JPH0827348A - Thermosetting resin composition and resin composition containing same and used for protective film for color filter - Google Patents
Thermosetting resin composition and resin composition containing same and used for protective film for color filterInfo
- Publication number
- JPH0827348A JPH0827348A JP16760994A JP16760994A JPH0827348A JP H0827348 A JPH0827348 A JP H0827348A JP 16760994 A JP16760994 A JP 16760994A JP 16760994 A JP16760994 A JP 16760994A JP H0827348 A JPH0827348 A JP H0827348A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin composition
- copolymer resin
- parts
- component
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 13
- 230000001681 protective effect Effects 0.000 title claims description 20
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 59
- -1 acrylic ester Chemical class 0.000 claims abstract description 33
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 7
- 125000004185 ester group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 48
- 239000011248 coating agent Substances 0.000 abstract description 45
- 239000000203 mixture Substances 0.000 abstract description 26
- 239000000126 substance Substances 0.000 abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 54
- 239000000243 solution Substances 0.000 description 42
- 238000004519 manufacturing process Methods 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 31
- 239000002904 solvent Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 18
- 239000000178 monomer Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 238000011282 treatment Methods 0.000 description 14
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 5
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 241000272814 Anser sp. Species 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 150000008360 acrylonitriles Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- LBHPSYROQDMVBS-UHFFFAOYSA-N (1-methylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCCC1 LBHPSYROQDMVBS-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- SKKHNUKNMQLBTJ-QIIDTADFSA-N [(1s,4r)-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C(=C)C)C[C@@H]1C2 SKKHNUKNMQLBTJ-QIIDTADFSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical group O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PHPRWKJDGHSJMI-UHFFFAOYSA-N 1-adamantyl prop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C=C)C3 PHPRWKJDGHSJMI-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-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
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- DUERRGNERQTBAB-UHFFFAOYSA-N 2-(oxiran-2-ylmethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)CC1CO1 DUERRGNERQTBAB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-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
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 101150000419 GPC gene Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- IQYMRQZTDOLQHC-ZQTLJVIJSA-N [(1R,4S)-2-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C=C)C[C@@H]1C2 IQYMRQZTDOLQHC-ZQTLJVIJSA-N 0.000 description 1
- PSGCQDPCAWOCSH-OPQQBVKSSA-N [(1s,3r,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@]2(C)[C@H](OC(=O)C=C)C[C@H]1C2(C)C PSGCQDPCAWOCSH-OPQQBVKSSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 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
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- HNBQFKZSMFFZQY-UHFFFAOYSA-L chembl1559341 Chemical compound [Na+].[Na+].C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=C(N=NC=2C(=CC(=CC=2)C=2C=C(C)C(N=NC=3C4=C(C=C(C=C4C=CC=3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=2)C)C=C1 HNBQFKZSMFFZQY-UHFFFAOYSA-L 0.000 description 1
- 239000003638 chemical reducing agent Substances 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
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 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
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- LJZJMIZQMNDARW-UHFFFAOYSA-N decan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCCCC(CC)OC(=O)C(C)=C LJZJMIZQMNDARW-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 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
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 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
- 239000001044 red dye Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Optical Filters (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、熱硬化性樹脂組成物お
よびこれを用いたカラーフィルタ保護膜用樹脂組成物に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition and a color filter protective film resin composition using the same.
【０００２】[0002]
【従来の技術】各種物品の表面の劣化や損傷を防止する
目的でコーティング膜を形成することがしばしば行われ
ている。このような、コーティング膜においては、平滑
な塗膜が得られること、基体との密着性が高いこと、強
靱であること、耐水性及び耐薬品性、耐溶剤性が優れて
いること、耐熱性及び耐光性が高くて長期間変質を起こ
さないこと等の性能が要求される。2. Description of the Related Art A coating film is often formed for the purpose of preventing deterioration and damage of the surface of various articles. In such coating film, a smooth coating film can be obtained, high adhesion to the substrate, toughness, excellent water resistance, chemical resistance, solvent resistance, heat resistance In addition, it is required to have performance such as high light resistance and no deterioration for a long period of time.
【０００３】また、近年では液晶表示素子、太陽電池、
光ディスク等に用いられるコーティング膜として前述の
性能に加えて透明性等の要求される用途が増加してい
る。In recent years, liquid crystal display devices, solar cells,
As a coating film used for optical disks and the like, applications requiring transparency and the like in addition to the above-mentioned performance are increasing.
【０００４】例えば、近年、カラーフィルタを内蔵した
カラー液晶表示素子が種々発表されている。このカラー
液晶表示素子の作製にあたっては、ガラス等の透明基板
上にカラーフィルタを設け、この上にインジウムチンオ
キシド（ＩＴＯ）等からなる無機薄膜を蒸着し、フォト
リソグラフィー法によってパターニングして透明電極を
形成した後、さらにこの上に液晶を配置する方法が主流
となりつつある。この場合、カラーフィルタには、この
上にＩＴＯを蒸着して、フォトリソグラフィー法で透明
電極を形成するプロセスに耐え得るだけの耐熱性、耐薬
品性が備わっていないため、ＩＴＯを蒸着する前にカラ
ーフィルタ上に保護膜を形成しておく必要がある。For example, in recent years, various color liquid crystal display devices incorporating a color filter have been announced. In the production of this color liquid crystal display element, a color filter is provided on a transparent substrate such as glass, an inorganic thin film made of indium tin oxide (ITO) or the like is vapor-deposited thereon, and a transparent electrode is formed by patterning by a photolithography method. After the formation, a method of disposing liquid crystal on the liquid crystal is becoming mainstream. In this case, the color filter does not have sufficient heat resistance and chemical resistance to withstand the process of depositing ITO on the color filter and forming the transparent electrode by the photolithography method. It is necessary to form a protective film on the color filter.
【０００５】このカラーフィルタ保護膜に要求される特
性としては、耐熱性、耐薬品性の他にガラス基板やカラ
ーフィルタとの密着性、コーティング性、透明性、耐傷
性等があげられる。このうち耐熱性は、保護膜上にＩＴ
Ｏ等の透明電極を蒸着によって形成する際に、保護膜表
面が、通常２００℃以上に加熱されるため、この条件下
で安定であることが必要である。Properties required of this color filter protective film include heat resistance and chemical resistance, as well as adhesion to a glass substrate or a color filter, coating properties, transparency, and scratch resistance. Of these, heat resistance is
When forming a transparent electrode such as O by vapor deposition, the surface of the protective film is usually heated to 200 ° C. or higher, and therefore it is necessary that the surface is stable under these conditions.
【０００６】このような耐熱性、耐薬品性等に優れたコ
ーティング用材料としては、特開昭５８−１９６５０６
号公報や特開昭６２−１１９５０１号公報記載のアクリ
ル系樹脂、特開昭６０−２１６３０７号公報記載のポリ
グリシジル（メタ）アクリレート系樹脂、特開昭６３−
１３１１０３号公報記載のメラミン樹脂、エポキシ樹
脂、その他ポリイミド樹脂等が提案されている。As a coating material having such excellent heat resistance and chemical resistance, there is disclosed in Japanese Patent Laid-Open No. 58-196506.
Acrylic resins described in JP-A-62-119501, polyglycidyl (meth) acrylate-based resins described in JP-A-60-216307, and JP-A-63-
A melamine resin, an epoxy resin, and other polyimide resins described in Japanese Patent No. 131103 have been proposed.
【０００７】しかしながら、従来提案されている材料で
はそれぞれ欠点があり、全ての要求特性を満足するバラ
ンスのとれた材料は無い。However, the materials proposed hitherto have their respective drawbacks, and there is no well-balanced material satisfying all the required characteristics.
【０００８】例えば、アクリル系樹脂では耐熱性が不十
分であり、ＩＴＯ等の蒸着時に膜の表面にシワやクラッ
クを生じるという問題がある。For example, acrylic resins have insufficient heat resistance, and there is a problem that wrinkles and cracks are generated on the surface of the film during the vapor deposition of ITO or the like.
【０００９】メラミン樹脂は、比較的耐熱性は高いもの
のガラス基板やカラーフィルタとの密着性が極端に悪
く、基板やフィルタ上でハジキを生じ易い。Although the melamine resin has relatively high heat resistance, it has extremely poor adhesion to a glass substrate or a color filter and is likely to cause cissing on the substrate or filter.
【００１０】エポキシ樹脂は密着性の良いものは、耐熱
性が不十分であり、耐熱性の高いものは密着性やコーテ
ィング性が劣るため要求特性のバランスをとることがで
きない。If the epoxy resin has good adhesion, the heat resistance is insufficient, and if the epoxy resin has high heat resistance, the adhesion and coating properties are poor and the required properties cannot be balanced.
【００１１】またポリイミド樹脂は、透明性が不十分な
上に、ワニスの保存安定性に欠ける点や、カラーフィル
タを浸すような溶剤しか使用できないというような問題
点がある。Further, the polyimide resin has problems that it is insufficient in transparency, storage stability of the varnish is insufficient, and only a solvent for immersing the color filter can be used.
【００１２】これらに対して、ポリグリシジル（メタ）
アクリレート系樹脂は、耐熱性、透明性は良好である
が、密着性、耐アルカリ性に問題がある。In contrast to these, polyglycidyl (meth)
Acrylate-based resins have good heat resistance and transparency, but have problems in adhesion and alkali resistance.
【００１３】このため、高温高湿下における密着性を向
上させる保護膜材料として特開平６−１４５５９４号公
報では、グリシジル（メタ）アクリレート及び脂環式炭
化水素基を有する（メタ）アクリレートを成分として含
む共重合体並びにＮ−置換マレイミド及び（メタ）アク
リル酸を成分として含む共重合体を含有してなる硬化性
組成物が提案されている。Therefore, in JP-A-6-145594, as a protective film material for improving the adhesion under high temperature and high humidity, glycidyl (meth) acrylate and (meth) acrylate having an alicyclic hydrocarbon group are used as components. A curable composition containing a copolymer containing N-substituted maleimide and a copolymer containing N-substituted maleimide and (meth) acrylic acid as components has been proposed.
【００１４】しかし、上記公報に具体的に開示される材
料を用いて形成される塗膜であっても、高温高湿下に長
期間置いたあとの塗膜特性が不満足なものであることが
わかった。例えば、カラーフィルタの最上層に上記の材
料で保護膜を形成した後、高温高湿下に長期間置くと、
保護膜を通して吸水するため、カラーフィルタへのイン
ジウムチンオキサイド（ＩＴＯ）の蒸着時に保護膜にし
わ、クラックが発生するという問題があることがわかっ
た。However, even a coating film formed by using the material specifically disclosed in the above publication may have unsatisfactory coating properties after being left under high temperature and high humidity for a long time. all right. For example, after forming a protective film of the above material on the uppermost layer of the color filter, if you place it under high temperature and high humidity for a long time,
Since water is absorbed through the protective film, it has been found that there is a problem that wrinkles and cracks are generated in the protective film during indium tin oxide (ITO) vapor deposition on the color filter.
【００１５】[0015]
【発明が解決しようとする課題】本発明は前記した従来
の材料の欠点を解決し、耐熱性、耐薬品性、密着性、コ
ーティング性、透明性、耐傷性等の全ての要求特性を満
足した上で、さらに、高温高湿下に長期間置いたあとの
塗膜特性にも優れる熱硬化性樹脂組成物およびこれを用
いたカラーフィルタ保護膜用樹脂組成物を提供するもの
である。The present invention solves the above-mentioned drawbacks of conventional materials and satisfies all required properties such as heat resistance, chemical resistance, adhesion, coating property, transparency and scratch resistance. Further, the present invention provides a thermosetting resin composition having excellent coating film properties after being left under high temperature and high humidity for a long time, and a resin composition for a color filter protective film using the same.
【００１６】[0016]
【課題を解決するための手段】本発明における熱硬化性
樹脂組成物は、 Ａ．（１）環内に３級炭素を含み、炭素数が７〜２０で
ある脂環式の基がエステル基に結合しているメタクリル
酸エステルまたはアクリル酸エステル１０重量％以上で
４０重量％未満及び（２）メタクリル酸グリシジルエス
テルまたはアクリル酸グリシジルエステル６０重量％を
超えて９０重量％以下を含む共重合樹脂ならびに Ｂ．（イ）Ｎ置換マレイミド及び（ロ）アクリル酸また
はメタクリル酸を必須成分として含む共重合樹脂を含有
してなるものである。このコーティング用樹脂組成物
は、特にカラーフィルタ保護膜用樹脂組成物に適してい
る。The thermosetting resin composition of the present invention comprises: (1) Methacrylic acid ester or acrylic acid ester containing tertiary carbon in the ring and having an alicyclic group having 7 to 20 carbon atoms bonded to an ester group is 10% by weight or more and less than 40% by weight, and (2) Copolymer resin containing more than 60% by weight and 90% by weight or less of glycidyl methacrylate or glycidyl acrylic acid, and B. (B) A copolymer resin containing N-substituted maleimide and (b) acrylic acid or methacrylic acid as essential components. This coating resin composition is particularly suitable for a color filter protective film resin composition.
【００１７】本発明におけるＡ成分である共重合樹脂を
構成するモノマー成分としての環内に３級炭素を含み、
炭素数が７〜２０である脂環式の基がエステル基に結合
しているメタクリル酸エステルまたはアクリル酸エステ
ル〔成分（１）〕としては、メタクリル酸ノルボルニ
ル、メタクリル酸ノルボルニルメチル、メタクリル酸ア
ダマンチル、メタクリル酸トリシクロ［５．２．１．０
2,6］デカン−８−イル、メタクリル酸トリシクロ
［５．２．１．０2,6］デカン−３（または４）−イル
メチル、メタクリル酸ボルニル、メタクリル酸イソボル
ニル、メタクリル酸メチルシクロヘキシル等のメタクリ
ル酸エステル、アクリル酸ノルボルニル、アクリル酸ノ
ルボルニルメチル、アクリル酸アダマンチル、アクリル
酸トリシクロ［５．２．１．０2,6］デカン−８−イ
ル、アクリル酸トリシクロ［５．２．１．０2,6］デカ
ン−３（または４）−イルメチル、アクリル酸ボルニ
ル、アクリル酸イソボルニル、メタクリル酸メチルシク
ロヘキシル等のアクリル酸エステルがある。これらは、
単独で使用され、また２種以上併用される。A tertiary carbon is contained in the ring as a monomer component constituting the copolymer resin which is the component A in the present invention,
Examples of the methacrylic acid ester or acrylic acid ester [component (1)] in which an alicyclic group having 7 to 20 carbon atoms is bonded to an ester group include norbornyl methacrylate, norbornyl methyl methacrylate, and methacrylic acid. Adamantyl, tricyclomethacrylate [5.2.1.0]
Methacryl such as 2,6 ] decane-8-yl, tricyclo [5.2.1.0 2,6 ] decan-3 (or 4) -ylmethyl methacrylate, bornyl methacrylate, isobornyl methacrylate, methylcyclohexyl methacrylate, etc. Acid ester, norbornyl acrylate, norbornyl methyl acrylate, adamantyl acrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl acrylate, tricyclo acrylate [5.2.1.0] 2,6 ] decane-3 (or 4) -ylmethyl, bornyl acrylate, isobornyl acrylate, methyl cyclohexyl methacrylate, and other acrylic acid esters. They are,
Used alone or in combination of two or more.
【００１８】本発明におけるＡ成分である共重合樹脂を
構成するモノマー成分としてのメタクリル酸グリシジル
エステルまたはアクリル酸グリシジルエステル〔成分
（２）〕は２種以上併用してもよい。Two or more kinds of glycidyl methacrylate or glycidyl acrylate [component (2)] as a monomer component constituting the copolymer resin as the component A in the present invention may be used in combination.
【００１９】本発明におけるＡ成分である共重合樹脂
は、それを構成するモノマーとして前記の成分以外に、
他の共重合可能な不飽和単量体〔成分（３）〕を含んで
いてもよい。このようなものとしては、不飽和脂肪酸エ
ステル、芳香族ビニル化合物、Ｎ−置換マレイミド、シ
アン化ビニル化合物等がある。The copolymer resin, which is the component A in the present invention, contains, in addition to the above-mentioned components as the monomer constituting the copolymer resin,
It may contain other copolymerizable unsaturated monomer [component (3)]. Examples of such compounds include unsaturated fatty acid esters, aromatic vinyl compounds, N-substituted maleimides, vinyl cyanide compounds and the like.
【００２０】上記不飽和脂肪酸エステルとしては、アク
リル酸メチル、アクリル酸エチル、アクリル酸ブチル、
アクリル酸２−エチルヘキシル等のアクリル酸アルキル
エステル、アクリル酸シクロヘキシル等のアクリル酸シ
クロアルキルエステル、アクリル酸フェニル、アクリル
酸ベンジル等のアクリル酸芳香族エステル、アクリル酸
グリシジル、アクリル酸２−ヒドロキシエチル等のアク
リル酸エステル、メタクリル酸メチル、メタクリル酸エ
チル、メタクリル酸ブチル、メタクリル酸２−エチルヘ
キシル等のメタクリル酸アルキルエステル、メタクリル
酸シクロヘキシル等のメタクリル酸シクロアルキルエス
テル、メタクリル酸フェニル、メタクリル酸ベンジル等
のメタクリル酸芳香族エステル、メタクリル酸グリシジ
ル、メタクリル酸２−ヒドロキシエチル等のメタクリル
酸エステルなどがある。Examples of the unsaturated fatty acid ester include methyl acrylate, ethyl acrylate, butyl acrylate,
Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, Cycloalkyl acrylates such as cyclohexyl acrylate, Acrylic aromatic esters such as phenyl acrylate and benzyl acrylate, Glycidyl acrylate, 2-Hydroxyethyl acrylate, etc. Acrylic esters, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and other methacrylic acid alkyl esters, cyclohexyl and other methacrylic acid cycloalkyl esters, and methacrylic acid, such as phenyl methacrylate and benzyl methacrylate. Examples thereof include aromatic esters, glycidyl methacrylate, and methacrylic acid esters such as 2-hydroxyethyl methacrylate.
【００２１】前記芳香族ビニル化合物としては、スチレ
ンまたはα−メチルスチレン、α−エチルスチレン等の
α−置換スチレン、クロロスチレン、ビニルトルエン、
ｔ−ブチルスチレン等の核置換スチレン等がある。Examples of the aromatic vinyl compound include styrene or α-substituted styrene such as α-methylstyrene and α-ethylstyrene, chlorostyrene, vinyltoluene,
Nuclear substituted styrenes such as t-butylstyrene are available.
【００２２】前記Ｎ−置換マレイミドとしては、Ｎ−置
換マレイミドとしては、公知のものが使用できるが、Ｎ
−メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−プロ
ピルマレイミド、Ｎ−ブチルマレイミド等のＮ−アルキ
ル基置換マレイミド、Ｎ−シクロヘキシルマレイミド等
のＮ−シクロアルキル基置換マレイミド、Ｎ−フェニル
マレイミド等のＮ−アリール基置換マレイミドからなる
群より選ばれる少なくとも１種の化合物を使用すること
ができる。As the N-substituted maleimide, known N-substituted maleimides can be used.
N-aryl such as N-alkyl group-substituted maleimide such as methyl-maleimide, N-ethylmaleimide, N-propylmaleimide and N-butylmaleimide, N-cycloalkyl group-substituted maleimide such as N-cyclohexylmaleimide and N-phenylmaleimide At least one compound selected from the group consisting of group-substituted maleimides can be used.
【００２３】前記シアン化ビニル化合物としては、アク
リロニトリル、メタクリロニトリル等がある。Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
【００２４】前記した各単量体は、これらの総量を基準
として、成分（１）を１０重量％以上で４０重量％未
満、成分（２）を６０重量％を超えて９０重量％以下お
よび成分（３）を０重量％又は３０重量％未満の範囲内
の割合で使用することが好ましい。成分（１）が１０重
量％未満になると得られる塗膜の密着性が低下し、４０
重量％以上になると耐熱性が低下する傾向がある。成分
（２）が６０重量％以下になると得られる塗膜の架橋密
度が低下するため耐湿性が低下し、９０重量％を超える
と密着性が低下する。成分（３）が多すぎると本発明の
効果が不十分となる傾向がある。好ましくは、成分
（１）２０〜３５重量％、成分（２）６５〜８０重量％
及び成分（３）０〜１５重量％の割合で使用される。Each of the above-mentioned monomers, based on the total amount thereof, contains 10% by weight or more and less than 40% by weight of the component (1), more than 60% by weight and 90% by weight or less of the component (2), and the components. It is preferable to use (3) at a ratio within the range of 0% by weight or less than 30% by weight. When the content of the component (1) is less than 10% by weight, the adhesion of the resulting coating film decreases,
If it is more than 5% by weight, the heat resistance tends to decrease. When the content of the component (2) is 60% by weight or less, the cross-linking density of the obtained coating film is lowered, so that the moisture resistance is lowered, and when it exceeds 90% by weight, the adhesion is lowered. If the component (3) is too much, the effect of the present invention tends to be insufficient. Preferably, component (1) 20 to 35% by weight, component (2) 65 to 80% by weight
And component (3) in an amount of 0 to 15% by weight.
【００２５】Ａ成分である共重合樹脂は、前記成分
（１）、成分（２）及び必要に応じて成分（３）の各単
量体を配合し、共重合させることにより製造することが
できる。ラジカル重合やイオン重合等の公知の方法を使
用できる。例えば、重合開始剤の存在下で塊状重合法、
溶液重合法、懸濁重合法、乳化重合法等の方法で製造す
ることができる。The copolymer resin as the component A can be produced by blending the above-mentioned components (1), (2) and, if necessary, the respective monomers of the component (3) and copolymerizing them. . Known methods such as radical polymerization and ionic polymerization can be used. For example, a bulk polymerization method in the presence of a polymerization initiator,
It can be produced by a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like.
【００２６】上記重合開始剤としては例えば、過酸化ベ
ンゾイル、過酸化ラウロイル、ジ−ｔ−ブチルペルオキ
シヘキサヒドロフタレート、ｔ−ブチルペルオキシ−２
−エチルヘキサノエート、１，１−ジ−ｔ−ブチルペル
オキシ−３，３，５−トリメチルシクロヘキサン等の有
機過酸化物、アゾビスイソブチロニトリル、アゾビス−
４−メトキシ−２，４−ジメチルバレロニトリル、アゾ
ビスシクロヘキサノン−１−カルボニトリル、アゾジベ
ンゾイル等のアゾ化合物、過硫酸カリウム、過硫酸アン
モニウムに代表される水溶性触媒及び過酸化物あるいは
過硫酸塩と還元剤の組み合わせによるレドックス触媒
等、通常のラジカル重合に使用できるものはいずれも使
用することができる。重合触媒は前記モノマーの総量に
対して０．０１〜１０重量％の範囲で使用するのが好ま
しい。Examples of the above-mentioned polymerization initiator include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydrophthalate and t-butylperoxy-2.
-Ethyl hexanoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane and other organic peroxides, azobisisobutyronitrile, azobis-
Azo compounds such as 4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile and azodibenzoyl, water-soluble catalysts represented by potassium persulfate and ammonium persulfate, and peroxides or persulfates. Any redox catalyst that can be used in ordinary radical polymerization, such as a redox catalyst obtained by combining a solvent and a reducing agent, can be used. The polymerization catalyst is preferably used in the range of 0.01 to 10% by weight based on the total amount of the above monomers.
【００２７】また、重合調節剤としてメルカプタン系化
合物、チオグリコール、四臭化炭素、α−メチルスチレ
ンダイマー等が分子量調節のために必要に応じて添加す
ることができる。Further, a mercaptan compound, thioglycol, carbon tetrabromide, α-methylstyrene dimer and the like can be added as a polymerization regulator, if necessary, for controlling the molecular weight.
【００２８】重合温度は０〜２００℃の範囲で選択する
のが好ましく、特に５０〜１２０℃であるのが好まし
い。The polymerization temperature is preferably selected in the range of 0 to 200 ° C, particularly preferably 50 to 120 ° C.
【００２９】溶液重合における溶媒としては、通常のラ
ジカル重合に使用される溶媒が使用できる。具体例とし
ては、ベンゼン、トルエン、キシレン等の芳香族系溶
剤；アセトン、メチルエチルケトン、メチルイソブチル
ケトン、シクロヘキサノン等のケトン系溶剤；ジエチル
エーテル、イソプロピルエーテル、テトラヒドロフラ
ン、ジオキサン、エチレングリコールジメチルエーテ
ル、エチレングリコールジエチルエーテル、ジエチレン
グリコールジメチルエーテル、ジチレングリコールジエ
チルエーテル等のエーテル系溶剤；酢酸エチル、酢酸−
ｎ−プロピル、酢酸イソプロピル、酢酸−ｎ−ブチル、
エチレングリコールモノメチルエーテルアセタート、エ
チレングリコールモノエチルエーテルアセタート、エチ
レングリコールモノブチルエーテルアセタート、ジエチ
レングリコールモノメチルエーテルアセタート、ジエチ
レングリコールモノエチルエーテルアセタート、プロピ
レングリコールモノメチルエーテルアセタート、プロピ
レングリコールモノエチルエーテルアセタート、γ−ブ
チロラクトン等のエステル系溶剤；ジメチルホルムアミ
ド、ジメチルアセトアミド、Ｎ−メチルピロリドン等の
アミド系溶剤などが挙げられる。これらの溶剤のうち、
エステル系溶剤及びケトン系溶剤が好ましく、単独で、
または、２種類以上を混合して使用することができる。
なお、通常、コーティング用樹脂組成物として用いる場
合は溶剤を含有しているので同じ溶剤を用いて溶液重合
法によって重合するのが好ましいが、重合体製造後メタ
ノール再沈法等の方法によりポリマを単離し、他の溶剤
に溶解して使用に供することも可能である。As the solvent in the solution polymerization, a solvent used in ordinary radical polymerization can be used. Specific examples include aromatic solvents such as benzene, toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether. , Ether solvents such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether; ethyl acetate, acetic acid-
n-propyl, isopropyl acetate, -n-butyl acetate,
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Examples include ester solvents such as γ-butyrolactone; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Of these solvents,
Ester solvent and ketone solvent are preferred, alone,
Alternatively, two or more kinds can be mixed and used.
In addition, usually, when used as a coating resin composition, since it contains a solvent, it is preferable to polymerize by a solution polymerization method using the same solvent, but the polymer is prepared by a method such as methanol reprecipitation method after polymer production. It is also possible to isolate and dissolve in another solvent before use.
【００３０】前記Ａ成分の共重合樹脂の分子量は、特に
制限はないが、５，０００〜３００，０００（標準ポリ
スチレン換算の重量平均分子量）であることが好まし
く、形成する塗膜の膜厚、塗布方法等の塗膜形成の目的
条件を考慮して適宜決定される。The molecular weight of the copolymer resin as the component A is not particularly limited, but is preferably 5,000 to 300,000 (weight average molecular weight in terms of standard polystyrene), and the film thickness of the coating film to be formed, It is appropriately determined in consideration of the target conditions for coating film formation such as the coating method.
【００３１】本発明におけるＢ成分である共重合樹脂を
構成するモノマー成分としてのＮ−置換マレイミド〔成
分（イ）〕としては、前記したＡ成分である共重合樹脂
の成分とすることができるＮ−置換マレイミドと同様の
ものを使用することができる。この成分の使用は耐熱性
および基材との密着性の観点から好ましい。これらのう
ちでもＮ−シクロヘキシルマレイミドおよびＮフェニル
マレイミドが特に好ましい。The N-substituted maleimide [component (a)] as a monomer component constituting the copolymer resin which is the component B in the present invention can be the component of the copolymer resin which is the component A described above. -Similar to substituted maleimides can be used. The use of this component is preferable from the viewpoints of heat resistance and adhesion to the substrate. Of these, N-cyclohexylmaleimide and N-phenylmaleimide are particularly preferable.
【００３２】アクリル酸またはメタクリル酸〔成分
（ロ）〕を使用する際、これらを併用してもよい。When acrylic acid or methacrylic acid [component (b)] is used, these may be used together.
【００３３】Ｂ成分の共重合樹脂のモノマー成分として
Ｎ−置換マレイミドおよびアクリル酸若しくはメタクリ
ル酸以外他の共重合可能な不飽和単量体〔成分（ハ）〕
を使用してもよい。このような不飽和単量体としては、
不飽和脂肪酸エステル、芳香族ビニル化合物、シアン化
ビニル化合物等があり、これらの具体例としては、Ａ成
分の共重合樹脂のモノマー成分としての他の共重合可能
な不飽和単量体〔成分（３）〕として例示したものを挙
げることができる。A copolymerizable unsaturated monomer other than N-substituted maleimide and acrylic acid or methacrylic acid as a monomer component of the component B copolymer resin [component (c)]
May be used. As such an unsaturated monomer,
There are unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds, and the like. Specific examples of these include other copolymerizable unsaturated monomers [component (component ( 3)] can be mentioned as examples.
【００３４】上記不飽和脂肪酸エステルとしては、前記
したＡ成分である共重合樹脂の成分とすることができる
不飽和脂肪酸エステルがあり、前記成分（１）である環
内に３級炭素を含み、炭素数が７〜２０である脂環式の
基がエステル基に結合しているメタクリル酸エステルま
たはアクリル酸エステルを使用してもよい。The unsaturated fatty acid ester includes an unsaturated fatty acid ester which can be a component of the above-mentioned component A copolymer resin, and contains a tertiary carbon atom in the ring which is the component (1), A methacrylic acid ester or an acrylic acid ester in which an alicyclic group having 7 to 20 carbon atoms is bonded to an ester group may be used.
【００３５】前記芳香族ビニル化合物としては、前記し
たＡ成分である共重合樹脂の成分とすることができる芳
香族ビニル化合物がある。As the aromatic vinyl compound, there is an aromatic vinyl compound which can be used as a component of the above-mentioned component A copolymer resin.
【００３６】シアン化ビニル化合物としては、アクリロ
ニトリル、メタクリロニトリル等がある。Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.
【００３７】前記した各単量体は、これらの総量を基準
として、成分（イ）を２０〜７０重量％、成分（ロ）を
５〜３０重量％および成分（ハ）を０〜７５重量％の範
囲内の割合で使用することが好ましい。成分（イ）が少
なすぎると得られるコーティング膜の耐熱性が不十分と
なる傾向があり、逆に多すぎると密着性や塗布性（ハジ
キ、ピンホール等がなく、きれいに塗れること）に不都
合を生じる傾向がある。成分（ロ）が少なすぎると、得
られる硬化物の耐熱性、耐傷性が不十分となる傾向があ
り、逆に多すぎると塗布性や硬化物の耐薬品性が低下す
る傾向がある。成分（ハ）が多すぎると本発明の効果が
不十分となりやすい。さらに好ましくは、成分（イ）３
０〜６０重量％、成分（ロ）１０〜３０重量％および成
分（ハ）１０〜６０重量％の範囲内の割合で使用され
る。Each of the above-mentioned monomers, based on the total amount thereof, contains 20 to 70% by weight of component (A), 5 to 30% by weight of component (B) and 0 to 75% by weight of component (C). It is preferable to use it in a ratio within the range. If the amount of component (a) is too small, the heat resistance of the resulting coating film tends to be insufficient, and conversely, if it is too large, there is an inconvenience in adhesion and applicability (no cissing, pinholes, etc., and good application). Tends to occur. If the component (b) is too small, the heat resistance and scratch resistance of the resulting cured product will tend to be insufficient, and conversely, if it is too large, the coatability and the chemical resistance of the cured product will tend to decrease. If the amount of the component (C) is too large, the effect of the present invention tends to be insufficient. More preferably, component (a) 3
It is used in a proportion within the range of 0 to 60% by weight, the component (B) 10 to 30% by weight and the component (C) 10 to 60% by weight.
【００３８】Ｂ成分である共重合樹脂は、前記成分
（イ）、成分（ロ）および成分（ハ）の各単量体を配合
し、共重合させることにより製造することができる。こ
の場合における、重合法、使用しうる重合開始剤、重合
調節剤、重合温度、溶液重合における溶媒については、
Ａ成分である共重合樹脂の場合と同様である。The copolymer resin as the component B can be produced by blending the monomers of the above-mentioned component (a), the component (b) and the component (c) and copolymerizing them. In this case, the polymerization method, the polymerization initiator that can be used, the polymerization regulator, the polymerization temperature, the solvent in the solution polymerization,
It is the same as in the case of the copolymer resin which is the component A.
【００３９】本発明の熱硬化性樹脂組成物には、必要に
応じて、Ａ成分およびＢ成分以外にも種々の成分（Ｃ成
分）を配合することができる。Ｃ成分として多価カルボ
ン酸無水物および多価カルボン酸からなる群より選ばれ
る少なくとも１種の化合物を使用することが、耐熱性、
耐薬品性向上の点から好ましい。The thermosetting resin composition of the present invention may optionally contain various components (component C) in addition to the components A and B. It is preferable to use at least one compound selected from the group consisting of polycarboxylic acid anhydrides and polycarboxylic acids as the C component,
It is preferable from the viewpoint of improving chemical resistance.
【００４０】上記多価カルボン酸無水物としては、無水
イタコン酸、無水マレイン酸、無水コハク酸、無水シト
ラコン酸、無水ドデセニルコハク酸、無水テトラヒドロ
フタル酸、無水ヘキサヒドロフタル酸、無水メチルテト
ラヒドロフタル酸、無水メチルヘキサヒドロフタル酸、
無水エンドメチレンテトラヒドロフタル酸、無水メチル
エンドメチレンテトラヒドロフタル酸等の脂肪族ジカル
ボン酸無水物；シクロペンタンテトラカルボン酸二無水
物、１，２，３，４−ブタンテトラカルボン酸二無水物
等の脂肪族多価カルボン酸二無水物；無水フタル酸、無
水トリメット酸、無水ピロメリット酸、無水ベンゾフェ
ノンテトラカルボン酸、３，３′，４，４′−ジフェニ
ルスルホンテトラカルボン酸二無水物等の芳香族多価カ
ルボン酸無水物；エチレングリコールビストリメリテー
ト、グリセリントリストリメリテート等のエステル基含
有酸無水物などを挙げることができる。また上記多価カ
ルボン酸としては、イタコン酸、マレイン酸、コハク
酸、シトラコン酸、テトラヒドロフタル酸、ヘキサヒド
ロフタル酸、メチルテトラヒドロフタル酸、シクロペン
タンテトラカルボン酸等の脂肪族多価カルボン酸；フタ
ル酸、テレフタル酸、イソフタル酸、トリメリット酸、
ピロメリット酸、ベンゾフェノンテトラカルボン酸等の
芳香族多価カルボン酸などを挙げることができる。Examples of the polycarboxylic acid anhydrides include itaconic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methyl hexahydrophthalic anhydride,
Aliphatic dicarboxylic acid anhydrides such as endomethylenetetrahydrophthalic anhydride and methylendomethylenetetrahydrophthalic anhydride; Fats such as cyclopentanetetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride Group polycarboxylic acid dianhydrides; aromatics such as phthalic anhydride, trimetic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride Polyhydric carboxylic acid anhydrides; ester group-containing acid anhydrides such as ethylene glycol bis trimellitate and glycerin tris trimellitate can be mentioned. Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as itaconic acid, maleic acid, succinic acid, citraconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid and cyclopentanetetracarboxylic acid; phthalic acid. Acid, terephthalic acid, isophthalic acid, trimellitic acid,
Examples thereof include aromatic polyvalent carboxylic acids such as pyromellitic acid and benzophenonetetracarboxylic acid.
【００４１】上記多価カルボン酸無水物および多価カル
ボン酸は１種類のみで用いても、２種類以上を組み合わ
せてもよい。耐熱性の点から芳香族多価カルボン酸無水
物および芳香族多価カルボン酸は耐熱性の点から好まし
く、耐熱性と溶剤に対する溶解性のバランスの点から無
水トリメリット酸が特に好ましい。The polycarboxylic acid anhydride and polycarboxylic acid may be used alone or in combination of two or more. From the viewpoint of heat resistance, aromatic polycarboxylic acid anhydrides and aromatic polycarboxylic acids are preferable from the viewpoint of heat resistance, and trimellitic anhydride is particularly preferable from the viewpoint of the balance between heat resistance and solubility in solvents.
【００４２】本発明の組成物において、Ａ成分の共重合
樹脂１００重量部に対してＢ成分の共重合樹脂３０〜３
００重量部を配合することが好ましく、５０〜２００重
量部配合されるのが特に好ましい。Ｂ成分の共重合樹脂
が少な過ぎると密着性が低下する傾向があり、多過ぎる
場合は耐薬品性が低下する傾向がある。Ｃ成分としての
多価カルボン酸無水物および多価カルボン酸からなる群
より選ばれる少なくとも１種の化合物は、Ｂ成分の共重
合樹脂１００重量部に対して０〜５０重量部使用するの
が好ましく、特に０〜４０重量部使用するのが好まし
い。多価カルボン酸無水物または多価カルボン酸が多す
ぎると塗布性、耐薬品性等が低下する傾向がある。使用
の効果を発揮させるためには５重量部以上使用すること
が好ましく、特に１０重量部以上使用することが好まし
い。In the composition of the present invention, 100 to 100 parts by weight of the component A copolymer resin is used, and the component B copolymer resin 30 to 3 is used.
It is preferable to add 100 parts by weight, and particularly preferably 50 to 200 parts by weight. If the amount of the component B copolymer resin is too small, the adhesion tends to decrease, and if it is too large, the chemical resistance tends to decrease. At least one compound selected from the group consisting of polycarboxylic acid anhydrides and polycarboxylic acids as the component C is preferably used in an amount of 0 to 50 parts by weight based on 100 parts by weight of the component B copolymer resin. It is particularly preferable to use 0 to 40 parts by weight. If the amount of polyvalent carboxylic acid anhydride or polyvalent carboxylic acid is too large, the coating properties, chemical resistance, etc. tend to be reduced. In order to exert the effect of use, it is preferable to use 5 parts by weight or more, and particularly preferably 10 parts by weight or more.
【００４３】また、本発明の組成物の密着性を向上させ
るために、この組成物にカップリング剤を添加すること
ができる。カップリング剤としては、官能性シランカッ
プリング剤が好ましくビニル基、メタクリロイル基、水
酸基、カルボキシル基、アミノ基、イソシアネート基、
エポキシ基等の反応性置換基を有するシランカップリン
グ剤、具体的にはビニルトリメトキシシラン、ビニルト
リエトキシシラン、γ−メタクリロキシプロピルトリメ
トキシシラン、γ−イソシアナートプロピルトリエトキ
シシラシ、γ−グリシドキシプロピルトリメトキシシラ
ン等が挙げられ、特にエポキシ基を有するシランカップ
リング剤が接着性、耐溶剤性等に優れているため好まし
い。これらの官能性シランカップリング剤は、１種類の
みで用いても、２種類以上を組み合わせても良い。官能
性シランカップリング剤の使用量は、Ａ成分の共重合樹
脂とＢ成分の共重合樹脂との合計量を１００重量部とし
た場合、０〜２０重量部の範囲が好ましく、特に０〜１
０重量部の範囲が好ましい。多すぎると耐薬品性等が低
下する傾向がある。また、使用の効果を発揮させるため
には０．１重量部以上使用することが好ましく、特に１
重量部以上使用することが好ましい。A coupling agent may be added to the composition of the present invention in order to improve the adhesion thereof. The coupling agent is preferably a functional silane coupling agent vinyl group, methacryloyl group, hydroxyl group, carboxyl group, amino group, isocyanate group,
A silane coupling agent having a reactive substituent such as an epoxy group, specifically vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glyce Examples thereof include sidoxypropyltrimethoxysilane and the like. Particularly, a silane coupling agent having an epoxy group is preferable because it has excellent adhesiveness and solvent resistance. These functional silane coupling agents may be used alone or in combination of two or more. The amount of the functional silane coupling agent used is preferably in the range of 0 to 20 parts by weight, particularly 0 to 1 when the total amount of the component A copolymer resin and the component B copolymer resin is 100 parts by weight.
A range of 0 parts by weight is preferred. If it is too much, the chemical resistance tends to decrease. Further, in order to exert the effect of use, it is preferable to use 0.1 part by weight or more, and particularly 1
It is preferable to use more than parts by weight.
【００４４】本発明の組成物は、通常、溶剤に溶解して
塗布し、加熱硬化させることによって塗膜を形成させる
ことができる。溶剤としては、本発明の組成物を溶解
し、かつこれらの成分と反応しないものであれば、特に
限定されるものではない。具体的には、本発明のＡ成分
である共重合樹脂を、溶液重合させる際の溶媒として例
示した溶剤が挙げられる。これらの溶剤のうちエステル
系溶剤及びケトン系溶剤が好ましく、単独でまたは２種
類以上を混合して使用することができる。The composition of the present invention can usually be dissolved in a solvent, applied, and cured by heating to form a coating film. The solvent is not particularly limited as long as it dissolves the composition of the present invention and does not react with these components. Specific examples thereof include the solvents exemplified as the solvent for solution polymerization of the copolymer resin which is the component A of the present invention. Of these solvents, ester solvents and ketone solvents are preferable, and they can be used alone or in admixture of two or more.
【００４５】本発明の組成物を溶剤に溶解して、組成物
溶液を調整する方法は特に限定されるものではなく、全
成分を同時に溶剤に溶解して組成物溶液を調整してもよ
く、必要に応じて各成分を適宜２つ以上の溶液としてお
いて、使用時にこれらを混合して組成物溶液としてもよ
い。このようにして組成物溶液を調整する場合の溶剤の
使用量は、塗布に供せられる最終的な組成物溶液全量の
うちの５０〜９５重量％とすることが好ましい。５０重
量％未満では固形分濃度が高すぎて塗膜のレベリング性
が低下したり、塗膜の透明性が低下したりする場合があ
り、一方９５重量％を超える場合は固形分濃度が低すぎ
て塗膜の耐薬品性等が不十分となる場合がある。固形分
濃度は６０〜９５重量％であることが好ましい。また、
本発明の組成物には必要に応じて、エピビス型、ノボラ
ック型等のエポキシ樹脂、カルボキシル基含有高分子化
合物、エポキシ樹脂の硬化に使用される硬化促進剤、酸
化防止剤や紫外線吸収剤等の安定剤等を添加してもよ
い。The method of dissolving the composition of the present invention in a solvent to prepare a composition solution is not particularly limited, and all components may be dissolved in a solvent at the same time to prepare a composition solution, If necessary, two or more solutions may be prepared for each component, and these may be mixed at the time of use to form a composition solution. When the composition solution is prepared as described above, the amount of the solvent used is preferably 50 to 95% by weight of the total amount of the final composition solution used for coating. If it is less than 50% by weight, the solid content concentration is too high, and the leveling property of the coating film may be lowered, or the transparency of the coating film may be reduced, while if it exceeds 95% by weight, the solid content concentration is too low. Therefore, the chemical resistance of the coating film may be insufficient. The solid content concentration is preferably 60 to 95% by weight. Also,
In the composition of the present invention, if necessary, an epoxy resin such as epibis type or novolac type, a carboxyl group-containing polymer compound, a curing accelerator used for curing the epoxy resin, an antioxidant or an ultraviolet absorber, etc. Stabilizers and the like may be added.
【００４６】本発明の組成物溶液を塗布する方法は特に
制限されず、浸漬法、スプレー法、ロールコート法、回
転塗布法等の他、スクリーン印刷、オフセット印刷等の
印刷による塗布法法等がある。本発明の組成物の加熱硬
化条件は組成物の各成分の具体的種類、配合割合等によ
って適宜選択されるが、通常、５０〜３００℃で０．１
〜１０時間、好ましくは１００〜２５０℃で１〜５時間
程度である。The method for applying the composition solution of the present invention is not particularly limited, and may include a dipping method, a spray method, a roll coating method, a spin coating method and the like, as well as a coating method such as screen printing and offset printing. is there. The heat curing conditions for the composition of the present invention are appropriately selected depending on the specific type of each component of the composition, the compounding ratio, etc.
-10 hours, preferably 1 to 5 hours at 100 to 250 ° C.
【００４７】本発明の組成物により形成されるコーティ
ング膜はガラス、金属、プラスチック等の種々の材料に
対して優れた密着性を示し、平滑、強靱で耐光性、耐熱
性、耐水性、耐溶剤性、透明性に優れているため、各種
物品のコーティング膜として有用である。特にカラーフ
ィルタ保護膜として、ゼラチン、グリュー、ポリビニル
アルコール、アクリル系樹脂等の種々のバインダー樹脂
を染料による染色や、顔料分散によって着色して得られ
る種々のカラーフィルタの表面保護層、防染保護層とし
て有用である。カラーフィルタ保護膜として用いる場合
は加熱硬化後の膜厚が０．０５〜３０μｍ、好ましくは
０．１〜１０μｍ程度となるように、適宜、塗布して用
いることができる。The coating film formed from the composition of the present invention exhibits excellent adhesion to various materials such as glass, metal and plastic, and is smooth and tough, and has light resistance, heat resistance, water resistance and solvent resistance. Since it has excellent properties and transparency, it is useful as a coating film for various articles. In particular, as a color filter protective film, a surface protective layer or a dye protective layer of various color filters obtained by dyeing various binder resins such as gelatin, glue, polyvinyl alcohol, and acrylic resin with a dye or coloring by dispersing a pigment. Is useful as When it is used as a color filter protective film, it can be appropriately applied and used so that the film thickness after heat curing is 0.05 to 30 μm, preferably 0.1 to 10 μm.
【００４８】本発明者らの研究によれば、従来のポリグ
リシジル（メタ）アクリレート樹脂を用いる技術はこの
樹脂を低分子量の多価カルボン酸無水物又は多価カルボ
ン酸と反応させるものであるが、得られる塗膜は、脆弱
すぎて密着性が悪いこと、また、架橋にあずかるエステ
ル結合の数が多すぎるため、耐アルカリ性が悪いことが
判明した。また、従来技術では、コーティング性、密着
性、耐熱性等の全ての要求特性を満足させるものはなか
ったが、本発明における組成物は、特定の構造の化合物
を組み合わせることにより、これらの各要求特性をバラ
ンス良く満足させることができる。According to the studies by the present inventors, the conventional technique using a polyglycidyl (meth) acrylate resin is to react this resin with a low molecular weight polyvalent carboxylic acid anhydride or polyvalent carboxylic acid. It was found that the obtained coating film was too fragile and had poor adhesion, and that the number of ester bonds involved in crosslinking was too large and therefore had poor alkali resistance. Further, in the prior art, none of the properties satisfying all the required properties such as coating property, adhesiveness, and heat resistance were satisfied, but the composition of the present invention can meet each of these requirements by combining compounds having a specific structure. It is possible to satisfy the characteristics in good balance.
【００４９】[0049]
【実施例】以下実施例により本発明を具体的に説明する
が、本発明はこれら実施例によって限定されるものでは
ない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
【００５０】製造例１（共重合樹脂溶液Ａ−１の製造） 撹拌機、温度計、窒素導入管、還流冷却器及び滴下ロー
トの備わった１リットルフラスコに、セロソルブアセテ
ート（アセトキシエトキシエタン）２６０重量部を仕込
みフラスコ内を窒素置換した。メタクリル酸トリシクロ
［５．２．１．０2,6］デカン−８−イルを６０重量
部、メタクリル酸グリシジル１４０重量部及びアゾビス
イソブチロニトリル１．０重量部をセロソルブアセテー
ト１００重量部に溶解し、前述の１リットルフラスコに
窒素気流中９０℃で３時間かけて滴下した。さらに９０
℃で１時間撹拌した後、アゾビスイソブチロニトリル
０．２重量部をセロソルブアセテート４０重量部に溶解
した溶液を添加し、その後１２０℃に昇温して２時間保
った。得られた共重合樹脂溶液は粘度が３２０ポアズ
（２５℃）であり、この共重合樹脂をＨＬＣ分析（ＧＰ
Ｃモード。カラムはゲルパックＡ−１２０＋ゲルパック
Ａ−１４０＋ゲルパックＡ−１５０、いずれも日立化成
工業（株）商品名。溶離液はテトラヒドロフラン。検出
器は示差屈折計。）したところ、標準ポリスチレン換算
の重量平均分子量は約５０，０００であった。Production Example 1 (Production of Copolymer Resin Solution A-1) A 1 liter flask equipped with a stirrer, thermometer, nitrogen introducing tube, reflux condenser and dropping funnel was charged with 260 parts by weight of cellosolve acetate (acetoxyethoxyethane). The inside of the flask was replaced with nitrogen. 60 parts by weight of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, 140 parts by weight of glycidyl methacrylate and 1.0 part by weight of azobisisobutyronitrile were added to 100 parts by weight of cellosolve acetate. It melt | dissolved and was dripped at the said 1 liter flask at 90 degreeC in nitrogen stream over 3 hours. 90 more
After stirring at 0 ° C for 1 hour, a solution prepared by dissolving 0.2 parts by weight of azobisisobutyronitrile in 40 parts by weight of cellosolve acetate was added, and then the temperature was raised to 120 ° C and kept for 2 hours. The obtained copolymer resin solution had a viscosity of 320 poise (25 ° C.), and this copolymer resin was subjected to HLC analysis (GP
C mode. The columns are Gel Pack A-120 + Gel Pack A-140 + Gel Pack A-150, all trade names of Hitachi Chemical Co., Ltd. The eluent is tetrahydrofuran. The detector is a differential refractometer. ), The weight average molecular weight in terms of standard polystyrene was about 50,000.
【００５１】製造例２（共重合樹脂溶液Ａ−２の製造） 製造例１において、メタクリル酸トリシクロ［５．２．
１．０2,6］デカン−８−イル６０重量部の代わりにメ
タクリル酸ボルニル６０重量部を用いたこと以外、製造
例１に準じて行った。得られた共重合樹脂溶液の粘度は
２４０センチポアズ（２５℃）であり、得られた共重合
樹脂の標準ポリスチレン換算の重量平均分子量は約４
５，０００であった。Production Example 2 (Production of Copolymer Resin Solution A-2) In Production Example 1, tricyclomethacrylate [5.2.
1.0 2,6 ] Decan-8-yl 60 parts by weight was used instead of 60 parts by weight of bornyl methacrylate, and the procedure of Production Example 1 was followed. The viscosity of the obtained copolymer resin solution was 240 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 4
It was 5,000.
【００５２】製造例３（共重合樹脂溶液Ａ−３の製造） 製造例１において、メタクリル酸トリシクロ［５．２．
１．０2,6］デカン−８−イル６０重量部の代わりにメ
タクリル酸イソボルニル６０重量部を用いたこと以外、
製造例１に準じて行った。得られた共重合樹脂溶液の粘
度は２２０センチポアズ（２５℃）であり、得られた共
重合樹脂の標準ポリスチレン換算の重量平均分子量は約
４２，０００であった。Production Example 3 (Production of Copolymer Resin Solution A-3) In Production Example 1, tricyclomethacrylate [5.2.
1.0 2,6 ] Decan-8-yl 60 parts by weight were used in place of 60 parts by weight of isobornyl methacrylate,
It carried out according to manufacture example 1. The viscosity of the obtained copolymer resin solution was 220 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 42,000.
【００５３】製造例４（共重合樹脂溶液Ａ−４の製造） 製造例１において、メタクリル酸トリシクロ［５．２．
１．０2,6］デカン−８−イル６０重量部の代わりにメ
タクリル酸ノルボルニル６０重量部を用いたこと以外、
製造例１に準じて行った。得られた共重合樹脂溶液の粘
度は２７０センチポアズ（２５℃）であり、得られた共
重合樹脂の標準ポリスチレン換算の重量平均分子量は約
４０，０００であった。Production Example 4 (Production of Copolymer Resin Solution A-4) In Production Example 1, tricyclomethacrylate [5.2.
1.0 2,6 ] Decan-8-yl 60 parts by weight were used in place of 60 parts by weight norbornyl methacrylate,
It carried out according to manufacture example 1. The viscosity of the obtained copolymer resin solution was 270 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 40,000.
【００５４】製造例５（共重合樹脂溶液Ａ−５の製造） 製造例１において、メタクリル酸トリシクロ［５．２．
１．０2,6］デカン−８−イルを１００重量部、メタク
リル酸グリシジルを１００重量部用いたこと以外、製造
例１に準じて行った。得られた共重合樹脂溶液の粘度は
２８０センチポアズ（２５℃）であり、得られた共重合
樹脂の標準ポリスチレン換算の重量平均分子量は約７
０，０００であった。Production Example 5 (Production of Copolymer Resin Solution A-5) In Production Example 1, tricyclomethacrylate [5.2.
1.0 2,6 ] Decan-8-yl was used according to Production Example 1 except that 100 parts by weight of decid-8-yl and 100 parts by weight of glycidyl methacrylate were used. The viscosity of the obtained copolymer resin solution was 280 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 7
It was 10,000.
【００５５】製造例６（共重合樹脂溶液Ｂ−１の製造） 撹拌機、温度計、窒素導入管、還流冷却器及び滴下ロー
トが備わった１リットルフラスコにセロソルブアセテー
ト（アセトキシエトキシエタン）１５０重量部を仕込み
フラスコ内を窒素置換した。Ｎ−フェニルマレイミド１
４０重量部、メタクリル酸４０重量部、アクリル酸エチ
ル２０重量部およびアゾビスイソブチロニトリル３．０
重量部をセロソルブアセテート３００重量部に溶解し、
前述の１リットルフラスコに窒素気流中９０℃で３時間
かけて滴下した。さらに９０℃で１時間撹拌した後、ア
ゾビスイソブチロニトリル０．２重量部をセロソルブア
セテート１６．７重量部に溶解した溶液を添加し、その
後１２０℃に昇温して２時間保った。得られた共重合樹
脂溶液の粘度は５６０センチポアズ（２５℃）であり、
得られた共重合樹脂の標準ポリスチレン換算の重量平均
分子量（製造例１におけるのと同じ方法で分析）は約２
２，０００であった。Production Example 6 (Production of Copolymer Resin Solution B-1) 150 parts by weight of cellosolve acetate (acetoxyethoxyethane) in a 1 liter flask equipped with a stirrer, thermometer, nitrogen introducing tube, reflux condenser and dropping funnel. The inside of the charged flask was replaced with nitrogen. N-phenylmaleimide 1
40 parts by weight, 40 parts by weight of methacrylic acid, 20 parts by weight of ethyl acrylate and 3.0 of azobisisobutyronitrile
Parts by weight dissolved in 300 parts by weight of cellosolve acetate,
The above-mentioned 1-liter flask was added dropwise in a nitrogen stream at 90 ° C. over 3 hours. After further stirring at 90 ° C. for 1 hour, a solution of 0.2 parts by weight of azobisisobutyronitrile dissolved in 16.7 parts by weight of cellosolve acetate was added, and then the temperature was raised to 120 ° C. and maintained for 2 hours. The viscosity of the obtained copolymer resin solution was 560 centipoise (25 ° C.),
The weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene (analyzed by the same method as in Production Example 1) was about 2.
It was 2,000.
【００５６】製造例７（共重合樹脂溶液Ｂ−２の製造） 製造例５において、使用するモノマーをＮ−シクロマレ
イミド１２０重量部、メタクリル酸４０重量部、メタク
リル酸メチル４０重量部としたこと以外、製造例５に準
じて行った。得られた共重合樹脂溶液の粘度は４８０セ
ンチポアズ（２５℃）であり、得られた共重合樹脂の標
準ポリスチレン換算の重量平均分子量は約２０，０００
であった。Production Example 7 (Production of Copolymer Resin Solution B-2) Except that in Production Example 5, the monomers used were 120 parts by weight of N-cyclomaleimide, 40 parts by weight of methacrylic acid and 40 parts by weight of methyl methacrylate. Was carried out according to Production Example 5. The viscosity of the obtained copolymer resin solution was 480 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 20,000.
Met.
【００５７】製造例８（共重合樹脂溶液Ｂ−３の製造） 製造例５において、使用するモノマーをＮ−フェニルマ
レイミド１００重量部、メタクリル酸４０重量部、メタ
クリル酸トリシクロ［５．２．１．０2,6］デカン−８
−イル６０重量部としたこと以外、製造例５に準じて行
った。得られた共重合樹脂溶液の粘度は３５０センチポ
アズ（２５℃）であり、得られた共重合樹脂の標準ポリ
スチレン換算の重量平均分子量は約１２，０００であっ
た。Production Example 8 (Production of Copolymer Resin Solution B-3) In Production Example 5, the monomers used were 100 parts by weight of N-phenylmaleimide, 40 parts by weight of methacrylic acid and tricyclomethacrylate [5.2.1. 0 2,6 ] decane-8
-Ill It was carried out according to Production Example 5 except that the amount was 60 parts by weight. The viscosity of the obtained copolymer resin solution was 350 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 12,000.
【００５８】実施例１〜１２及び比較例１〜３ 共重合樹脂溶液Ａ−１〜Ａ−５のうちいずれか一種 １
００重量部に共重合樹脂溶液Ｂ−１〜Ｂ−３のうちいず
れか一種 １１１重量部、無水トリメリット酸６．７重
量部（実施例１〜１２）又は４．５重量部（比較例１〜
３）、γ−グリシドキシプロピルトリメトキシシラン
２．０重量部、セロソルブアセテート１４０．７重量
部、ジエチレングリコール８８．９重量部を加えて室温
で均一に混合、溶解させた。共重合樹脂溶液Ａ−１〜Ａ
−５と共重合樹脂溶液Ｂ−１〜Ｂ−３の組合せを表１に
示す。Examples 1 to 12 and Comparative Examples 1 to 3 Any one of copolymer resin solutions A-1 to A-5 1
To 100 parts by weight, 111 parts by weight of any one of the copolymer resin solutions B-1 to B-3, 6.7 parts by weight of trimellitic anhydride (Examples 1 to 12) or 4.5 parts by weight (Comparative Example 1) ~
3), 2.0 parts by weight of γ-glycidoxypropyltrimethoxysilane, 140.7 parts by weight of cellosolve acetate and 88.9 parts by weight of diethylene glycol were added and uniformly mixed and dissolved at room temperature. Copolymer resin solution A-1 to A
Table 1 shows combinations of -5 and the copolymer resin solutions B-1 to B-3.
【００５９】この溶液を、孔径０．２μｍのメンブラン
フィルタで濾過した後、スピンコーターを用いてガラス
板（ダウコーニング社 ７０５９材、無アルカリガラ
ス）上に回転数１，０００ｒｐｍで回転塗布した。塗布
後ガラス板を１６０℃の恒温槽にて１時間加熱処理し、
塗膜を硬化させた。得られた塗膜の表面は極めて平滑で
あり、ピンホール等は全く見られなかった。触針式膜厚
計〔Ｓｕｒｆｃｏｍ；東京精密（株）商品名〕によって
測定した膜厚は１．３〜１．６μｍであった。This solution was filtered through a membrane filter having a pore size of 0.2 μm, and then spin-coated on a glass plate (Dow Corning 7059 material, non-alkali glass) using a spin coater at a rotation speed of 1,000 rpm. After coating, heat the glass plate in a constant temperature bath at 160 ° C for 1 hour,
The coating was cured. The surface of the obtained coating film was extremely smooth, and pinholes and the like were not observed at all. The film thickness measured by a stylus type film thickness meter [Surfcom; trade name of Tokyo Seimitsu Co., Ltd.] was 1.3 to 1.6 μm.
【００６０】このようにして作製した塗膜について以下
の試験を行った。塗膜のガラス板との密着性を調べるた
めにテープ剥離によるゴバン目試験（ＪＩＳ−Ｋ−５４
００）を行なった。その結果、残存数１００／１００で
あり、剥離は全く見られなかった。The following tests were conducted on the coating film thus produced. In order to check the adhesion of the coating film to the glass plate, a tape-like test by tape peeling (JIS-K-54
00) was performed. As a result, the remaining number was 100/100, and peeling was not observed at all.
【００６１】次に塗膜の４００ｎｍ〜８００ｎｍにおけ
る吸収スペクトルを塗布したものと同じガラス板をリフ
ァレンスとして測定したところ、光線透過率は全領域で
９５％以上であった。Next, when the same glass plate as the one coated with the absorption spectrum at 400 nm to 800 nm of the coating film was measured as a reference, the light transmittance was 95% or more in the entire region.
【００６２】また、この塗膜をつけたガラス板をプレッ
シャークッカーテスト（１２０℃、２気圧）１０時間
（以下、ＰＣＴ処理という）、Ｎ−メチルピロリドン中
に室温で３０分浸漬（以下、ＮＭＰ処理という）、５％
水酸化ナトリウム水溶液（以下、ＮａＯＨ処理という）
に室温で３０分浸漬及び２８０℃のキヤオーブン中に１
時間放置（以下、２８０℃処理という）の処理を別々に
行い、各処理後で上記のゴバン目試験及び光線透過率の
測定を行った。これらの結果を塗膜製造直後（硬化直
後）の試験結果と比較したところ、いずれの場合も接着
性や光線透過率は良好であった。なお、ゴバン目試験結
果を表２に、光線透過率試験結果を表３に示す。A glass plate having this coating film was subjected to a pressure cooker test (120 ° C., 2 atm) for 10 hours (hereinafter referred to as PCT treatment) and immersed in N-methylpyrrolidone for 30 minutes at room temperature (hereinafter referred to as NMP treatment). 5%)
Aqueous sodium hydroxide solution (hereinafter referred to as NaOH treatment)
Soak for 30 minutes at room temperature in a oven at 280 ° C for 1
The treatments that were left for a time (hereinafter referred to as 280 ° C. treatment) were separately performed, and after each treatment, the above-mentioned goggles test and the measurement of the light transmittance were performed. When these results were compared with the test results immediately after coating film production (immediately after curing), adhesiveness and light transmittance were good in all cases. Table 2 shows the results of the goose eye test and Table 3 shows the results of the light transmittance test.
【００６３】比較例４ クレゾールノボラックエポキシ樹脂（日本化薬（株）Ｅ
ＯＣＮ−１０３Ｓ）１００重量部、無水トリメリット酸
３０重量部、γ−グリシドキシプロピルトリメトキシシ
ラン１．０重量部、セロソルブアセテート４００重量部
を室温で均一に混合溶解し、得られた溶液を実施例と同
様にしてガラス板上に塗布、加熱硬化して、塗膜の各種
特性試験を行った。ゴバン目試験結果を表２に、光線透
過率試験結果を表３に示す。Comparative Example 4 Cresol novolac epoxy resin (Nippon Kayaku Co., Ltd. E
OCN-103S) 100 parts by weight, trimellitic anhydride 30 parts by weight, γ-glycidoxypropyltrimethoxysilane 1.0 part by weight, and cellosolve acetate 400 parts by weight are uniformly mixed and dissolved at room temperature, and the resulting solution is obtained. In the same manner as in the example, the composition was applied onto a glass plate and cured by heating, and various characteristics tests of the coating film were conducted. Table 2 shows the results of the goose eye test and Table 3 shows the results of the light transmittance test.
【００６４】比較例５ ポリメタクリル酸グリシジル（標準ポリスチレン換算の
重量平均分子量約８０，０００）１００重量部、無水ト
リメリット酸１０重量部、γ−グリシドキシプロピルト
リメトキシシラン１．０重量部、セロソルブアセテート
５８０重量部を室温で均一に混合溶解し、得られた溶液
を実施例と同様にしてガラス上に塗布、加熱硬化して、
塗膜の各種特性試験を行った。ゴバン目試験結果を表２
に、光線透過率試験結果を表３に示す。Comparative Example 5 100 parts by weight of glycidyl polymethacrylate (weight average molecular weight in terms of standard polystyrene of about 80,000), 10 parts by weight of trimellitic anhydride, 1.0 part by weight of γ-glycidoxypropyltrimethoxysilane, 580 parts by weight of cellosolve acetate were uniformly mixed and dissolved at room temperature, and the obtained solution was applied on glass and heat-cured in the same manner as in Example.
Various characteristics tests of the coating film were conducted. Table 2 shows the results of the goggle eye test.
Table 3 shows the results of the light transmittance test.
【００６５】比較例６ 共重合樹脂溶液Ａ−１ １００重量部、無水トリメリッ
ト酸７重量部、γ−グリシドキシプロピルトリメトキシ
シラン０．４重量部、セロソルブアセテート４７重量
部、ジエチレングリコール４９重量部を室温で均一に混
合溶解し、得られた溶液を実施例と同様にしてガラス上
に塗布、加熱硬化して、塗膜の各種特性試験を行った。
ゴバン目試験結果を表２に、光線透過率試験結果を表３
に示す。Comparative Example 6 Copolymer resin solution A-1 100 parts by weight, trimellitic anhydride 7 parts by weight, γ-glycidoxypropyltrimethoxysilane 0.4 parts by weight, cellosolve acetate 47 parts by weight, diethylene glycol 49 parts by weight. Was uniformly mixed and dissolved at room temperature, and the obtained solution was coated on glass and cured by heating in the same manner as in Examples, and various characteristics tests of coating films were conducted.
Table 2 shows the results of the goose eye test and Table 3 shows the results of the light transmittance test.
Shown in
【００６６】比較例７ 共重合樹脂溶液Ｂ−３ １００重量部、クレゾールノボ
ラックエポキシ樹脂（日本化薬（株）ＥＯＣＮ−１０３
Ｓ）３０重量部、無水トリメリット酸６重量部、γ−グ
リシドキシプロピルトリメトキシシラン０．７重量部、
セロソルブアセテート７０重量部、ジエチレングリコー
ル６０重量部を室温で均一に混合溶解し、得られた溶液
を実施例と同様にしてガラス上に塗布、加熱硬化して、
塗膜の各種特性試験を行った。ゴバン目試験結果を表２
に、光線透過率試験結果を表３に示す。Comparative Example 7 100 parts by weight of Copolymer resin solution B-3, cresol novolac epoxy resin (EOCN-103, Nippon Kayaku Co., Ltd.)
S) 30 parts by weight, trimellitic anhydride 6 parts by weight, γ-glycidoxypropyltrimethoxysilane 0.7 parts by weight,
70 parts by weight of cellosolve acetate and 60 parts by weight of diethylene glycol were uniformly mixed and dissolved at room temperature, and the obtained solution was coated on glass and cured by heating in the same manner as in the example.
Various characteristics tests of the coating film were conducted. Table 2 shows the results of the goggle eye test.
Table 3 shows the results of the light transmittance test.
【００６７】[0067]
【表１】 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 表１ 共重合樹脂溶液ＡとＢの組合せ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 共重合樹脂溶液Ａ 共重合樹脂溶液Ｂ ─────────────────────────────────── 実施例１ Ａ−１ Ｂ−１ 実施例２ Ａ−１ Ｂ−２ 実施例３ Ａ−１ Ｂ−３ 実施例４ Ａ−２ Ｂ−１ 実施例５ Ａ−２ Ｂ−２ 実施例６ Ａ−２ Ｂ−３ 実施例７ Ａ−３ Ｂ−１ 実施例８ Ａ−３ Ｂ−２ 実施例９ Ａ−３ Ｂ−３ 実施例１０ Ａ−４ Ｂ−１ 実施例１１ Ａ−４ Ｂ−２ 実施例１２ Ａ−４ Ｂ−３ 比較例１ Ａ−５ Ｂ−１ 比較例２ Ａ−５ Ｂ−２ 比較例３ Ａ−５ Ｂ−３ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 1 Combination of copolymer resin solutions A and B ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Copolymer resin solution A Copolymer resin solution B ───── ────────────────────────────── Example 1 A-1 B-1 Example 2 A-1 B-2 Example 3 A-1 B-3 Example 4 A-2 B-1 Example 5 A-2 B-2 Example 6 A-2 B-3 Example 7 A-3 B-1 Example 8 A-3 B -2 Example 9 A-3 B-3 Example 10 A-4 B-1 Example 11 A-4 B-2 Example 12 A-4 B-3 Comparative Example 1 A-5 B-1 Comparative Example 2 A-5 B-2 Comparative Example 3 A-5 B-3 ━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━
【００６８】[0068]
【表２】 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 表２ ゴバン目試験結果（残存数／１００） ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 硬化直後 ＰＣＴ ＮＭＰ ＮａＯＨ ２８０℃ 処理後 処理後 処理後 処理後 ─────────────────────────────────── 実施例１ 100/100 100/100 100/100 100/100 100/100 実施例２ 100/100 100/100 100/100 100/100 100/100 実施例３ 100/100 100/100 100/100 100/100 100/100 実施例４ 100/100 100/100 100/100 100/100 100/100 実施例５ 100/100 100/100 100/100 100/100 100/100 実施例６ 100/100 100/100 100/100 100/100 100/100 実施例７ 100/100 100/100 100/100 100/100 100/100 実施例８ 100/100 100/100 100/100 100/100 100/100 実施例９ 100/100 100/100 100/100 100/100 100/100 実施例１０ 100/100 100/100 100/100 100/100 100/100 実施例１１ 100/100 100/100 100/100 100/100 100/100 実施例１２ 100/100 100/100 100/100 100/100 100/100 比較例１ 100/100 100/100 100/100 100/100 100/100 比較例２ 100/100 100/100 100/100 100/100 100/100 比較例３ 100/100 100/100 100/100 100/100 100/100 比較例４ 100/100 0/100 100/100 100/100 100/100 比較例５ 100/100 0/100 100/100 0/100 100/100 比較例６ 100/100 0/100 100/100 0/100 100/100 比較例７ 100/100 90/100 100/100 100/100 100/100 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 2 Gobang eye test results (remaining number / 100 ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Immediately after curing PCT NMP NaOH 280 ℃ After treatment After treatment After treatment After treatment After ─────────────────────────────────── Example 1 100/100 100/100 100/100 100 / 100 100/100 Example 2 100/100 100/100 100/100 100/100 100/100 Example 3 100/100 100/100 100/100 100/100 100/100 Example 4 100/100 100/100 100 / 100 100/100 100/100 Example 5 100/100 100/100 100/100 100/100 100/100 Example 6 100/100 100/100 100/100 100/100 100/100 Example 7 100/100 100/100 100/100 100/100 100/100 Example 8 100/100 100/100 100/100 100/100 100/100 Example 9 100/100 100/100 100/100 100/100 100/100 Example 10 100/100 100/100 10 0/100 100/100 100/100 Example 11 100/100 100/100 100/100 100/100 100/100 Example 12 100/100 100/100 100/100 100/100 100/100 Comparative Example 1 100 / 100 100/100 100/100 100/100 100/100 Comparative example 2 100/100 100/100 100/100 100/100 100/100 Comparative example 3 100/100 100/100 100/100 100/100 100/100 Comparative Example 4 100/100 0/100 100/100 100/100 100/100 Comparative Example 5 100/100 0/100 100/100 0/100 100/100 Comparative Example 6 100/100 0/100 100/100 0/100 100/100 Comparative Example 7 100/100 90/100 100/100 100/100 100/100 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━
【００６９】[0069]
【表３】 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 表３ 光線透過率試験結果（４００〜８００ｎｍ） ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 硬化直後 ＰＣＴ ＮＭＰ ＮａＯＨ ２８０℃ 処理後 処理後 処理後 処理後 ─────────────────────────────────── 実施例１ 95%以上 95%以上 95%以上 95%以上 90% 実施例２ 95%以上 95%以上 95%以上 95%以上 90% 実施例３ 95%以上 95%以上 95%以上 95%以上 90% 実施例４ 95%以上 95%以上 95%以上 95%以上 95%以上 実施例５ 95%以上 95%以上 95%以上 95%以上 95%以上 実施例６ 95%以上 95%以上 95%以上 95%以上 95%以上 実施例７ 95%以上 95%以上 95%以上 95%以上 90% 実施例８ 95%以上 95%以上 95%以上 95%以上 90% 実施例９ 95%以上 95%以上 95%以上 95%以上 90% 実施例１０ 95%以上 95%以上 95%以上 95%以上 95%以上 実施例１１ 95%以上 95%以上 95%以上 95%以上 95%以上 実施例１２ 95%以上 95%以上 95%以上 95%以上 95%以上 比較例１ 95%以上 95%以上 95%以上 95%以上 90% 比較例２ 95%以上 95%以上 95%以上 95%以上 90% 比較例３ 95%以上 95%以上 95%以上 95%以上 90% 比較例４ 95%以上 95%以上 90%以上 80% 60% 比較例５ 95%以上 50%以下 80% 50%以下 95%以上 比較例６ 95%以上 80% 95%以上 80% 95%以上 比較例７ 95%以上 95%以上 95%以上 95%以上 50%以下 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━[Table 3] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 3 Light transmittance test results (400 to 800 nm ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Immediately after curing PCT NMP NaOH 280 ℃ After treatment After treatment After treatment After treatment After ─────────────────────────────────── Example 1 95% or more 95% or more 95% or more 95% 90% or more Example 2 95% or more 95% or more 95% or more 95% or more 90% Example 3 95% or more 95% or more 95% or more 95% or more 90% Example 4 95% or more 95% or more 95% or more 95 Example 5 95% or more 95% or more 95% or more 95% or more 95% or more 95% or more Example 6 95% or more 95% or more 95% or more 95% or more 95% or more Example 7 95% or more 95% or more 95% or more 95% or more 90% Example 8 95% or more 95% or more 95% or more 95% or more 90% Example 9 95% or more 95% Top 95% or more 95% or more 90% Example 10 95% or more 95% or more 95% or more 95% or more 95% or more Example 11 95% or more 95% or more 95% or more 95% or more 95% or more Example 12 95% 95% or more 95% or more 95% or more 95% or more Comparative example 1 95% or more 95% or more 95% or more 95% or more 90% Comparative example 2 95% or more 95% or more 95% or more 95% or more 90% Comparative example 3 95% or more 95% or more 95% or more 95% or more 90% Comparative Example 4 95% or more 95% or more 90% or more 80% 60% Comparative Example 5 95% or more 50% or less 80% 50% or less 95% or more Comparative Example 6 95% or more 80% 95% or more 80% 95% or more Comparative Example 7 95% or more 95% or more 95% or more 95% or more 50% or less ━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━
【００７０】試験例 実施例１〜１２及び比較例１〜７で調製した組成物溶液
を用いてカラーフィルタ基材への適性を調べた。試験法
としては一般的に知られている方法でカラーフィルタ基
材を作製し、この基材上への塗布性と耐熱性を調べた。
カラーフィルタ基材の作製はまず透明ガラス基板上にゼ
ラチン−重クロム酸アンモニウム（１０：１、重量比）
の水溶液を乾燥後の膜厚が１μｍとなるように回転塗布
した後、８０℃で１０分間乾燥し、得られた塗膜に紫外
線を照射した後、純水で現像することにより、染色基質
層を得た。これを下記組成の赤色染色浴に浸漬し、水洗
後、１５０℃で３０分間乾燥することにより、赤色に染
色されたカラーフィルタ基材を形成した。 染色浴の組成 スミノール・ミリングレッドＲＳ（住友化学工業（株）製） ２ｇ 酢酸 ３ｇ 蒸留水 １００ｇTest Example The composition solutions prepared in Examples 1 to 12 and Comparative Examples 1 to 7 were used to examine suitability for color filter substrates. As a test method, a color filter substrate was prepared by a generally known method, and the coating property and heat resistance on this substrate were examined.
The color filter substrate is prepared by first gelatin-ammonium dichromate (10: 1, weight ratio) on a transparent glass substrate.
After spin-coating the aqueous solution of to give a film thickness after drying of 1 μm, it is dried at 80 ° C. for 10 minutes, the resulting coating film is irradiated with ultraviolet rays and then developed with pure water to give a dyed substrate layer. Got This was immersed in a red dye bath having the following composition, washed with water, and dried at 150 ° C. for 30 minutes to form a color filter substrate dyed red. Composition of dyeing bath Suminol Milling Red RS (Sumitomo Chemical Co., Ltd.) 2g Acetic acid 3g Distilled water 100g
【００７１】次に、このカラーフィルタ基材上に前記組
成物溶液を１，０００ｒｐｍで回転塗布し、１８０℃で
１時間乾燥することにより保護層を形成した。このよう
にして作製された保護膜つきカラーフィルタを前記した
プレッシャークッカー試験（１２０℃、２気圧）１０時
間処理した後、保護膜の上にインジウムチンオキサイド
（ＩＴＯ）を常法に従い蒸着した後、ホトリソグラフィ
ーによりパターニングした。このＩＴＯのパターンを有
するカラーフィルタを光学顕微鏡で詳細に観察したが、
実施例１〜１２の組成物を用いて作製したカラーフィル
タや保護膜にシワやクラック等は全く認められず、カラ
ーフィルタと保護膜との接着性、密着性も表４に示すよ
うに良好であった。Next, the composition solution was spin-coated on this color filter substrate at 1,000 rpm and dried at 180 ° C. for 1 hour to form a protective layer. The color filter with a protective film thus produced was treated for 10 hours under the pressure cooker test (120 ° C., 2 atm) described above, and then indium tin oxide (ITO) was vapor-deposited on the protective film by a conventional method. It was patterned by photolithography. The color filter having this ITO pattern was observed in detail with an optical microscope.
No wrinkles or cracks were observed in the color filters or protective film produced using the compositions of Examples 1 to 12, and the adhesiveness and adhesion between the color filter and the protective film were good as shown in Table 4. there were.
【００７２】[0072]
【表４】 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 表４ カラーフィルター基材適正試験結果 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 組成物 ＩＴＯ蒸着後の カラーフィルター 表面状態 との密着性 ─────────────────────────────────── 実施例１ 〇 △ 実施例２ 〇 〇 実施例３ 〇 〇 実施例４ 〇 〇 実施例５ 〇 〇 実施例６ 〇 〇 実施例７ 〇 △ 実施例８ 〇 〇 実施例９ 〇 〇 実施例１０ 〇 〇 実施例１１ 〇 〇 実施例１２ 〇 〇 比較例１ × 〇 比較例２ × 〇 比較例３ × 〇 比較例４ 〇 × 比較例５ × × 比較例６ 〇 × 比較例７ 〇 × ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 表４中、ＩＴＯ蒸着後の表面状態は、異常のなかったも
のを〇、シワ、クラックが発生したものを×とし、カラ
ーフィルターとの密着性は、ゴナン目試験で剥がれなか
ったものを〇、部分的に剥がれたものを△、完全に剥が
れたものを×とした。[Table 4] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 4 Color filter substrate proper test results ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Composition Color filter after ITO deposition Adhesion with surface condition ─── ──────────────────────────────── Example 1 〇 △ Example 2 〇 〇 Example 3 〇 〇 Example 4 ○ ○ Example 5 ○ ○ ○ Example 6 ○ ○ ○ Example 7 ○ △ Example 8 ○ ○ Example 9 ○ ○ Example 10 ○ ○ Example 11 ○ ○ Example 12 ○ ○ Comparative Example 1 × ○ Comparative Example 2 × ○ Comparative example 3 × ○ Comparative example 4 ○ × Comparative example 5 × × Comparative example 6 ○ × Comparative example 7 ○ × ━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━ In Table 4, ITO The surface condition after vapor deposition was ◯ when there was no abnormality, x when there were wrinkles and cracks, and the adhesiveness with the color filter was ◯ when it did not peel off in the gonan eye test, and it partially peeled off. The sample was rated as Δ and the one completely peeled was rated as x.
【００７３】[0073]
【発明の効果】請求項１または請求項２における熱硬化
性樹脂組成物は、その組成物から形成される塗膜は、平
滑であり、透明性、接着性、耐湿性、耐薬品性、耐熱
性、耐傷性等に極めて優れている。請求項３における熱
硬化性樹脂組成物は、上記の特性において特に優れる。
請求項４におけるカラーフィルタ保護膜用樹脂組成物
は、請求項１〜４におけるいずれかの熱硬化性樹脂組成
物を含有してなり、カラーフィルタ保護膜用として有用
であり、前記樹脂組成物と同様の効果を有し、特に、高
温高湿下における長期信頼性に格段に優れた特性を示
す。According to the thermosetting resin composition of claim 1 or 2, the coating film formed from the composition is smooth and has transparency, adhesiveness, moisture resistance, chemical resistance, and heat resistance. Extremely excellent in scratch resistance and scratch resistance. The thermosetting resin composition according to claim 3 is particularly excellent in the above properties.
The color filter protective film resin composition according to claim 4 contains the thermosetting resin composition according to any one of claims 1 to 4, and is useful as a color filter protective film. It has the same effect, and exhibits particularly excellent long-term reliability under high temperature and high humidity.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０２Ｆ 1/1335 ５０５ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location G02F 1/1335 505
Claims (4)
数が７〜２０である脂環式の基がエステル基に結合して
いるメタクリル酸エステルまたはアクリル酸エステル１
０重量％以上で４０重量％未満及び（２）メタクリル酸
グリシジルエステルまたはアクリル酸グリシジルエステ
ル６０重量％を超えて９０重量％以下を含む共重合樹脂
ならびに Ｂ．（イ）Ｎ置換マレイミド及び（ロ）アクリル酸また
はメタクリル酸を必須成分として含む共重合樹脂を含有
してなる熱硬化性樹脂組成物。1. A. First Embodiment (1) Methacrylic acid ester or acrylic acid ester 1 in which an alicyclic group having a carbon number of 7 to 20 is bonded to an ester group, which contains tertiary carbon in the ring.
A copolymer resin containing 0 wt% or more and less than 40 wt% and (2) more than 60 wt% and not more than 90 wt% of glycidyl methacrylate or glycidyl acrylate; and B. (A) A thermosetting resin composition containing an N-substituted maleimide and (b) a copolymer resin containing acrylic acid or methacrylic acid as essential components.
０である脂環式の基がエステル基に結合しているメタク
リル酸エステルまたはアクリル酸エステルが、ノルボル
ニルメタクリル酸エステル、ボルニルメタクリル酸エス
テル、ノルボルニルアクリル酸エステル、ボルニルアク
リル酸エステルである請求項１記載の熱硬化性樹脂組成
物。2. A ring containing tertiary carbon and having 7 to 2 carbon atoms.
The methacrylic acid ester or acrylic acid ester in which an alicyclic group having 0 is bonded to an ester group is norbornyl methacrylic acid ester, bornyl methacrylic acid ester, norbornyl acrylic acid ester, bornyl acrylic acid ester. The thermosetting resin composition according to claim 1, which is
び多価カルボン酸からなる群より選ばれる少なくとも１
種の化合物を含有してなる請求項１または請求項２記載
の熱硬化性樹脂組成物。3. At least one selected from the group consisting of C, polycarboxylic acid anhydride and polycarboxylic acid.
The thermosetting resin composition according to claim 1 or 2, which comprises one kind of compound.
の熱硬化性樹脂組成物を含有してなるカラーフィルタ保
護膜用樹脂組成物。4. A resin composition for a color filter protective film, which comprises the thermosetting resin composition according to claim 1, claim 2, or claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16760994A JPH0827348A (en) | 1994-07-20 | 1994-07-20 | Thermosetting resin composition and resin composition containing same and used for protective film for color filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16760994A JPH0827348A (en) | 1994-07-20 | 1994-07-20 | Thermosetting resin composition and resin composition containing same and used for protective film for color filter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0827348A true JPH0827348A (en) | 1996-01-30 |
Family
ID=15852956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16760994A Pending JPH0827348A (en) | 1994-07-20 | 1994-07-20 | Thermosetting resin composition and resin composition containing same and used for protective film for color filter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0827348A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006176746A (en) * | 2004-11-26 | 2006-07-06 | Jsr Corp | Copolymer, resin composition, protecting film and method for forming protecting film |
| KR100777582B1 (en) * | 2005-12-01 | 2007-11-28 | 주식회사 엘지화학 | Composition for preparing thermosetting resin, thermosetting resin prepared by the same, and thermosetting resin composition comprising the same |
| KR100845692B1 (en) * | 2004-12-29 | 2008-07-11 | 제일모직주식회사 | Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same |
| JP2014037480A (en) * | 2012-08-15 | 2014-02-27 | Idemitsu Kosan Co Ltd | Epoxy copolymer |
-
1994
- 1994-07-20 JP JP16760994A patent/JPH0827348A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006176746A (en) * | 2004-11-26 | 2006-07-06 | Jsr Corp | Copolymer, resin composition, protecting film and method for forming protecting film |
| KR100845692B1 (en) * | 2004-12-29 | 2008-07-11 | 제일모직주식회사 | Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same |
| KR100777582B1 (en) * | 2005-12-01 | 2007-11-28 | 주식회사 엘지화학 | Composition for preparing thermosetting resin, thermosetting resin prepared by the same, and thermosetting resin composition comprising the same |
| JP2014037480A (en) * | 2012-08-15 | 2014-02-27 | Idemitsu Kosan Co Ltd | Epoxy copolymer |
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