solubility of Polyhydroxyamide 1 g of the produced polyhydroxyamide was placed in 20 g of NMP, stirred at room temperature for 48 hours, and redissolved.
The results are also shown in Table 1. The evaluation criteria for solubility are as follows.
◯: Dissolves during polymerization and redissolves after purification.
Δ: Dissolves during polymerization, but does not redissolve after purification.
X: Precipitates during polymerization.
[2]ポリベンゾオキサゾール樹脂フィルムの作製、及びその評価
[キュア前膜厚・剥離方法]
実施例1〜2及び比較例5で作製したポリヒドロキシアミド1gを、NMP20mLに溶解させ、ポリヒドロキシアミド組成物を調製した。
得られた各組成物を、100mm×100mmガラス基板上にバーコーターを用いて塗布し、ホットプレート上で80℃30分ベークした。その後、140℃で30分間加熱し、加熱温度を210℃まで昇温(10℃/分、以下同様)し、210℃で30分間、加熱温度を300℃まで昇温し、300℃で30分間、加熱温度を400℃まで昇温し、400℃で60分間加熱した。昇温の間、膜付き基板をオーブンから取り出すことはせず、オーブン内で加熱した。得られた塗布膜の膜厚は、接触式膜厚測定器((株)ULVAC製Dektak 3ST)で測定した。膜厚の測定結果を表2に示す。その後、ガラス基板ごと、1Lビーカー内の70℃の純水中に静置し、フィルムの剥離を行った。
[2] Preparation of polybenzoxazole resin film and its evaluation [pre-cure film thickness / peeling method]
1 g of the polyhydroxyamide prepared in Examples 1 and 2 and Comparative Example 5 was dissolved in 20 mL of NMP to prepare a polyhydroxyamide composition.
Each of the obtained compositions was applied onto a 100 mm × 100 mm glass substrate using a bar coater, and baked on a hot plate at 80 ° C. for 30 minutes. Then, it is heated at 140 ° C. for 30 minutes, the heating temperature is raised to 210 ° C. (10 ° C./min, the same applies hereinafter), the heating temperature is raised to 210 ° C. for 30 minutes, the heating temperature is raised to 300 ° C., and the heating temperature is raised to 300 ° C. for 30 minutes. The heating temperature was raised to 400 ° C. and heated at 400 ° C. for 60 minutes. During the temperature rise, the substrate with the membrane was not removed from the oven and was heated in the oven. The film thickness of the obtained coating film was measured with a contact type film thickness measuring instrument (Dektak 3ST manufactured by ULVAC, Inc.). The measurement results of the film thickness are shown in Table 2. Then, the whole glass substrate was allowed to stand in pure water at 70 ° C. in a 1 L beaker to peel off the film.
[線膨張係数]
得られたフィルムから20mm×5mmの短冊を作製し、TMA-4000SA(ブルカー・エイエックスエス(株)製)を用いて、50℃から400℃まで、10℃/分の条件で昇温し、線膨張係数を測定した。結果を表2に示す。
[Coefficient of linear expansion]
A strip of 20 mm × 5 mm was prepared from the obtained film, and the temperature was raised from 50 ° C. to 400 ° C. at 10 ° C./min using TMA-4000SA (manufactured by Bruker AXS Co., Ltd.). The coefficient of linear expansion was measured. The results are shown in Table 2.
[5%重量減少温度]
得られたフィルムから20mm×3mmの短冊を作製し、TGA-DTA-2000SR(ブルカー・エイエックスエス(株)製)を用いて、50℃から600℃まで重量減少を測定し、5%重量減少温度を確認した。結果を表2に示す。なお、600℃で5%重量減少しない場合は、600℃<と記載した。
[5% weight loss temperature]
A 20 mm x 3 mm strip was prepared from the obtained film, and the weight loss was measured from 50 ° C to 600 ° C using TGA-DTA-2000SR (manufactured by Bruker AXS Co., Ltd.), and the weight was reduced by 5%. I checked the temperature. The results are shown in Table 2. When the weight did not decrease by 5% at 600 ° C, it was described as 600 ° C <.
[自己支持性]
作製したフィルムを剥離し、その後、全方向に90°曲げた後、特に変化が無いものを自己支持性があるものとした。
結果を表2に示す。なお、自己支持性の評価基準は、以下のとおりである。
○:自己支持性あり。90度にまげても割れない
△:自己支持性はあるが、曲げて割れる
×:自己支持性なし
××:基板上で分解
[Self-supporting]
The produced film was peeled off, then bent by 90 ° in all directions, and then the film having no particular change was regarded as having self-supporting property.
The results are shown in Table 2. The evaluation criteria for self-support are as follows.
○: Self-supporting. Does not crack even when bent 90 degrees Δ: Self-supporting, but bends and cracks ×: No self-supporting ××: Disassembled on the substrate
Claims (24)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016057144 | 2016-03-22 | ||
JP2016057144 | 2016-03-22 | ||
JP2018507311A JP6904332B2 (en) | 2016-03-22 | 2017-03-17 | Organic electroluminescence device |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2018507311A Division JP6904332B2 (en) | 2016-03-22 | 2017-03-17 | Organic electroluminescence device |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2021178962A true JP2021178962A (en) | 2021-11-18 |
Family
ID=59900382
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2018507311A Active JP6904332B2 (en) | 2016-03-22 | 2017-03-17 | Organic electroluminescence device |
JP2021101262A Pending JP2021178962A (en) | 2016-03-22 | 2021-06-18 | Polyhydroxyamide composition for manufacturing substrates for electronic devices, and polybenzoxazole resin film |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2018507311A Active JP6904332B2 (en) | 2016-03-22 | 2017-03-17 | Organic electroluminescence device |
Country Status (5)
Country | Link |
---|---|
JP (2) | JP6904332B2 (en) |
KR (2) | KR102382236B1 (en) |
CN (1) | CN108884316B (en) |
TW (1) | TWI774667B (en) |
WO (1) | WO2017164129A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108752580B (en) * | 2018-05-24 | 2019-08-13 | 安徽农业大学 | A kind of double anti-forge material, antifalsification label and preparation method and false-proof detection method |
CN108383998B (en) * | 2018-05-24 | 2019-10-08 | 安徽农业大学 | A high-strength humidity-responsive polyhydroxyamide and its preparation method |
CN115884864B (en) * | 2021-03-31 | 2024-04-09 | 尤尼吉可株式会社 | Semi-aromatic polyamide film and laminate obtained therefrom |
CN113651956B (en) * | 2021-08-23 | 2022-09-16 | 安徽农业大学 | Preparation method of ultrahigh-toughness branched polyamide copolymer and prepared polyamide copolymer |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6440530A (en) * | 1987-08-06 | 1989-02-10 | Prod Dev Res Inst | Production of polybenzo-oxy or thio-azole |
JP2004118123A (en) * | 2002-09-27 | 2004-04-15 | Sumitomo Bakelite Co Ltd | Positive photosensitive material for plastic optical waveguide and optical waveguide |
JP2005242343A (en) * | 2004-01-27 | 2005-09-08 | Sumitomo Bakelite Co Ltd | Positive photosensitive resin composition, semiconductor device and display component using the positive photosensitive resin composition, and method for producing semiconductor device and display component |
WO2005114724A1 (en) * | 2004-05-21 | 2005-12-01 | Jsr Corporation | Laminated body and semiconductor device |
JP2009109541A (en) * | 2007-10-26 | 2009-05-21 | Asahi Kasei Electronics Co Ltd | Negative photosensitive resin composition |
WO2011027866A1 (en) * | 2009-09-04 | 2011-03-10 | Jsr株式会社 | Process for producing substrate and composition for use in same |
WO2015087831A1 (en) * | 2013-12-11 | 2015-06-18 | 富士フイルム株式会社 | Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000128986A (en) * | 1998-10-28 | 2000-05-09 | Sumitomo Bakelite Co Ltd | Polybenzoxazole precursor and polybenzoxazole |
JP3862202B2 (en) | 2000-06-16 | 2006-12-27 | 共同印刷株式会社 | Active matrix layer and transfer method |
JP4550437B2 (en) * | 2004-01-20 | 2010-09-22 | ポリマテック株式会社 | Polybenzazole molded body and method for producing the same |
KR20070022775A (en) * | 2004-05-21 | 2007-02-27 | 제이에스알 가부시끼가이샤 | Laminates and Semiconductor Devices |
JP5299607B2 (en) | 2006-10-04 | 2013-09-25 | 東洋紡株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
CN103459467B (en) * | 2011-04-08 | 2016-04-06 | 三菱瓦斯化学株式会社 | Polybenzoxazole resin and precursor thereof |
US20160053116A1 (en) * | 2013-04-08 | 2016-02-25 | Sumitomo Bakelite Co., Ltd. | Polymer solution, polymer film, stacked composite, display element, optical element, illumination element, and production method therefor |
WO2015012385A1 (en) * | 2013-07-26 | 2015-01-29 | 日産化学工業株式会社 | Resin composition for display substrate, thin resin film for display substrate, and process for producing thin resin film for display substrate |
KR101813310B1 (en) * | 2014-06-09 | 2017-12-28 | 주식회사 엘지화학 | Composition for forming polyimide-based film and polyimide-based film prepared by using same |
-
2017
- 2017-03-17 WO PCT/JP2017/010970 patent/WO2017164129A1/en active Application Filing
- 2017-03-17 CN CN201780018985.2A patent/CN108884316B/en active Active
- 2017-03-17 KR KR1020217025205A patent/KR102382236B1/en active IP Right Grant
- 2017-03-17 KR KR1020187028067A patent/KR20180127376A/en active Application Filing
- 2017-03-17 JP JP2018507311A patent/JP6904332B2/en active Active
- 2017-03-22 TW TW106109576A patent/TWI774667B/en active
-
2021
- 2021-06-18 JP JP2021101262A patent/JP2021178962A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6440530A (en) * | 1987-08-06 | 1989-02-10 | Prod Dev Res Inst | Production of polybenzo-oxy or thio-azole |
JP2004118123A (en) * | 2002-09-27 | 2004-04-15 | Sumitomo Bakelite Co Ltd | Positive photosensitive material for plastic optical waveguide and optical waveguide |
JP2005242343A (en) * | 2004-01-27 | 2005-09-08 | Sumitomo Bakelite Co Ltd | Positive photosensitive resin composition, semiconductor device and display component using the positive photosensitive resin composition, and method for producing semiconductor device and display component |
WO2005114724A1 (en) * | 2004-05-21 | 2005-12-01 | Jsr Corporation | Laminated body and semiconductor device |
JP2009109541A (en) * | 2007-10-26 | 2009-05-21 | Asahi Kasei Electronics Co Ltd | Negative photosensitive resin composition |
WO2011027866A1 (en) * | 2009-09-04 | 2011-03-10 | Jsr株式会社 | Process for producing substrate and composition for use in same |
WO2015087831A1 (en) * | 2013-12-11 | 2015-06-18 | 富士フイルム株式会社 | Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device |
Also Published As
Publication number | Publication date |
---|---|
TW201802184A (en) | 2018-01-16 |
TWI774667B (en) | 2022-08-21 |
KR20210100761A (en) | 2021-08-17 |
KR102382236B1 (en) | 2022-04-08 |
CN108884316B (en) | 2021-09-24 |
JPWO2017164129A1 (en) | 2019-01-31 |
WO2017164129A1 (en) | 2017-09-28 |
KR20180127376A (en) | 2018-11-28 |
CN108884316A (en) | 2018-11-23 |
JP6904332B2 (en) | 2021-07-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2021178962A (en) | Polyhydroxyamide composition for manufacturing substrates for electronic devices, and polybenzoxazole resin film | |
JP6061012B2 (en) | Photocurable film-forming composition and method for producing cured film | |
TWI687456B (en) | Triazine ring-containing polymer and composition containing it | |
TWI686424B (en) | Polymer containing triazine ring and composition containing it | |
JP6094579B2 (en) | Film forming composition and embedding material | |
JP6292221B2 (en) | Film forming composition | |
JP6191603B2 (en) | Aromatic polyamide and film-forming composition containing the same | |
WO2021079977A1 (en) | Triazine ring-containing polymer and film-forming composition containing same | |
TW201730239A (en) | Triazine ring-containing polymer and film-forming composition containing same | |
TWI838589B (en) | Polymer containing triazine ring and film-forming composition containing the same | |
JP2019085492A (en) | Film-forming composition containing triazine ring-containing polymer | |
WO2022225002A1 (en) | Triazine ring-containing polymer and film-forming composition containing same | |
TW202020019A (en) | Composition for forming protective film for transparent conductive film | |
WO2022225015A1 (en) | Triazine ring-containing polymer and film-forming composition containing same | |
WO2022225005A1 (en) | Solvent-free composition | |
JP2020015825A (en) | Triazine ring-containing polymer | |
JP2013079345A (en) | Highly transparent polyimide |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210621 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220418 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220510 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220706 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20220906 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20221205 |
|
C60 | Trial request (containing other claim documents, opposition documents) |
Free format text: JAPANESE INTERMEDIATE CODE: C60 Effective date: 20221205 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20221212 |
|
C21 | Notice of transfer of a case for reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C21 Effective date: 20221213 |
|
A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20230210 |
|
C211 | Notice of termination of reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C211 Effective date: 20230214 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240913 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20241120 |