JP6299156B2 - Thermosetting resin composition suitable for color filter protective film, and color filter provided with the cured film - Google Patents
Thermosetting resin composition suitable for color filter protective film, and color filter provided with the cured film Download PDFInfo
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- JP6299156B2 JP6299156B2 JP2013230152A JP2013230152A JP6299156B2 JP 6299156 B2 JP6299156 B2 JP 6299156B2 JP 2013230152 A JP2013230152 A JP 2013230152A JP 2013230152 A JP2013230152 A JP 2013230152A JP 6299156 B2 JP6299156 B2 JP 6299156B2
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- JP
- Japan
- Prior art keywords
- component
- color filter
- resin composition
- thermosetting resin
- protective film
- Prior art date
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- 230000001681 protective effect Effects 0.000 title claims description 41
- 239000011342 resin composition Substances 0.000 title claims description 28
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 28
- 239000003822 epoxy resin Substances 0.000 claims description 42
- 229920000647 polyepoxide Polymers 0.000 claims description 42
- -1 carboxylic acid hemiacetal ester Chemical class 0.000 claims description 35
- 125000003700 epoxy group Chemical group 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- 125000003566 oxetanyl group Chemical group 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 125000002723 alicyclic group Chemical group 0.000 claims description 11
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- 150000002373 hemiacetals Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 description 16
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004129 EU approved improving agent Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 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
- 150000002576 ketones Chemical class 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 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
- 239000002798 polar solvent Substances 0.000 description 2
- 229920001515 polyalkylene glycol Chemical group 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- CGILRHVKKLYKNE-UHFFFAOYSA-N (3-methyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(C)COC1 CGILRHVKKLYKNE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AQOSPGCCTHGZFL-UHFFFAOYSA-N 1-(3a-hydroxy-7-methoxy-1,2,4,8b-tetrahydropyrrolo[2,3-b]indol-3-yl)ethanone Chemical compound COC1=CC=C2NC3(O)N(C(C)=O)CCC3C2=C1 AQOSPGCCTHGZFL-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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- OADIZUFHUPTFAG-UHFFFAOYSA-N 2-[2-(2-ethylhexoxy)ethoxy]ethanol Chemical compound CCCCC(CC)COCCOCCO OADIZUFHUPTFAG-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
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
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- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
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- IXAUCJBNZILGEG-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate;3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C.CCO[Si](C)(OCC)CCCOC(=O)C(C)=C IXAUCJBNZILGEG-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Optical Filters (AREA)
Description
本発明は、液晶表示装置などに用いられるカラーフィルター保護膜用として好適な熱硬化性樹脂組成物、及びその組成物を硬化してなる、表面平滑性に優れる保護膜を有するカラーフィルターに関する。 The present invention relates to a thermosetting resin composition suitable for a color filter protective film used in a liquid crystal display device and the like, and a color filter having a protective film excellent in surface smoothness formed by curing the composition.
近年、液晶表示装置が急速に普及したことに伴い、液晶表示装置に用いられる高品質なカラーフィルターの需要も高まっている。カラーフィルターは、透明基板上に、所定パターンに形成されたブラックマトリックス層や赤、緑、青などの複数の色が所定順序に配列された着色層と、保護膜とを重ねた構造であり、着色層の通過光を赤、緑、青の３つの基本色にし、それらの光を加法混合することにより中間色や白色を含む映像の色を作り出す役割を有している。その保護膜は、液晶表示装置の製造時又は使用時においてカラーフィルターを物理的及び化学的に保護する役割を担っており、カラーフィルターによる発色の再現性を向上するために、当該保護膜の透明性あるいは表面平滑性を改善すると共に、外的衝撃から液晶部を保護するために硬度を高めることが従来から行われてきた（特許文献１参照）。 In recent years, with the rapid spread of liquid crystal display devices, the demand for high-quality color filters used in liquid crystal display devices has also increased. The color filter is a structure in which a protective layer and a black matrix layer formed in a predetermined pattern or a colored layer in which a plurality of colors such as red, green, and blue are arranged in a predetermined order on a transparent substrate, The light passing through the colored layer has three basic colors of red, green, and blue, and these lights are additively mixed to create an image color including intermediate colors and white. The protective film plays a role of physically and chemically protecting the color filter at the time of manufacture or use of the liquid crystal display device. In order to improve the reproducibility of color development by the color filter, the protective film is transparent. In order to improve the property or the surface smoothness, and to protect the liquid crystal part from external impact, it has been conventionally performed to increase the hardness (see Patent Document 1).
また、カラーフィルターは、酸・アルカリ溶液への浸漬処理等の過酷な工程を経て製造されるため、このような製造過程によりカラーフィルターが劣化したり損傷したりすることによる性能低下や作動不良を防止するために、硬化性、密着性、耐ＩＴＯ（錫ドープ酸化インジウム層）形成プロセス性など、保護膜の様々な性能向上が図られてきた。 In addition, since color filters are manufactured through harsh processes such as immersion in acid / alkaline solutions, performance deterioration and malfunction due to deterioration or damage of the color filter due to such manufacturing processes. In order to prevent this, various performance improvements of protective films such as curability, adhesion, and ITO (tin-doped indium oxide layer) formation process properties have been attempted.
本出願人も、特許文献２において、カラーフィルター保護膜用熱硬化性樹脂組成物の密着性、ＩＴＯ形成プロセス性を向上するために、重量平均分子量が５０００〜４００００であり、且つ、エポキシ当量が１４０〜６００ｇ／ｍｏｌであり、炭素−炭素不飽和結合とエポキシ基を含有するモノマーを少なくとも用いて重合されたエポキシ基含有重合体（Ａ）と、分子量が３３０〜７０００であり、且つ、エポキシ当量が１５０〜３５００ｇ／ｍｏｌであり、エポキシ基を２個以上有しビスフェノールＡの誘導体であるエポキシ基含有化合物（Ｂ）と、特定構造の構造を有するカルボン酸（ｃ１）がビニルエーテル化合物（ｃ２）によりブロック化された多価カルボン酸誘導体（Ｃ）とを含有する、カラーフィルター保護膜用熱硬化性樹脂組成物を提案している。 In the patent document 2, in order to improve the adhesion and ITO forming processability of the thermosetting resin composition for color filter protective film, the present applicant also has a weight average molecular weight of 5000 to 40000 and an epoxy equivalent of 140-600 g / mol, an epoxy group-containing polymer (A) polymerized using at least a monomer containing a carbon-carbon unsaturated bond and an epoxy group, a molecular weight of 330-7000, and an epoxy equivalent Is an epoxy group-containing compound (B) which is a derivative of bisphenol A having two or more epoxy groups, and a carboxylic acid (c1) having a specific structure by vinyl ether compound (c2). Thermosetting resin set for color filter protective film, containing blocked polycarboxylic acid derivative (C) It has proposed a thing.
最近の液晶ディスプレイは、スマートフォンやタブレットなどの携帯端末の波及に伴い、従来以上に高い性能(高画質、高精細等)が要望されている。それに伴い、コントラストの向上が求められ、ブラックマトリックスのＯＤ値（光学濃度）の向上が必須となっている。ＯＤ値向上のためには、ブラックマトリックスの樹脂中の顔料濃度を上げる手法と、ブラックマトリックスの膜厚を厚くする手法が挙げられる。前者の手法は、その他物性の低下が懸念されるため、後者の手法が主に適用されている。しかしながら、ブラックマトリックスの膜厚が厚くなることで、その上に形成される赤、青、緑等の着色層の段差が従来よりも大きくなってしまう。そのため、カラーフィルター保護膜の表面平滑性がより高いことが求められている。カラーフィルター保護膜の表面平滑性が低いと、液晶配向が乱れることにより、液晶表示性能が劣ってしまうため、表面平滑性は重要な性能の一つである。この要求を実現するためには、従来のカラーフィルター保護膜では十分ではなく、更なる改善が必要であった。 Recent liquid crystal displays are required to have higher performance (higher image quality, higher definition, etc.) than ever before with the spread of mobile terminals such as smartphones and tablets. Accordingly, improvement in contrast is required, and improvement in the OD value (optical density) of the black matrix is essential. In order to improve the OD value, there are a method of increasing the pigment concentration in the resin of the black matrix and a method of increasing the film thickness of the black matrix. The former method is mainly applied because there is a concern about deterioration of other physical properties. However, as the film thickness of the black matrix increases, the level difference of the colored layers such as red, blue, and green formed thereon becomes larger than before. Therefore, the surface smoothness of the color filter protective film is required to be higher. If the surface smoothness of the color filter protective film is low, the liquid crystal display performance is inferior because the liquid crystal alignment is disturbed, so the surface smoothness is one of the important performances. In order to realize this requirement, the conventional color filter protective film is not sufficient, and further improvement is necessary.
そこで、本発明の目的とするところは、従来より求められている密着性および透明性等の特性を維持したまま、表面平滑性に優れるカラーフィルター保護膜を形成可能な熱硬化性樹脂組成物と、これを硬化させてなる保護膜を備えるカラーフィルターを提供することにある。 Accordingly, an object of the present invention is to provide a thermosetting resin composition capable of forming a color filter protective film excellent in surface smoothness while maintaining properties such as adhesion and transparency that have been conventionally required. Another object of the present invention is to provide a color filter provided with a protective film obtained by curing this.
そのための手段として、本発明は、下記のＡ成分〜Ｃ成分と、必要に応じて下記Ｄ成分を任意成分として含む熱硬化性樹脂組成物であって、Ａ成分〜Ｄ成分の合計１００重量部中に、Ｃ成分を５〜５０重量部含む熱硬化性樹脂組成物。
Ａ成分：（ａ１）炭素−炭素不飽和結合とエポキシ基又はオキセタニル基を有するモノマーと、（ａ２）（ａ１）以外の炭素−炭素不飽和結合を有するモノマーとからなる、重量平均分子量３，０００〜１００，０００の、エポキシ基又はオキセタニル基含有重合体
Ｂ成分：多価カルボン酸化合物のカルボキシル基が、ビニルエーテル化合物によりヘミアセタールエステルとしてブロック化された、多価カルボン酸ヘミアセタールエステル
Ｃ成分：下記式（１）の構造を有す、４官能脂環式エポキシ樹脂
Ｄ成分：Ｃ成分以外の多官能エポキシ樹脂
（ｌ，ｍ，ｎ，ｏは、それぞれ０以上の整数、ｌ＋ｍ＋ｎ＋ｏは０〜２０の整数）
As a means for that, the present invention is a thermosetting resin composition containing the following A component to C component and optionally the following D component as an optional component, and a total of 100 parts by weight of the A component to D component. A thermosetting resin composition containing 5 to 50 parts by weight of the C component therein.
Component A: Weight average molecular weight 3,000, comprising (a1) a monomer having a carbon-carbon unsaturated bond and an epoxy group or oxetanyl group, and a monomer having a carbon-carbon unsaturated bond other than (a2) and (a1). Epoxy group or oxetanyl group-containing polymer of ˜100,000 B component: polyvalent carboxylic acid hemiacetal ester in which carboxyl group of polyvalent carboxylic acid compound is blocked by vinyl ether compound as hemiacetal ester C component: Tetrafunctional alicyclic epoxy resin having the structure of formula (1) D component: polyfunctional epoxy resin other than C component
(L, m, n, o are each an integer of 0 or more, l + m + n + o is an integer of 0-20)
本発明の熱硬化性樹脂組成物は、さらにシランカップリング剤（Ｅ成分）と、レベリング剤（Ｆ成分）とを含有し、カラーフィルター保護膜用として好適である。 The thermosetting resin composition of the present invention further contains a silane coupling agent (E component) and a leveling agent (F component), and is suitable for a color filter protective film.
また、本発明によれば、前記熱硬化性樹脂組成物を硬化させてなる保護膜を有する、カラーフィルターも提供することができる。 Moreover, according to this invention, the color filter which has a protective film formed by hardening | curing the said thermosetting resin composition can also be provided.
なお、本発明において数値範囲を示す「○○〜××」とは、特に明示しない限り「○○以上××以下」を意味する。 In the present invention, “XX to XX” indicating a numerical range means “XX or more and XX or less” unless otherwise specified.
本発明の熱硬化性樹脂組成物によれば、Ｃ成分として脂環式エポキシ樹脂の中でも上記式（１）で示される所定の構造を有する４官能の脂環式エポキシ樹脂を適量使用していることで、表面平滑性に優れる保護膜を形成することができる。 According to the thermosetting resin composition of the present invention, an appropriate amount of a tetrafunctional alicyclic epoxy resin having a predetermined structure represented by the above formula (1) is used as the C component among the alicyclic epoxy resins. Thus, a protective film having excellent surface smoothness can be formed.
≪カラーフィルター保護膜用熱硬化性樹脂組成物≫
本発明の熱硬化性樹脂組成物は、カラーフィルターの保護膜として好適に使用できるものであって、（Ａ）エポキシ基又はオキセタニル基含有重合体、（Ｂ）多価カルボン酸ヘミアセタールエステル、及び（Ｃ）４官能脂環式エポキシ樹脂を必須成分として含み、さらに必要に応じて（Ｄ）Ｃ成分以外の多官能エポキシ樹脂を任意成分として含んでもよい。
≪Thermosetting resin composition for color filter protective film≫
The thermosetting resin composition of the present invention can be suitably used as a protective film for a color filter, and includes (A) an epoxy group or oxetanyl group-containing polymer, (B) a polyvalent carboxylic acid hemiacetal ester, and (C) A tetrafunctional alicyclic epoxy resin may be included as an essential component, and a polyfunctional epoxy resin other than the (D) component C may be included as an optional component as required.
＜（Ａ）エポキシ基又はオキセタニル基含有重合体＞
Ａ成分は、エポキシ基又はオキセタニル基含有重合体であって、（ａ１）炭素−炭素不飽和結合とエポキシ基又はオキセタニル基を有するモノマーと、（ａ２）（ａ１）以外の炭素−炭素不飽和結合を有するモノマーとからなる重合体である。
<(A) Epoxy group or oxetanyl group-containing polymer>
Component A is an epoxy group or oxetanyl group-containing polymer (a1) a monomer having a carbon-carbon unsaturated bond and an epoxy group or oxetanyl group, and (a2) a carbon-carbon unsaturated bond other than (a1). It is a polymer consisting of a monomer having
（ａ１）炭素−炭素不飽和結合とエポキシ基又はオキセタニル基を有するモノマーは、炭素−炭素不飽和結合と、エポキシ基又はオキセタニル基とを有していれば良く、このような用途に周知のいかなるモノマーも利用することができる。エポキシ基を有するモノマーとしては、例えば下記の式（２）〜（４）で表されるモノマーが好ましい例として挙げられる。
（式中、Ｒ１は水素原子または炭素数１〜５のアルキル基、kは１〜５の整数を示す。）
（式中、Ｒ２は水素原子または炭素数１〜５のアルキル基、Ｒ３は−ＣＨ２Ｏ−基または−ＣＨ２−基、Ｒ４は水素原子または炭素数１〜２のアルキル基、mは１〜７の整数を示す。）
（式中、Ｒ５は水素原子または炭素数１〜５のアルキル基、ｎは１〜８の整数を示す。）
(A1) The monomer having a carbon-carbon unsaturated bond and an epoxy group or oxetanyl group may have a carbon-carbon unsaturated bond and an epoxy group or oxetanyl group. Monomers can also be used. As a monomer which has an epoxy group, the monomer represented, for example by following formula (2)-(4) is mentioned as a preferable example.
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k represents an integer of 1 to 5)
(In the formula, R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 3 is a —CH 2 O— group or —CH 2 — group, R 4 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, m represents an integer of 1 to 7.)
(In the formula, R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 8)
また、オキセタニル基を有するモノマーとしては、例えば下記の式（５）で表されるモノマーが好ましい例として挙げられる。
（式中、Ｒ６、Ｒ７、およびＲ８は水素原子または炭素数１〜５のアルキル基、ｊは１〜８の整数を示す。）
Moreover, as a monomer which has oxetanyl group, the monomer represented, for example by following formula (5) is mentioned as a preferable example.
(In the formula, R 6 , R 7 and R 8 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and j represents an integer of 1 to 8)
（ａ２）（ａ１）以外の炭素−炭素不飽和結合を有するモノマーは、炭素−炭素不飽和結合を有し、上記（ａ１）に該当しない化合物であれば良く、このような用途に周知のいかなるモノマーも利用することができる。例えば、下記の式（６）〜（９）で表されるモノマーが挙げられる。
（式中、Ｒ９は水素原子または炭素数１〜５のアルキル基、Ｒ１０は炭素数１〜１２のアルキル基、アリール基、アリールオキシ基、またはポリアルキレングリコール残基、もしくは主環構成炭素数３〜１２の脂環式炭素水素基を示す。）
（式中、Ｒ１１は水素原子または炭素数１〜５のアルキル基、Ｒ１２は水素原子、炭素数１〜１２のアルキル基、アルコキシ基、ヒドロキシアルキル基、ヒドロキシル基、シロキシアルキル基、または芳香族炭化水素基を示す。）
（式中、Ｒ１３は水素原子または炭素数１〜１２のアルキル基、シクロアルキル基、または芳香族炭化水素基を示す。）
（式中、Ｒ１４は水素原子または炭素数１〜５のアルキル基、ｐは１〜５の整数、Ｒ１５、Ｒ１６、Ｒ１７はそれぞれ独立にメチル基またはエチル基を示す。）
(A2) The monomer having a carbon-carbon unsaturated bond other than (a1) may be any compound that has a carbon-carbon unsaturated bond and does not fall under the above (a1). Monomers can also be used. Examples thereof include monomers represented by the following formulas (6) to (9).
(Wherein R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 10 is an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, or a polyalkylene glycol residue, or a main ring-constituting carbon. (The alicyclic carbon hydrogen group of several 3-12 is shown.)
Wherein R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 12 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a hydroxyalkyl group, a hydroxyl group, a siloxyalkyl group, or an aromatic Represents a hydrocarbon group.)
(In the formula, R 13 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or an aromatic hydrocarbon group.)
(In the formula, R 14 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is an integer of 1 to 5, and R 15 , R 16 and R 17 each independently represents a methyl group or an ethyl group.)
（Ａ）エポキシ基又はオキセタニル基含有重合体は、（ａ１）成分と（ａ２）成分とを共重合することによって得ることができ、その重合態様としては直鎖状であっても分岐していても良く、ランダム共重合体、ブロック共重合体、グラフト共重合体等のいずれであっても良い。なお、（ａ１）成分及び（ａ２）成分は、それぞれ単独でも２種以上を併用しても良い。 (A) The epoxy group or oxetanyl group-containing polymer can be obtained by copolymerizing the component (a1) and the component (a2), and the polymerization mode is branched even if it is linear. Any of a random copolymer, a block copolymer, a graft copolymer, and the like may be used. In addition, (a1) component and (a2) component may each be individual, or may use 2 or more types together.
（ａ１）成分と（ａ２）成分との重合方法は特に限定されず、ラジカル重合、イオン重合等の重合法を用いることができる。より具体的には、重合開始剤の存在下において、塊状重合法、溶液重合法、懸濁重合法、乳化重合法などの重合法を用いることができる。また、必要に応じて触媒や溶媒などの添加物を重合反応系に添加しても良い。このときの配合割合としては、（ａ１）成分１５〜７０％、（ａ２）成分２５〜７５％、重合開始剤３〜８％（（ａ１）成分、（ａ２）成分、及び重合開始剤の合計含有量は１００％である）程度とすればよい。 The polymerization method of the component (a1) and the component (a2) is not particularly limited, and a polymerization method such as radical polymerization or ionic polymerization can be used. More specifically, polymerization methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used in the presence of a polymerization initiator. Moreover, you may add additives, such as a catalyst and a solvent, to a polymerization reaction system as needed. As a blending ratio at this time, the total of (a1) component 15 to 70%, (a2) component 25 to 75%, polymerization initiator 3 to 8% ((a1) component, (a2) component, and polymerization initiator) The content may be about 100%).
（Ａ）エポキシ基又はオキセタニル基含有重合体の重量平均分子量（Ｍｗ）は３，０００〜１００，０００であり、好ましくは３，０００〜８０，０００である。重量平均分子量が３，０００未満であると、保護膜の硬度が低下し、１００，０００を超えると塗布硬化後の外観が悪化する恐れがある。 (A) The weight average molecular weight (Mw) of an epoxy group or oxetanyl group containing polymer is 3,000-100,000, Preferably it is 3,000-80,000. When the weight average molecular weight is less than 3,000, the hardness of the protective film decreases, and when it exceeds 100,000, the appearance after coating and curing may be deteriorated.
＜（Ｂ）多価カルボン酸ヘミアセタールエステル＞
Ｂ成分は、多価カルボン酸ヘミアセタールエステルであって、多価カルボン酸化合物のカルボキシル基がビニルエーテル化合物によりヘミアセタールエステルとして潜在化、すなわちブロック化されたビニルエーテルブロック多価カルボン酸である。
<(B) Polycarboxylic acid hemiacetal ester>
The component B is a polyvalent carboxylic acid hemiacetal ester, which is a vinyl ether block polyvalent carboxylic acid in which the carboxyl group of the polyvalent carboxylic acid compound is latentized as a hemiacetal ester by a vinyl ether compound, that is, blocked.
（Ｂ）多価カルボン酸ヘミアセタールエステルの多価カルボン酸としては、炭素数４〜２０で２〜８価のカルボン酸であることが好ましい。好ましい例としては、例えばイタコン酸、マレイン酸、コハク酸、シトラコン酸等の直鎖または分岐を有する脂肪族多価カルボン酸；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、シクロヘキサンジカルボン酸、シクロペンタンテトラカルボン酸、シクロヘキサントリカルボン酸等の脂環式多価カルボン酸；フタル酸、テレフタル酸、イソフタル酸、メリット酸、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が挙げられる。また、多価カルボン酸としては、アルコール化合物と酸無水物との反応によって得られるハーフエステル体も利用できる。 (B) The polyvalent carboxylic acid of the polyvalent carboxylic acid hemiacetal ester is preferably a divalent to octavalent carboxylic acid having 4 to 20 carbon atoms. Preferred examples include linear or branched aliphatic polyvalent carboxylic acids such as itaconic acid, maleic acid, succinic acid, citraconic acid; tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanedicarboxylic acid, Cycloaliphatic polycarboxylic acids such as cyclopentanetetracarboxylic acid and cyclohexanetricarboxylic acid; aromatic polyvalent carboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, merit acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid Examples include acids. Moreover, as polyvalent carboxylic acid, the half ester body obtained by reaction with an alcohol compound and an acid anhydride can also be utilized.
一方、ビニルエーテル化合物の具体例としては、例えばメチルビニルエーテル、エチルビニルエーテル、ｉ−プロピルビニルエーテル、ｎ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、ｉ−ブチルビニルエーテル、ｔ−ブチルビニルエーテル、２−エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル等の脂肪族ビニルエーテル化合物が挙げられる。それらの中でも、入手性および硬化温度が保護膜のプロセスに適合する点から、ｎ−プロピルビニルエーテルおよびｉ−プロピルビニルエーテルが好ましく挙げられる。なお、ビニルエーテル化合物は、単独で、または２種以上を組み合わせて用いることができる。 On the other hand, specific examples of the vinyl ether compound include, for example, methyl vinyl ether, ethyl vinyl ether, i-propyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether and the like. These aliphatic vinyl ether compounds are mentioned. Among these, n-propyl vinyl ether and i-propyl vinyl ether are preferable because they are available and the curing temperature is compatible with the process of the protective film. In addition, a vinyl ether compound can be used individually or in combination of 2 or more types.
（Ｂ）多価カルボン酸ヘミアセタールエステルは、多価カルボン酸とビニルエーテル化合物とを室温ないし１５０℃の範囲の温度で反応させることによって得ることができる。ブロック化反応は平衡反応であるため、多価カルボン酸に対してビニルエーテル化合物を若干多くすると反応が促進され、収率を向上させることができる。なお、多価カルボン酸とビニルエーテル化合物との反応には、目的に応じて触媒や溶媒を添加することもできる。 (B) The polycarboxylic acid hemiacetal ester can be obtained by reacting a polyvalent carboxylic acid and a vinyl ether compound at a temperature in the range of room temperature to 150 ° C. Since the blocking reaction is an equilibrium reaction, if the amount of the vinyl ether compound is slightly increased with respect to the polyvalent carboxylic acid, the reaction is promoted and the yield can be improved. In addition, a catalyst or a solvent can be added to the reaction between the polyvalent carboxylic acid and the vinyl ether compound depending on the purpose.
触媒としては、３級アミン類、イミダゾール類、有機リン系化合物、４級ホスホニウム塩類
ジアザビシクロアルケン類、有機金属化合物類、４級アンモニウム塩類、ホウ素化合物、金属ハロゲン化物等が挙げられる。
Examples of the catalyst include tertiary amines, imidazoles, organic phosphorus compounds, quaternary phosphonium salts diazabicycloalkenes, organometallic compounds, quaternary ammonium salts, boron compounds, metal halides and the like.
溶媒としては、芳香族炭化水素、エーテル類、エステルおよびエーテルエステル類、ケトン類、リン酸エステル類、ニトリル類、非プロトン性極性溶媒、プロピレングリコールアルキルエーテルアセテート類等が挙げられる。 Examples of the solvent include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphate esters, nitriles, aprotic polar solvents, propylene glycol alkyl ether acetates, and the like.
＜（Ｃ）４官能脂環式エポキシ樹脂＞
（Ｃ）４官能脂環式エポキシ樹脂としては、下記式（１）の構造を有するものを使用する。これにより、保護膜の表面平滑性が大きく向上する。
（ｌ，ｍ，ｎ，ｏは、それぞれ０以上の整数、ｌ＋ｍ＋ｎ＋ｏは０〜２０の整数）
<(C) Tetrafunctional alicyclic epoxy resin>
(C) As a tetrafunctional alicyclic epoxy resin, what has a structure of following formula (1) is used. Thereby, the surface smoothness of the protective film is greatly improved.
(L, m, n, o are each an integer of 0 or more, l + m + n + o is an integer of 0-20)
＜（Ｄ）その他のエポキシ樹脂＞
なお、本発明の熱硬化性樹脂組成物には、必要に応じて（任意成分として）、Ｃ成分以外の多官能エポキシ樹脂を含有していても良い。例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、３官能型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、ジシクロペンタジエンフェノール型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡ含核ポリオール型エポキシ樹脂、ポリプロピレングリコール型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリオキザール型エポキシ樹脂、脂環式型エポキシ樹脂、複素環型エポキシ樹脂などが挙げられる。また、Ｄ成分としての多官能エポキシ樹脂は、単独で用いても２種以上を組み合わせて用いても良い。
<(D) Other epoxy resins>
In addition, in the thermosetting resin composition of this invention, you may contain polyfunctional epoxy resins other than C component as needed (as an arbitrary component). For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type Epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A Type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Fat, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. Moreover, the polyfunctional epoxy resin as D component may be used independently, or may be used in combination of 2 or more type.
本発明の熱硬化性樹脂組成物は、さらにシランカップリング剤（Ｅ成分）と、レベリング剤（Ｆ成分）とを含有する。 The thermosetting resin composition of the present invention further contains a silane coupling agent (E component) and a leveling agent (F component).
＜（Ｅ）シランカップリング剤＞
シランカップリング剤は、シランを利用して有機材料と無機材料とを結合する連結剤であり、有機材料と反応結合する官能基として一般にビニル基、エポキシ基、アミノ基などを有する。具体的には、ビニルトリアセトキシシラン、ビニルトリス（メトキシエトキシ）シラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、アリルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、ビス（３−（トリエトキシシリル）プロピル）ジスルフィド、ビス（３−（トリエトキシシリル）プロピル）テトラスルフィド、スルフィドシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシラン、３−アミノプロピルトリエトキシシラン、３−（２−アミノエチル）アミノプロピルトリメトキシシラン、３−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、３−（２−アミノエチル）アミノプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−フェニルアミノプロピルトリメトキシシラン、３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン等が挙げられる。これらシランカップリング剤は、単独でも２種以上を併用しても良い。
<(E) Silane coupling agent>
The silane coupling agent is a linking agent that bonds an organic material and an inorganic material using silane, and generally has a vinyl group, an epoxy group, an amino group, or the like as a functional group that reacts with the organic material. Specifically, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bis (3- (tri Ethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, sulfide silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2 -Aminoethyl) aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butyl) Isopropylidene) propylamine, and the like. These silane coupling agents may be used alone or in combination of two or more.
＜（Ｆ）レベリング剤＞
レベリング剤は得られる塗膜の外観を向上させる目的で配合されるものであって、シリコン系、フッ素系、アクリル系等を特に制限無く使用することができる。
<(F) Leveling agent>
The leveling agent is blended for the purpose of improving the appearance of the obtained coating film, and silicon-based, fluorine-based, acrylic-based and the like can be used without particular limitation.
レベリング剤の市販品としては、例えばメガファックＦ−４１０（ＤＩＣ（株））、同Ｆ−４３０（同）、同Ｆ−４４４（同）、同Ｆ−４７２ＳＦ（同）、同Ｆ−４７７（同）、同Ｆ−５５２（同）、同Ｆ−５５３（同）、同Ｆ−５５４（同）、同Ｆ−５５５（同）、同Ｆ−５５６（同）、同Ｆ−５５８（同）、同Ｆ−５５９（同）、同Ｆ−５６１（同）、同Ｒ−９４（同）、同ＲＳ−７２−Ｋ（同）、同ＲＳ−７５（同）、ノベックＦＣ−４４３０（住友スリーエム（株））、ＦＣ−４４３２（同）、サーフロンＳ−６１１（ＡＧＣセイミケミカル(株)）、同Ｓ−６５１（同）、Ｓ−３８６（同）、フタージェント２０８Ｇ（ネオス（株））、同２０９Ｆ（同）、同２１２Ｐ（同）、同２２０Ｐ（同）、同２２２Ｆ（同）、同２２８Ｐ（同）、同２４０Ｇ（同）、同６０２Ａ（同）、同６５０Ａ（同）、同７１０ＦＬ（同）、同７１０ＦＭ（同）、ＦＴＸ−２１８（同）、ＢＹＫ―３０２（ビックケミー・ジャパン（株））、ＢＹＫ−３０７（同）、ＢＹＫ−３１５（同）、ＢＹＫ−３２０（同）、ＢＹＫ−３２２（同）、ＢＹＫ−３２３（同）、ＢＹＫ−３２５（同）、ＢＹＫ−３３０（同）、ＢＹＫ−３３１（同）、ＢＹＫ−３３７（同）、ＢＹＫ−３４７（同）、ＢＹＫ−３７０（同）、ＢＹＫ−ＵＶ３５００（同）、ＢＹＫ−ＵＶ３５１０（同）、ＢＹＫ−３５０（同）、ＢＹＫ−３５４（同）、ＢＹＫ−３９２（同）、ポリフローＫＬ−４００ＨＦ（共栄社化学（株））、同ＫＬ−４０１（同）、同ＫＬ−４０２（同）、同ＫＬ−４０３（同）、同ＫＬ−４０４（同）、同ＫＬ−１００（同）、同ＫＬ−６００（同）、同ＫＬ−７００（同）、同ＷＳ−３０（同）、同Ｎｏ．７５（同）、同Ｎｏ．７７（同）、同Ｎｏ．９０（同）、同Ｎｏ．９５（同）、同ＬＥ−６０４（同）等を使用できる。 Commercially available leveling agents include, for example, MegaFuck F-410 (DIC Corporation), F-430 (same), F-444 (same), F-472SF (same), and F-477 (same). Same), F-552 (same), F-553 (same), F-554 (same), F-555 (same), F-556 (same), F-558 (same) F-559 (same), F-561 (same), R-94 (same), RS-72-K (same), RS-75 (same), Novec FC-4430 (Sumitomo 3M) Co., Ltd.), FC-4432 (same), Surflon S-611 (AGC Seimi Chemical Co., Ltd.), S-651 (same), S-386 (same), Footgent 208G (Neos), 209F (same), 212P (same), 220P (same), 222F (same), 228P (same) 240G (same), 602A (same), 650A (same), 710FL (same), 710FM (same), FTX-218 (same), BYK-302 (Bicchemy Japan K.K.), BYK-307 (same), BYK-315 (same), BYK-320 (same), BYK-322 (same), BYK-323 (same), BYK-325 (same), BYK-330 (same), BYK -331 (same), BYK-337 (same), BYK-347 (same), BYK-370 (same), BYK-UV3500 (same), BYK-UV3510 (same), BYK-350 (same), BYK- 354 (same), BYK-392 (same), Polyflow KL-400HF (Kyoeisha Chemical Co., Ltd.), KL-401 (same), KL-402 (same), KL-403 (same), KL -404 (same as above) KL-100 (same), KL-600 (same), KL-700 (same), WS-30 (same), No. 75 (same), No. 77 (same), No. 90 (same), No. 95 (same), LE-604 (same), etc. can be used.
（カラーフィルター保護膜用熱硬化性樹脂組成物の製造）
本発明のカラーフィルター保護膜用熱硬化性樹脂組成物は、Ａ成分〜Ｄ成分の合計１００重量部中に、Ｃ成分を５〜５０重量部、好ましくは５〜４０重量部、より好ましくは５〜３５重量部含有する。Ｃ成分が５重量部未満であると保護膜の表面平滑性が低下し、５０重量部を超えると保護膜の密着性を損なう。
(Manufacture of thermosetting resin composition for color filter protective film)
In the thermosetting resin composition for a color filter protective film of the present invention, 5 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 5 parts by weight of C component in a total of 100 parts by weight of components A to D. Contains ~ 35 parts by weight. If the C component is less than 5 parts by weight, the surface smoothness of the protective film is lowered, and if it exceeds 50 parts by weight, the adhesion of the protective film is impaired.
その他の成分の含有量としては、Ａ成分〜Ｄ成分の合計１００重量部中に、Ａ成分は２０〜８０重量部、好ましくは２５〜７０重量部、より好ましくは３５〜６５重量部、Ｂ成分は５〜５０重量部、好ましくは１０〜４５重量部、より好ましくは１０〜４０重量部であればよい。Ａ成分が２０重量部未満であると、保護膜の強靭性を損なう可能性があり、８０重量部を超えると保護膜の密着性等の性能が低下する可能性がある。Ｂ成分が５重量部未満であると保護膜として求められる十分な硬度が得られず、５０重量部を超えるとカルボン酸が過剰となり透明性が低下することがある。 As content of other components, A component is 20 to 80 parts by weight, preferably 25 to 70 parts by weight, more preferably 35 to 65 parts by weight, and B component in 100 parts by weight of A component to D component. 5 to 50 parts by weight, preferably 10 to 45 parts by weight, more preferably 10 to 40 parts by weight. If the A component is less than 20 parts by weight, the toughness of the protective film may be impaired, and if it exceeds 80 parts by weight, performance such as adhesion of the protective film may be deteriorated. If the component B is less than 5 parts by weight, sufficient hardness required as a protective film cannot be obtained, and if it exceeds 50 parts by weight, the carboxylic acid becomes excessive and the transparency may be lowered.
一方、Ｄ成分は任意成分なので、その含有量は、Ａ成分〜Ｄ成分の合計１００重量部に対し、０〜３０重量部、好ましくは０〜２０重量部、より好ましくは０〜１５重量部であればよい。Ｄ成分が３０重量部を超えると、保護膜の透明性が低下する。 On the other hand, since the D component is an optional component, the content thereof is 0 to 30 parts by weight, preferably 0 to 20 parts by weight, more preferably 0 to 15 parts by weight with respect to 100 parts by weight of the total of the A component to the D component. I just need it. When D component exceeds 30 weight part, the transparency of a protective film will fall.
樹脂組成物の混合方法は特に限定されず、全成分を同時に混合しても良いし、各成分を順次溶解しても良いが、Ｂ成分の多価カルボン酸ヘミアセタールエステルは熱により脱ブロック反応が進行するため、多価カルボン酸ヘミアセタールエステルを含有する組成物を取り扱う際には８０℃以下とすることが好ましい。 The mixing method of the resin composition is not particularly limited, and all the components may be mixed at the same time, or each component may be dissolved sequentially, but the B component polycarboxylic acid hemiacetal ester is deblocked by heat. Therefore, when a composition containing a polyvalent carboxylic acid hemiacetal ester is handled, the temperature is preferably set to 80 ° C. or lower.
また、Ｅ成分の含有量は、Ａ成分〜Ｄ成分の合計１００重量部に対して１〜１０重量部程度とし、Ｆ成分の含有量は、Ａ成分〜Ｄ成分の合計１００重量部に対して０．１〜５重量部程度とすればよい。Ｅ成分が１重量部未満であると、保護膜の密着性等の性能が低下する場合があり、１０重量部を超えると硬化プロセスにおけるアウトガス量が増加する可能性がある。また、Ｆ成分が０．１重量部未満であると、保護膜の外観が損なわれる場合があり、５重量部を超えると保護膜の濡れ性が劣ることでリコート性が低下する可能性がある。 Moreover, content of E component shall be about 1-10 weight part with respect to a total of 100 weight part of A component-D component, and content of F component is with respect to a total of 100 weight part of A component-D component. What is necessary is just to be about 0.1-5 weight part. When the E component is less than 1 part by weight, the performance such as the adhesion of the protective film may be deteriorated, and when it exceeds 10 parts by weight, the outgas amount in the curing process may increase. Further, if the F component is less than 0.1 parts by weight, the appearance of the protective film may be impaired, and if it exceeds 5 parts by weight, the wettability of the protective film may be inferior and the recoatability may be reduced. .
＜（Ｇ）触媒＞
本発明の熱硬化性樹脂組成物には、Ａ成分〜Ｆ成分以外にも、本発明の効果を阻害しない範囲で種々の触媒を添加することができる。具体的には、ベンジルジメチルアミントリス（ジメチルアミノメチル）フェノール、ジメチルシクロヘキシルアミン等の３級アミン類；１−シアノエチル−２−エチル−４−メチルイミダゾール、２−エチル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール等のイミダゾール類；トリフェニルホスフィン、亜リン酸トリフェニル等の有機リン系化合物；テトラフェニルホスホニウムブロマイド、テトラ−ｎ−ブチルホスホニウムブロマイド等の４級ホスホニウム塩類；１，８−ジアザビシクロ［５．４．０］ウンデセン−７等やその有機酸塩等のジアザビシクロアルケン類；オクチル酸亜鉛、オクチル酸錫、オクチル酸ジルコニウム、アルミニウムアセチルアセトネート錯体等の有機金属化合物類などが挙げられる。
<(G) Catalyst>
In addition to the A component to the F component, various catalysts can be added to the thermosetting resin composition of the present invention as long as the effects of the present invention are not impaired. Specifically, tertiary amines such as benzyldimethylamine tris (dimethylaminomethyl) phenol and dimethylcyclohexylamine; 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1- Imidazoles such as benzyl-2-methylimidazole; organic phosphorus compounds such as triphenylphosphine and triphenyl phosphite; quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; 1,8- Diazabicycloalkenes such as diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate, zirconium octylate, and aluminum acetylacetonate complex Can be mentioned.
＜（Ｈ）溶剤＞
本発明の熱硬化性樹脂組成物には、使用に際して粘度等を調整する目的で有機溶剤を添加しても良い。具体的には、ベンゼン、トルエン、キシレン、エチルベンゼン、芳香族石油ナフサ、テトラリン、テレビン油、ソルベッソ＃１００（エクソン化学（株）登録商標）ソルベッソ＃１５０（エクソン化学（株）登録商標）等の芳香族炭化水素；ジオキサン、テトラヒドロフラン等のエーテル類；酢酸メチル、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、酢酸イソブチル、酢酸第二ブチル、酢酸アミル、モノメチルエーテル、酢酸メトキシブチル、エチルエトキシプロピオネート、３−メトキシ−３−メチル−１−ブチルアセテート等のエステルおよびエーテルエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノン、イソホロン、メシチルオキサイド、メチルイソアミルケトン、エチルブチルケトン、エチルアミルケトン、ジイソブチルケトン、ジエチルケトン、メチルプロピルケトン、ジイソプロピルケトン等のケトン類；トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート等のリン酸エステル類；ジメチルスルホキシド、Ｎ，Ｎ−ジメチルホルムアミド等の非プロトン性極性溶剤；トリエチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールメチルエチルエーテル、プロピレングリコールモノエチルエーテルアセテート、エチレングリコールモノフェニルエーテル、ジエチレングリコールモノフェニルエーテル、ジプロピレングリコール、ジエチレングリコール−２−エチルヘキシルエーテル、テトラエチレングリコールジメチルエーテル等のグリコール誘導体が挙げられる。より好ましくは、プロピレングリコールモノメチルエーテルアセテートが挙げられる。
<(H) solvent>
An organic solvent may be added to the thermosetting resin composition of the present invention for the purpose of adjusting viscosity and the like when used. Specifically, aromatics such as benzene, toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine oil, Solvesso # 100 (registered trademark of Exxon Chemical Co., Ltd.) and Solvesso # 150 (registered trademark of Exxon Chemical Co., Ltd.) Hydrocarbons; ethers such as dioxane and tetrahydrofuran; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, monomethyl ether, methoxybutyl acetate, ethylethoxy Esters and ether esters such as propionate and 3-methoxy-3-methyl-1-butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone, mesityl oxide, methyl Ketones such as soamyl ketone, ethyl butyl ketone, ethyl amyl ketone, diisobutyl ketone, diethyl ketone, methyl propyl ketone, diisopropyl ketone; phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate; dimethyl sulfoxide, N, N-dimethyl Aprotic polar solvents such as formamide; triethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol methyl ethyl ether, propylene glycol monoethyl ether acetate, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether , Zipiropyre Glycol, diethylene glycol 2-ethylhexyl ether, glycol derivatives such as tetraethylene glycol dimethyl ether. More preferably, propylene glycol monomethyl ether acetate is used.
（その他の添加剤）
本発明の熱硬化性樹脂組成物には、本発明の硬化を損なわない範囲において、必要に応じて、エチレングリコール、プロピレングリコール等の脂肪族ポリオール、脂肪族または芳香族カルボン酸化合物、フェノール化合物等の炭酸ガス発生防止剤、ポリアルキレングリコール等の可撓性付与剤、酸化防止剤、可塑剤、滑剤、シラン系等のカップリング剤、無機充填材等の表面処理剤、難燃剤、帯電防止剤、着色剤、レベリング剤、イオントラップ剤、摺動性改良剤、各種ゴム、有機ポリマービーズ、ガラスビーズ、グラスファイバー等の無機充填材等の耐衝撃性改良剤、揺変性付与剤、界面活性剤、表面張力低下剤、消泡剤、沈降防止剤、光拡散剤、紫外線吸収剤、抗酸化剤、離型剤、蛍光剤、導電性充填材等の添加剤を配合することができる。
(Other additives)
In the thermosetting resin composition of the present invention, an aliphatic polyol such as ethylene glycol or propylene glycol, an aliphatic or aromatic carboxylic acid compound, a phenol compound, etc. Carbon dioxide generation inhibitor, flexibility imparting agent such as polyalkylene glycol, antioxidant, plasticizer, lubricant, silane-based coupling agent, surface treatment agent such as inorganic filler, flame retardant, antistatic agent , Colorants, leveling agents, ion trapping agents, slidability improving agents, various rubbers, impact resistance improving agents such as organic polymer beads, glass beads, glass fibers, etc., thixotropic agents, surfactants Additives such as surface tension reducing agents, antifoaming agents, anti-settling agents, light diffusing agents, UV absorbers, antioxidants, mold release agents, fluorescent agents, conductive fillers, etc. .
（カラーフィルター保護膜の形成）
本発明のカラーフィルターは、上記熱硬化性樹脂組成物を硬化させてなる硬化物の層を、保護膜として備える。当該熱硬化性樹脂組成物は、基板上に配置された着色層やブラックマトリックスを覆うように塗布される。その塗布方法は特に限定されることは無く、グラビアコート法、スピンコート法、ダイコート法等の従来公知の塗工方法を採用することができる。
(Formation of color filter protective film)
The color filter of this invention is equipped with the layer of the hardened | cured material formed by hardening | curing the said thermosetting resin composition as a protective film. The said thermosetting resin composition is apply | coated so that the colored layer and black matrix arrange | positioned on a board | substrate may be covered. The coating method is not particularly limited, and conventionally known coating methods such as a gravure coating method, a spin coating method, and a die coating method can be employed.
得られた塗膜を乾燥し、さらに必要に応じて予備加熱（以下、プリベーク）を行った後、本硬化加熱（以下、ポストベーク）を経て樹脂硬化物の層を形成する。この際には、プリベーク条件として４０〜１４０℃、０〜１時間、ポストベーク条件として１５０〜２８０℃、０．２〜２時間が好ましい条件として挙げられる。また、この際の加熱手法としては、特に限定されるものではなく、例えば、密閉式硬化炉や連続硬化が可能なトンネル炉等の硬化装置を採用することができる。加熱源は特に制約されることなく、熱風循環、赤外線加熱、高周波加熱等の方法で行うことができる。 The obtained coating film is dried, and further preheated (hereinafter referred to as prebaking) as necessary, and then subjected to main curing heating (hereinafter referred to as postbaking) to form a cured resin layer. In this case, 40 to 140 ° C. and 0 to 1 hour are preferable as prebaking conditions, and 150 to 280 ° C. and 0.2 to 2 hours are preferable as post baking conditions. In addition, the heating method in this case is not particularly limited, and for example, a curing apparatus such as a closed curing furnace or a tunnel furnace capable of continuous curing can be employed. The heating source is not particularly limited, and can be performed by a method such as hot air circulation, infrared heating, high frequency heating or the like.
以下に、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらに限られるものではない。
＜重合例−１：（Ａ）エポキシ基またはオキセタニル基を有する重合体（ａ−１）の合成＞
温度計、還流冷却器、攪拌機、滴下ロートを備えた容量５００ｍＬの４つ口フラスコに、溶剤としてプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）を仕込み、攪拌しながら加熱して８０℃に昇温した。次いで、８０℃の温度で、単量体成分（ａ１）としてグリシジルメタクリレート（ＧＭＡ）が６８．７重量％、単量体成分（ａ２）としてスチレン（以下、Ｓｔ）が２７．９重量％、日油（株）製の過酸化物系重合開始剤「パーヘキシルＯ（ＰＨＯ）」が３．４重量％となるように混合し、且つ、少量のＰＧＭＥＡも予め均一混合したもの（滴下成分）を、２時間かけて滴下ロートより等速滴下した。滴下終了後、８０℃の温度を５時間維持した後、反応を終了した。重量平均分子量（Ｍｗ）５０，０００のエポキシ基含有重合体（ａ−１）の５０％ＰＧＭＥＡ溶液を得た。なお、（ａ１）成分、（ａ２）成分、及び重合開始剤の全量（合計重量）に対して、最終的な溶剤の混合量は２００重量部とした。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these.
<Polymerization Example-1: (A) Synthesis of Polymer (a-1) Having Epoxy Group or Oxetanyl Group>
Propylene glycol monomethyl ether acetate (PGMEA) was charged as a solvent in a 500 mL four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, and heated to 80 ° C. while stirring. Subsequently, at a temperature of 80 ° C., 68.7% by weight of glycidyl methacrylate (GMA) as the monomer component (a1), 27.9% by weight of styrene (hereinafter referred to as St) as the monomer component (a2), A peroxide polymerization initiator “Perhexyl O (PHO)” manufactured by Oil Co., Ltd. was mixed so as to be 3.4% by weight, and a small amount of PGMEA was previously mixed uniformly (dropping component). It dropped at a constant speed from the dropping funnel over 2 hours. After completion of the dropping, the temperature was maintained at 80 ° C. for 5 hours, and then the reaction was terminated. A 50% PGMEA solution of an epoxy group-containing polymer (a-1) having a weight average molecular weight (Mw) of 50,000 was obtained. The final solvent mixing amount was 200 parts by weight with respect to the total amount (total weight) of the component (a1), the component (a2), and the polymerization initiator.
＜重合例−２〜９：エポキシ基またはオキセタニル基を有する重合体（ａ−２〜９）の合成＞
表１に示す原料を表１に示す条件で混合し、重合例−１と同様の方法でａ−２〜ａ−９の重合体を得た。なお、表１中の略号は次の通りである。
ＧＭＡ：グリシジルメタクリレート
Ｓｔ：スチレン
ＩＢＭＡ：イソブチルメタクリレート
ＢＭＡ：ブチルメタクリレート
ＣＨＭＩ：シクロヘキシルマレイミド
ＯＸＥ−３０：メタクリル酸３−メチル−３−オキセタン−イルメチルエステル
ＤＣＰＭＡ：ジシクロペンタニルメタクリレート
ＣＨＭＡ：シクロヘキシルメタクリレート
ＭＰＳ：メタクリロキシプロピルトリメトキシシラン
ＰＨＯ：過酸化物系重合開始剤 （商品名：「パーヘキシルＯ」）
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
<Polymerization Examples 2 to 9: Synthesis of Polymer (a-2 to 9) Having Epoxy Group or Oxetanyl Group>
The raw materials shown in Table 1 were mixed under the conditions shown in Table 1, and polymers a-2 to a-9 were obtained in the same manner as in Polymerization Example-1. The abbreviations in Table 1 are as follows.
GMA: glycidyl methacrylate St: styrene IBMA: isobutyl methacrylate BMA: butyl methacrylate CHMI: cyclohexylmaleimide OXE-30: methacrylic acid 3-methyl-3-oxetane-ylmethyl ester
DCPMA: dicyclopentanyl methacrylate CHMA: cyclohexyl methacrylate MPS: methacryloxypropyltrimethoxysilane PHO: peroxide-based polymerization initiator (trade name: “Perhexyl O”)
PGMEA: Propylene glycol monomethyl ether acetate
なお、重量平均分子量（Ｍｗ）は、東ソー（株）製ゲルパーミエーションクロマトグラフィー装置ＨＬＣ−８２２０ＧＰＣを用いて、カラムとして昭和電工（株）製ＳＨＯＤＥＸＫ−８０１を用い、ＴＨＦを溶離液とし、ＲＩ検出器により測定してポリスチレン換算により求めた。 The weight average molecular weight (Mw) is RI detection using a gel permeation chromatography device HLC-8220GPC manufactured by Tosoh Corporation, using SHODEXK-801 manufactured by Showa Denko KK as a column, and THF as an eluent. Measured with a vessel and determined by polystyrene conversion.
＜合成例−１：（Ｂ）多価カルボン酸ヘミアセタールエステル（ｂ−１）の合成＞
温度計、還流冷却器、攪拌機を備えた４つ口フラスコに、溶剤としてプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）２６．９重量部、多価カルボン酸として１，２，４−シクロヘキサントリカルボン酸（ＣＨＴＡ）２７．３重量部、ビニルエーテルとしてｎ−プロピルビニルエーテル（ｎＰｒ−ＶＥ）４５．７重量部を仕込み、攪拌しながら加熱し８０℃に昇温した。次いで、温度を保ちながら攪拌し続け、混合物の酸価が２．０ｍｇＫＯＨ／ｇ以下になったところで反応を終了し、溶液の酸価１．２ｍｇＫＯＨ／ｇの多価カルボン酸ヘミアセタールエステル（ｂ−１）の６０％ＰＧＭＥＡ溶液を得た。
<Synthesis Example-1: Synthesis of (B) polyvalent carboxylic acid hemiacetal ester (b-1)>
In a four-necked flask equipped with a thermometer, reflux condenser, and stirrer, 26.9 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and 1,2,4-cyclohexanetricarboxylic acid (CHTA) as a polyvalent carboxylic acid 27.3 parts by weight and 45.7 parts by weight of n-propyl vinyl ether (nPr-VE) as a vinyl ether were charged and heated with stirring to 80 ° C. Next, stirring was continued while maintaining the temperature, and when the acid value of the mixture became 2.0 mgKOH / g or less, the reaction was terminated, and the polycarboxylic acid hemiacetal ester (b- A 60% PGMEA solution of 1) was obtained.
＜合成例−２〜６：多価カルボン酸ヘミアセタールエステル（ｂ−２〜ｂ−６）の合成＞
表２に示す原料を表２に示す条件で混合し、合成例−１と同様の方法でｂ−２〜ｂ−６の重合体を得た。なお、表２中の略号は次の通りである。
ＣＨＴＡ：１，２，４−シクロヘキサントリカルボン酸
ＴＭＡ：１，２，４−トリメリット酸
ｎＰｒ−ＶＥ：ｎ−プロピルビニルエーテル
ｉＰｒ−ＶＥ：ｉ−プロピルビニルエーテル
ｔＢｕ−ＶＥ：ｔ−ブチルビニルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
<Synthesis Examples-2 to 6: Synthesis of polyvalent carboxylic acid hemiacetal ester (b-2 to b-6)>
The raw materials shown in Table 2 were mixed under the conditions shown in Table 2, and polymers b-2 to b-6 were obtained in the same manner as in Synthesis Example-1. The abbreviations in Table 2 are as follows.
CHTA: 1,2,4-cyclohexanetricarboxylic acid TMA: 1,2,4-trimellitic acid nPr-VE: n-propyl vinyl ether iPr-VE: i-propyl vinyl ether tBu-VE: t-butyl vinyl ether PGMEA: propylene glycol Monomethyl ether acetate
なお、酸価は、０．１Ｎ・ＫＯＨエタノール溶液で滴定し、算出した。 The acid value was calculated by titration with a 0.1 N · KOH ethanol solution.
＜実施例１〜８、比較例１〜５＞
表３に示す配合量で溶解混合した実施例１〜８および比較例１〜５の熱硬化性樹脂組成物を、メンブレンフィルター（材質：ＰＥ、孔径：０．２μｍ）で濾過した後、更に中空系フィルター（材質：ＰＰ、孔径：０．０２μｍ）で濾過して得た。なお、表３中の略号は次の通りである。
<Examples 1-8, Comparative Examples 1-5>
The thermosetting resin compositions of Examples 1 to 8 and Comparative Examples 1 to 5 dissolved and mixed in the blending amounts shown in Table 3 were filtered through a membrane filter (material: PE, pore diameter: 0.2 μm), and then hollow. Obtained by filtration through a system filter (material: PP, pore size: 0.02 μm). The abbreviations in Table 3 are as follows.
ｃ−１：式（１）でｌ＋ｍ＋ｎ＋ｏ＝１の４官能脂環式エポキシ樹脂
ｃ−２：式（１）でｌ＋ｍ＋ｎ＋ｏ＝３（平均）の４官能脂環式エポキシ樹脂
c-1: Tetrafunctional alicyclic epoxy resin of formula (1) with l + m + n + o = 1 c-2: Tetrafunctional alicyclic epoxy resin of formula (1) with l + m + n + o = 3 (average)
Ｅｐ−１５７：ビスフェノールＡノボラック型エポキシ樹脂（三菱化学（株）製、商品名：「ｊＥＲ１５７Ｓ７０」、エポキシ当量２１０ｇ／ｅｑ）
ＣＧ−５００：フルオレン系エポキシ樹脂（大阪ガスケミカル（株）製、商品名：「ＯＧＳＯＬＣＧ−５００」、エポキシ当量３１１ｇ／ｅｑ）
ＶＧ３１０１Ｌ：グリシジルエ−テル型エポキシ樹脂（三井化学（株）製、商品名：「テクモアＶＧ３１０１Ｌ」、エポキシ当量２１０ｇ／ｅｑ）
Ｃｅｌ−２０２１Ｐ：３’，４’−エポキシシクロヘキシルメチル３，４−エポキシシクロヘキサンカルボキシレート（ダイセル化学工業（株）製、商品名：「セロキサイド２０２１Ｐ」、エポキシ当量１３０ｇ／ｅｑ）
ＥＨＰＥ−３１５０：２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物（ダイセル化学工業（株）製、商品名：「ＥＨＰＥ−３１５０」、エポキシ当量１７９ｇ／ｅｑ）
Ep-157: Bisphenol A novolac type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: “jER157S70”, epoxy equivalent 210 g / eq)
CG-500: Fluorene epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., trade name: “OGSOLCG-500”, epoxy equivalent 311 g / eq)
VG3101L: Glycidyl ether type epoxy resin (Mitsui Chemicals, trade name: “Techmore VG3101L”, epoxy equivalent 210 g / eq)
Cel-2021P: 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, Ltd., trade name: “Celoxide 2021P”, epoxy equivalent 130 g / eq)
EHPE-3150: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (manufactured by Daicel Chemical Industries, Ltd., trade name: “EHPE-3150 ”, Epoxy equivalent 179 g / eq)
ｅ−１：３−グリシドキシプロピルトリメトキシシラン
ｅ−２：３−グリシドキシプロピルトリエトキシシラン
ｅ−３：３−グリシドキシプロピルメチルジエトキシシラン
ｅ−４：３−グリシドキシプロピルメチルジメトキシシラン
e-1: 3-glycidoxypropyltrimethoxysilane e-2: 3-glycidoxypropyltriethoxysilane e-3: 3-glycidoxypropylmethyldiethoxysilane e-4: 3-glycidoxypropyl Methyldimethoxysilane
ＢＹＫ−３０７：シリコーン系レベリング剤（ビックケミー・ジャパン（株）製、商品名：「ＢＹＫ−３０７」）
６０２Ａ：フッ素系レベリング剤（（株）ネオス製、商品名：「フタージェント６０２Ａ」）
Ｆ４７７：フッ素系レベリング剤（ＤＩＣ（株）製、商品名：「メガファックＦ４７７」）
ＢＹＫ−３３７：シリコーン系レベリング剤（ビックケミー・ジャパン（株）製、商品名：「ＢＹＫ−３３７」）
Ｆ５５４：フッ素系レベリング剤（ＤＩＣ（株）製、商品名：「メガファック Ｆ５５４」）
Ｆ５５９：フッ素系レベリング剤（ＤＩＣ（株）製、商品名：「メガファック Ｆ５５９」）
ＺｒＯｃｔ：２−エチルヘキシル酸ジルコニル（日本化学産業（株）製、商品名：「ニッカオクチックスジルコニウム１０％（Ｋ）」）
BYK-307: Silicone leveling agent (BIC Chemie Japan Co., Ltd., trade name: “BYK-307”)
602A: Fluorine leveling agent (manufactured by Neos Co., Ltd., trade name: “Furgent 602A”)
F477: Fluorine-based leveling agent (manufactured by DIC Corporation, trade name: “Megafuck F477”)
BYK-337: Silicone leveling agent (BIC Chemie Japan Co., Ltd., trade name: "BYK-337")
F554: Fluorine-based leveling agent (manufactured by DIC Corporation, trade name: “Megafuck F554”)
F559: Fluorine-based leveling agent (manufactured by DIC Corporation, trade name: “Megafuck F559”)
ZrOct: Zirconyl 2-ethylhexylate (manufactured by Nippon Chemical Industry Co., Ltd., trade name: “Nikka Octix Zirconium 10% (K)”)
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＥＥＰ：エチルエトキシプロピオネート
ＥＤＭ：ジエチレングリコールメチルエチルエーテル
ＭＭＢＡ：３−メトキシ−３−メチル−１−ブチルアセテート
PGMEA: Propylene glycol monomethyl ether acetate EEP: Ethyl ethoxypropionate EDM: Diethylene glycol methyl ethyl ether MMBA: 3-methoxy-3-methyl-1-butyl acetate
得られた熱硬化性樹脂組成物を、スピンコーター（型式１Ｈ−ＤＸ−２、ミカサ（株）製）により１０ｃｍ角のガラス基板上に回転塗布した。塗布後、ガラス基板を９０℃のクリーンオーブン中にて２分間乾燥処理後、２３０℃のクリーンオーブン中にて３０分間加熱することにより、膜厚１．５μｍの硬化膜（保護膜）を得た。 The obtained thermosetting resin composition was spin-coated on a 10 cm square glass substrate with a spin coater (model 1H-DX-2, manufactured by Mikasa Corporation). After coating, the glass substrate was dried in a 90 ° C. clean oven for 2 minutes and then heated in a 230 ° C. clean oven for 30 minutes to obtain a cured film (protective film) having a thickness of 1.5 μm. .
得られた硬化膜について、表面平滑性、透明性、および密着性を測定評価したその結果も表３に示す。
なお、表面平滑性、透明性、および密着性は、次のようにして測定評価した。
＜表面平滑性＞
表面平滑性評価用のダミーカラーフィルターで、赤色画素と緑色画素中心部分の高さの差、赤色画素と青色画素中心部分の高さの差、および緑色画素と青色画素中心部分の高さの差（画素間段差）を求めた。引き続き、前述の硬化膜作成方法に従い、膜厚が１．５±０．０５μｍの硬化膜を形成したのちに、同一部分の赤色画素と緑色画素中心部分の高さの差、赤色画素と青色画素中心部分の高さの差、および緑色画素と青色画素中心部分の高さの差を求めた。これらの段差は触針式表面粗度計（型式ＥＫ４０００ＡＫ、小坂研究所（株）製）にて測定した。保護膜塗布前の画素間段差の内、大きい値を塗布前最大画素間段差（ｄ１）とし、保護膜塗布後の画素間段差の内、大きい値を塗布後最大画素間段差（ｄ２）とし、これらのｄ１、ｄ２から下記の計算式（１）により、保護膜用組成物の表面平滑化率Ｘを求めた。
<Surface smoothness>
Dummy color filter for surface smoothness evaluation. Difference in height between red and green pixel center, difference between red and blue pixel center, and difference between green and blue pixel center. (Step difference between pixels) was obtained. Subsequently, after forming a cured film having a thickness of 1.5 ± 0.05 μm according to the above-described cured film preparation method, the difference in height between the red pixel and the green pixel central portion of the same part, the red pixel and the blue pixel The difference in the height of the central portion and the difference in the height of the green pixel and the central portion of the blue pixel were obtained. These steps were measured with a stylus type surface roughness meter (model EK4000AK, manufactured by Kosaka Laboratory Ltd.). Among the steps between pixels before coating the protective film, a large value is the maximum step between pixels (d1) before coating, and among the steps between pixels after coating the protective film, the large value is the maximum step between pixels (d2) after coating, From these d1 and d2, the surface smoothing rate X of the protective film composition was determined by the following calculation formula (1).
表面平滑性の判定基準は、次の通りである。
表面平滑化率Ｘ（％）が、
×： Ｘ＜３０
△： ３０≦Ｘ＜５０
○： ５０≦Ｘ＜７０
◎： ７０≦Ｘ
The criteria for determining surface smoothness are as follows.
Surface smoothing rate X (%) is
×: X <30
Δ: 30 ≦ X <50
○: 50 ≦ X <70
A: 70 ≦ X
＜透明性＞
透明性の評価として、透過率を測定した。硬化膜を作製したガラス基板を、紫外−可視光分光光度計（型式ＵＶ−３７００、（株）島津製作所製）を用いて波長３８０ｎｍ〜８００ｎｍまでスキャンし、光線透過率を測定した。
<Transparency>
As an evaluation of transparency, transmittance was measured. The glass substrate on which the cured film was produced was scanned from 380 nm to 800 nm using an ultraviolet-visible light spectrophotometer (model UV-3700, manufactured by Shimadzu Corporation), and the light transmittance was measured.
透明性の判定基準は、次の通りである。
波長４００ｎｍの光線透過率Ｙ（％）が、
×： Ｙ＜８０
△： ８０≦Ｙ＜９０
○： ９０≦Ｙ＜９５
◎： ９５≦Ｙ
The criteria for determining transparency are as follows.
Light transmittance Y (%) at a wavelength of 400 nm is
×: Y <80
Δ: 80 ≦ Y <90
○: 90 ≦ Y <95
A: 95 ≦ Y
＜密着性＞
硬化膜を作製したガラス基板を１ｃｍ角に断裁し、硬化膜上にエポキシ樹脂付きスタッドピン（品番：Ｐ／Ｎ９０１１０６、ＱＵＡＤＧＲＯＵＰ（株）製）を立てた後、マウントクリップ（ＱＵＡＤ ＧＲＯＵＰ（株）製）で固定したまま１５０℃のオーブン中で１時間加熱した。その後、５０℃以下になるまでオーブン内で徐冷し、マウントクリップを取り外して評価用サンプルを得た。この評価用サンプルについてプレッシャークッカー試験（以下、ＰＣＴ）後の密着力を測定することで密着性の評価とした。ＰＣＴ条件は、「温度１２０℃、相対湿度１００％、２気圧、試験時間２時間」とした。密着力の測定は、オートグラフ（型番：ＡＧ−Ｉ、（株）島津製作所製）を用いて、引張速度１０ｍｍ／分にて行った。
<Adhesion>
The glass substrate on which the cured film is produced is cut into a 1 cm square, and a stud pin with an epoxy resin (product number: P / N901106, manufactured by QUADGROUP) is set on the cured film, and then a mount clip (manufactured by QUAD GROUP, Inc.). ) And then heated in an oven at 150 ° C. for 1 hour. Then, it annealed in oven until it became 50 degrees C or less, the mount clip was removed, and the sample for evaluation was obtained. Adhesion was evaluated by measuring the adhesion after the pressure cooker test (hereinafter referred to as PCT) for this evaluation sample. The PCT conditions were “temperature 120 ° C., relative humidity 100%, 2 atmospheres, test time 2 hours”. The adhesion was measured using an autograph (model number: AG-I, manufactured by Shimadzu Corporation) at a tensile speed of 10 mm / min.
密着性の判定基準は、次の通りである。
密着力Ｚ（ＭＰａ）が、
×： Ｚ＜１５
△： １５≦Ｚ＜２０
○： ２０≦Ｚ＜２５
◎： ２５≦Ｚ
The criteria for determining adhesion are as follows.
Adhesion force Z (MPa) is
×: Z <15
Δ: 15 ≦ Z <20
○: 20 ≦ Z <25
A: 25 ≦ Z
表３の結果から、実施例１〜８では、Ａ〜Ｄ成分を適量含有し、且つＣ成分として特定の４官能脂環式エポキシ樹脂を使用していることで、表面平滑性、透明性、及び密着性に優れる保護膜となっていた。 From the result of Table 3, in Examples 1-8, it contains surface AD, an appropriate amount, and by using a specific tetrafunctional alicyclic epoxy resin as C component, surface smoothness, transparency, And a protective film having excellent adhesion.
一方、比較例１ではＣ成分の含有量が少ないため、表面平滑性が悪かった。比較例２では、Ｃ成分の含有量が多いため、密着性が悪かった。比較例３〜５では、Ｃ成分を含有しないため、表面平滑性が悪かった。
On the other hand, in Comparative Example 1, since the content of the C component was small, the surface smoothness was poor. In Comparative Example 2, the adhesiveness was poor because the content of the C component was large. In Comparative Examples 3 to 5, since the C component was not contained, the surface smoothness was poor.
Claims (4)
Ａ成分：（ａ１）炭素−炭素不飽和結合とエポキシ基又はオキセタニル基を有するモノマーと、（ａ２）（ａ１）以外の炭素−炭素不飽和結合を有するモノマーとからなる、重量平均分子量３，０００〜１００，０００の、エポキシ基又はオキセタニル基含有重合体
Ｂ成分：多価カルボン酸化合物のカルボキシル基が、ビニルエーテル化合物によりヘミアセタールエステルとしてブロック化された、多価カルボン酸ヘミアセタールエステル
Ｃ成分：下記式（１）の構造を有す、４官能脂環式エポキシ樹脂
Ｄ成分：Ｃ成分以外の多官能エポキシ樹脂
（ｌ，ｍ，ｎ，ｏは、それぞれ０以上の整数、ｌ＋ｍ＋ｎ＋ｏは０〜２０の整数） A thermosetting resin composition comprising the following A component to C component and optionally the following D component as an optional component, wherein 5 to 50 C components are added in a total of 100 parts by weight of the A component to D component. A thermosetting resin composition containing parts by weight.
Component A: Weight average molecular weight 3,000, comprising (a1) a monomer having a carbon-carbon unsaturated bond and an epoxy group or oxetanyl group, and a monomer having a carbon-carbon unsaturated bond other than (a2) and (a1). Epoxy group or oxetanyl group-containing polymer of ˜100,000 B component: polyvalent carboxylic acid hemiacetal ester in which carboxyl group of polyvalent carboxylic acid compound is blocked by vinyl ether compound as hemiacetal ester C component: Tetrafunctional alicyclic epoxy resin having the structure of formula (1) D component: polyfunctional epoxy resin other than C component
(L, m, n, o are each an integer of 0 or more, l + m + n + o is an integer of 0-20)
A color filter having a protective film formed by curing the thermosetting resin composition according to any one of claims 1 to 3.
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