JP2016132752A - Thermosetting resin composition, and color filter having the cured film - Google Patents
Thermosetting resin composition, and color filter having the cured film Download PDFInfo
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- JP2016132752A JP2016132752A JP2015009589A JP2015009589A JP2016132752A JP 2016132752 A JP2016132752 A JP 2016132752A JP 2015009589 A JP2015009589 A JP 2015009589A JP 2015009589 A JP2015009589 A JP 2015009589A JP 2016132752 A JP2016132752 A JP 2016132752A
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- resin composition
- thermosetting resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 27
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 25
- 230000001681 protective effect Effects 0.000 claims abstract description 43
- 239000004593 Epoxy Substances 0.000 claims abstract description 37
- -1 carboxylic acid hemiacetal ester Chemical class 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 125000003566 oxetanyl group Chemical group 0.000 claims abstract description 16
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 15
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 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 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229920003986 novolac Polymers 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-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
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011230 binding agent 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
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 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
- 239000000975 dye Substances 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
- 238000012812 general test Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 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
- 239000003973 paint Substances 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
- 239000002530 phenolic antioxidant Substances 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
- 239000000049 pigment Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 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
- 229940116423 propylene glycol diacetate Drugs 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
- 125000006850 spacer group Chemical group 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
- 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
- 238000009281 ultraviolet germicidal irradiation Methods 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
- 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
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SSMSBSWKLKKXGG-UHFFFAOYSA-N 1-(2-chlorophenyl)-2-isopropylaminoethanol Chemical compound CC(C)NCC(O)C1=CC=CC=C1Cl SSMSBSWKLKKXGG-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
- 150000004963 1-benzylimidazoles Chemical class 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
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-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
- 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
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-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
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber 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
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Optical Filters (AREA)
- Liquid Crystal (AREA)
Abstract
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、ＵＶ吸収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 UV absorption, which is obtained 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、硬度や密着性に優れることが求められる。また、保護膜は、着色層の色彩に悪影響を及ぼさないように、透明性や平坦性と言った性能にも優れることが求められる。さらに、保護膜用塗工液に粘度変化（特に粘度上昇）が生じると、当該塗工膜を均一な膜厚で塗工することが困難となるため、カラーフィルター保護膜用の塗工液には、充分な保存安定性が求められる。そこで、この種の保護膜において、これらの性能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 during manufacture or use of the liquid crystal display device, and is required to have excellent hardness and adhesion. The protective film is also required to be excellent in performance such as transparency and flatness so as not to adversely affect the color of the colored layer. Furthermore, when a change in viscosity (particularly an increase in viscosity) occurs in the coating liquid for the protective film, it becomes difficult to apply the coating film with a uniform film thickness. Is required to have sufficient storage stability. Thus, in this type of protective film, it has been conventionally performed to improve these performances (see Patent Document 1).
ところで、カラーフィルターは複数の材料を層状に重ねた構造であり、保護膜上には、さらにフォトスペーサーや配向膜が形成される。当該フォトスペーサーや配向膜は、塗工液の状態で保護膜上に塗布されるが、その際、塗布性（リコート性）向上のため、保護膜表面に対し塗布前洗浄が行われる。この塗布前洗浄にはＵＶオゾン洗浄が広く使用されており、保護膜はフォトスペーサーや配向膜の塗布前洗浄時に光源である低圧水銀灯から発せられる、主に１８５ｎｍと２５４ｎｍのＵＶ光に曝される。このとき、２５４ｎｍの光は１８５ｎｍの光と比較して強度が強く、且つ吸収されにくいため、保護膜のＵＶ吸収性が不十分だと、保護膜の下層（ＲＧＢ画素）に２５４ｎｍの光が到達してＲＧＢ画素の劣化を招く恐れがある。 By the way, the color filter has a structure in which a plurality of materials are stacked in layers, and a photo spacer and an alignment film are further formed on the protective film. The photospacer and the alignment film are applied on the protective film in the state of a coating solution. At this time, the surface of the protective film is washed before application in order to improve the application property (recoat property). UV ozone cleaning is widely used for this pre-coating cleaning, and the protective film is exposed to UV light of 185 nm and 254 nm mainly emitted from a low-pressure mercury lamp as a light source during pre-coating cleaning of the photo spacer and alignment film. . At this time, 254 nm light is stronger and harder to absorb than 185 nm light. If the UV absorption of the protective film is insufficient, 254 nm light reaches the lower layer (RGB pixels) of the protective film. As a result, the RGB pixels may be deteriorated.
さらに、近年ではＲＧＢ画素の薄膜化が進んでおり、従来の発色を維持するために、ＲＧＢ画素の顔料・染料の配合割合が増加し、アクリル樹脂等のバインダーの割合が少なくなってきている。ここで、顔料・染料はバインダー成分と比較してＵＶを吸収し易く劣化し易い。そのため、ＲＧＢ画素自体も、従来より劣化し易い組成となってきている。また、近年では配向膜の配向処理方法として、従来のラビング法に代わり、ＵＶ照射による光配向が採用され始めており、製造プロセス上でもＵＶ照射の負荷が増大しつつある。 Further, in recent years, the RGB pixels have been made thinner, and in order to maintain the conventional color development, the blending ratio of pigments / dyes of RGB pixels has increased, and the ratio of binders such as acrylic resins has decreased. Here, the pigment / dye tends to absorb UV and easily deteriorate compared to the binder component. Therefore, the RGB pixel itself has a composition that is more easily deteriorated than in the past. In recent years, photo-alignment by UV irradiation has begun to be adopted as an alignment treatment method of the alignment film instead of the conventional rubbing method, and the load of UV irradiation is increasing in the manufacturing process.
このような背景から、保護膜に高いＵＶ吸収性を持たせることでＲＧＢ画素の劣化を防止することが出来るため、従来にも増して保護膜に高いＵＶ吸収性が求められるようになってきている。一方、可視光域の透過率に関しては、高い画像視認性を確保するため従来通り高いことが望まれている。つまり、短波長（２５４ｎｍ）では高いＵＶ吸収性を有し、可視光域では、透過率の高い組成物が望まれている。 From such a background, since it is possible to prevent deterioration of RGB pixels by providing the protective film with high UV absorption, higher UV absorption is required for the protective film than ever before. Yes. On the other hand, the transmittance in the visible light region is desired to be high as before in order to ensure high image visibility. That is, a composition having high UV absorption at a short wavelength (254 nm) and high transmittance in the visible light region is desired.
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透明性や硬度等の物性を維持したまま、ＵＶ吸収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。 Therefore, the object of the present invention is to provide a thermosetting resin composition capable of forming a color filter protective film excellent in UV absorption while maintaining the properties such as transparency and hardness that have been conventionally required. An 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）成分及び（Ｂ）成分と、（Ｃ）エポキシ化合物とを含む熱硬化性樹脂組成物であって、前記（Ａ）成分〜前記（Ｃ）成分の合計１００重量部中に、前記（Ａ）成分を２０〜８０重量部、前記（Ｂ）成分を５〜４５重量部、及び前記（Ｃ）成分として、少なくとも（Ｃ１）下記一般式（１）の構造を有するナフチル基含有フルオレン型エポキシ化合物を２〜３５重量部含むことを特徴とする。
（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
（Ａは炭素数が２〜３のアルキレン基を示し、ｎは０〜１の整数である。）
なお、前記（Ｃ）成分として前記（Ｃ１）成分を少なくとも必須成分として含有している限り、その他の任意成分として（Ｃ２）（Ｃ１）以外の多官能エポキシ化合物を含有させることもできる。
As a means for that, the present invention is a thermosetting resin composition comprising the following components (A) and (B) and (C) an epoxy compound, wherein the component (A) to the component (C): In a total of 100 parts by weight of the components, the component (A) is 20 to 80 parts by weight, the component (B) is 5 to 45 parts by weight, and the component (C) is at least (C1) the following general formula (1 2) to 35 parts by weight of a naphthyl group-containing fluorene type epoxy compound having a structure of
(A) Component: (a1) Weight average molecular weight 3 consisting of a monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group, and a monomer having a carbon-carbon unsaturated bond other than (a2) and (a1) Polymer having an epoxy group or oxetanyl group of 1,000 to 100,000 (B) component: a polyvalent carboxylic acid hemiacetal ester in which a carboxyl group of a polyvalent carboxylic acid compound is blocked as a hemiacetal ester by a vinyl ether compound
(A represents an alkylene group having 2 to 3 carbon atoms, and n is an integer of 0 to 1.)
In addition, as long as it contains the said (C1) component as an essential component as said (C) component, polyfunctional epoxy compounds other than (C2) (C1) can also be contained as another arbitrary component.
当該熱硬化性樹脂組成物は、さらにレベリング剤（Ｄ成分）を含有することが好ましく、カラーフィルター保護膜用として好適である。 The thermosetting resin composition preferably further contains a leveling agent (component D), and is suitable for a color filter protective film.
また、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, 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）成分として少なくとも上記一般式（１）で示される所定の構造を有するナフチル基含有フルオレン型エポキシ化合物を適量使用していることで、従来より求められている可視光域における透明性や硬度等の物性を維持したまま、ＵＶ吸収性に優れるカラーフィルター用の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 naphthyl group-containing fluorene type epoxy compound having a predetermined structure represented by the general formula (1) is used as the component (C). A protective film for a color filter having excellent UV absorption can be formed while maintaining the properties such as transparency and hardness in the visible light region that are more demanded.
≪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）エポキシ樹脂を必須成分として含む。特に、（Ｃ）成分の中でも（Ｃ１）特定構造のナフチル基含有フルオレン型エポキシ化合物を少なくとも必須成分として含み、さらに、必要に応じて（Ｃ２）（Ｃ１）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。すなわち、（Ｃ）成分として（Ｃ１）成分のみを含有する場合と、（Ｃ１）成分と（Ｃ２）成分の双方を含有する場合がある。
≪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) An epoxy resin is included as an essential component. In particular, among the components (C), (C1) a naphthyl group-containing fluorene type epoxy compound having a specific structure is included as at least an essential component, and if necessary, a polyfunctional epoxy resin other than the components (C2) and (C1) is optionally added. May be included. That is, there are cases where the component (C) contains only the component (C1) and the case where both the component (C1) and the component (C2) are contained.
＜（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 non-carbon other than (a1). It is a polymer comprising a monomer having a saturated bond.
（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、例えば下記の一般式（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。
また、オキセタニル基を有するモノマーとしては、例えば下記の一般式（５）で表されるモノマーが好ましい例として挙げられる。
（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、下記の一般式（６）〜（９）で表されるモノマーが挙げられる。
（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１種のみを単独で重合してもよく、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 superpose | polymerize individually by 1 type, and 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。 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.
（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。当該（Ａ）成分は、１種のみを単独で用いてもよく、２種以上を組み合わせて用いても良い。 (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. As the component (A), only one type may be used alone, or two or more types may be used in combination.
＜（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）エポキシ化合物＞
（Ｃ）エポキシ化合物は構成元素がＣ、Ｈ、Ｏからなる化合物を使用することができる。必須成分である（Ｃ１）ナフチル基含有フルオレン型エポキシ化合物としては、下記一般式（１）の構造を有するものを使用する。これにより、保護膜のＵＶ吸収性が大きく向上する。
（Ａは炭素数が２〜３のアルキレン基を示し、ｎは０〜１の整数である。）
<(C) Epoxy compound>
(C) As the epoxy compound, a compound whose constituent elements are C, H, and O can be used. As the essential component (C1) fluorene type epoxy compound containing naphthyl group, one having a structure of the following general formula (1) is used. Thereby, the UV absorption of the protective film is greatly improved.
(A represents an alkylene group having 2 to 3 carbon atoms, and n is an integer of 0 to 1.)
任意成分（含有していても含有していなくても成り立つ成分）である（Ｃ２）多官能エポキシ化合物としては、この種のカラーフィルター用保護膜において従来から一般的に使用されている、（Ｃ１）成分とは異なる多官能エポキシ化合物を使用できる。例えば、ビスフェノールＡ型、ビスフェノールＦ型、ジフェニルエーテル型、ハイドロキノン型、ナフタレン型、ビフェニル型、ナフチル基非含有フルオレン型、ビスフェノールＡノボラック型、フェノールノボラック型、オルソクレゾールノボラック型、トリスヒドロキシフェニルメタン型、３官能型、テトラフェニロールエタン型、ジシクロペンタジエンフェノール型、水添ビスフェノールＡ型、ビスフェノールＡ含核ポリオール型、ポリプロピレングリコール型、グリシジルエステル型、グリシジルエーテル型、グリオキザール型、脂環式型、複素環型などのエポキシ化合物が挙げられる。当該（Ｃ２）多官能エポキシ樹脂は、１種のみを単独で用いても２種以上を組み合わせて用いても良い。脂環式型エポキシ化合物として好ましくは、セロキサイド２０２１Ｐ（（株）ダイセル）、ＥＨＰＥ−３１５０（同）、グリシジルエーテル型エポキシ化合物として好ましくは、テクモアＶＧ３１０１Ｌ（（株）プリンテック）、ビスフェノールＡノボラック型エポキシ化合物として好ましくは、ｊＥＲ１５７Ｓ７０（三菱化学（株））が挙げられる。 As the (C2) polyfunctional epoxy compound that is an optional component (a component that can be contained even if it is not contained), it has been conventionally used in this kind of protective film for color filters, (C1 Polyfunctional epoxy compounds different from the component) can be used. For example, bisphenol A type, bisphenol F type, diphenyl ether type, hydroquinone type, naphthalene type, biphenyl type, naphthyl group-free fluorene type, bisphenol A novolak type, phenol novolak type, orthocresol novolak type, trishydroxyphenylmethane type, 3 Functional type, tetraphenylolethane type, dicyclopentadienephenol type, hydrogenated bisphenol A type, bisphenol A nucleated polyol type, polypropylene glycol type, glycidyl ester type, glycidyl ether type, glioxal type, alicyclic type, heterocyclic ring Examples include epoxy compounds such as molds. The said (C2) polyfunctional epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more type. The alicyclic epoxy compound is preferably Celoxide 2021P (Daicel Co., Ltd.), EHPE-3150 (same), and the glycidyl ether type epoxy compound is preferably Techmore VG3101L (Printech Co., Ltd.), bisphenol A novolac type epoxy. The compound preferably includes jER157S70 (Mitsubishi Chemical Corporation).
熱硬化性樹脂組成物は、さらに（Ｄ）レベリング剤を含有することが好ましい。
＜（Ｄ）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、この種のカラーフィルター用保護膜において従来から一般的に使用されている、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。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。
The thermosetting resin composition preferably further contains (D) a leveling agent.
<(D) Leveling agent>
Leveling agents are formulated for the purpose of improving the appearance of the resulting coating film, and are conventionally used in this type of protective film for color filters, such as silicon-based, fluorine-based, acrylic-based, etc. Can be used without any particular limitation. 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.
（熱硬化性樹脂組成物の製造）
熱硬化性樹脂組成物は、（Ａ）成分〜（Ｃ）成分の合計１００重量部中に、少なくとも（Ｃ１）成分を２〜３５重量部、好ましくは３〜３０重量部含有する。（Ｃ１）成分が２重量部未満であると保護膜のＵＶ吸収性が不十分となり、３５重量部を超えると保護膜の透明性が低下する。
(Manufacture of thermosetting resin composition)
The thermosetting resin composition contains at least 2 to 35 parts by weight, preferably 3 to 30 parts by weight of the (C1) component in a total of 100 parts by weight of the components (A) to (C). When the component (C1) is less than 2 parts by weight, the UV absorption of the protective film becomes insufficient, and when it exceeds 35 parts by weight, the transparency of the protective film is lowered.
その他の成分の含有量としては、（Ａ）成分〜（Ｃ）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、（Ｂ）成分は５〜４５重量部、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、保護膜の硬度が低下し、８０重量部を超えると保護膜の密着性を損なう可能性がある。また、（Ｂ）成分が５重量部未満であると保護膜の耐熱性が低下し、４５重量部を超えると保護膜の透明性を損なう可能性がある。 As content of other components, (A) component is 20 to 80 parts by weight, preferably 25 to 70 parts by weight, and (B) component is in 100 parts by weight of the total of components (A) to (C). It may be 5 to 45 parts by weight, preferably 10 to 40 parts by weight. If the component (A) is less than 20 parts by weight, the hardness of the protective film is reduced, and if it exceeds 80 parts by weight, the adhesion of the protective film may be impaired. Further, when the component (B) is less than 5 parts by weight, the heat resistance of the protective film is lowered, and when it exceeds 45 parts by weight, the transparency of the protective film may be impaired.
一方、（Ｃ２）成分は任意成分なので、その含有量は、（Ａ）成分〜（Ｃ）成分の合計１００重量部に対し、０〜５０重量部、好ましくは５〜４５重量部であればよい。（Ｃ１）成分と（Ｃ２）成分を併用する場合、（Ｃ）成分全体（Ｃ１＋Ｃ２）の含有量は、（Ａ）成分〜（Ｃ）成分の合計１００重量部に対し７０重量部以下、好ましくは６５重量部以下とする。（Ｃ１＋Ｃ２）の含有量が（Ａ）成分〜（Ｃ）成分の合計１００重量部に対して７０重量部を超えると、保護膜の透明性が大きく低下する。 On the other hand, since the component (C2) is an optional component, its content may be 0 to 50 parts by weight, preferably 5 to 45 parts by weight, with respect to 100 parts by weight as a total of the components (A) to (C). . When the component (C1) and the component (C2) are used in combination, the content of the entire component (C) (C1 + C2) is 70 parts by weight or less, preferably 100 parts by weight or less, 65 parts by weight or less. When the content of (C1 + C2) exceeds 70 parts by weight with respect to 100 parts by weight as a total of the components (A) to (C), the transparency of the protective film is greatly reduced.
また、（Ｄ）成分の含有量は、（Ａ）成分〜（Ｃ）成分の合計１００重量部に対して０．０５〜５重量部、好ましくは０．１〜２重量部程度とすればよい。（Ｄ）成分が０．０５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。 In addition, the content of the component (D) may be 0.05 to 5 parts by weight, preferably about 0.1 to 2 parts by weight with respect to 100 parts by weight as a total of the components (A) to (C). . When the component (D) is less than 0.05 parts by weight, the appearance of the protective film may be impaired, and when it exceeds 5 parts by weight, the wettability of the protective film may be inferior and the recoatability may be reduced. .
熱硬化性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 thermosetting resin composition is not particularly limited, and all the components may be mixed at the same time or each component may be dissolved in sequence, but the (B) component polycarboxylic acid hemiacetal ester is Since the deblocking reaction proceeds by heat, when handling a composition containing a polyvalent carboxylic acid hemiacetal ester, the temperature is preferably 80 ° C. or lower.
（その他の添加剤）
熱硬化性樹脂組成物は、（Ｄ）レベリング剤以外にも、本発明の効果を阻害しない範囲で、シランカップリング剤、酸化防止剤、触媒、安定剤、有機溶剤、炭酸ガス発生防止剤、可撓性付与剤、可塑剤、滑剤、表面処理剤、難燃剤、帯電防止剤、着色剤、イオントラップ剤、摺動性改良剤、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、導電性充填材など、種々の添加剤を配合することができる。
(Other additives)
In addition to (D) the leveling agent, the thermosetting resin composition is a silane coupling agent, an antioxidant, a catalyst, a stabilizer, an organic solvent, a carbon dioxide generation inhibitor, as long as the effects of the present invention are not impaired. Flexibility imparting agent, plasticizer, lubricant, surface treatment agent, flame retardant, antistatic agent, colorant, ion trap agent, slidability improving agent, impact resistance improving agent, thixotropic agent, surfactant, Various additives such as a surface tension reducing agent, an antifoaming agent, an anti-settling agent, a light diffusing agent, an ultraviolet absorber, an antioxidant, a mold release agent, a fluorescent agent, and a conductive filler can be blended.
＜（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）酸化防止剤＞
酸化防止剤としては、ＩＲＧＡＮＯＸ１０１０（ＢＡＳＦ）、ＩＲＧＡＮＯＸ１０３５（同）、ＩＲＧＡＮＯＸ１０７６（同）、ＩＲＧＡＮＯＸ１０９８（同）、ＩＲＧＡＮＯＸ１１３５（同）、ＩＲＧＡＮＯＸ１３３０（同）、ＩＲＧＡＮＯＸ１７２６（同）、ＩＲＧＡＮＯＸ１４２５ＷＬ（同）、ＩＲＧＡＮＯＸ１５２０Ｌ（同）、ＩＲＧＡＮＯＸ２４５（同）、ＩＲＧＡＮＯＸ２５９（同）、ＩＲＧＡＮＯＸ３１１４（同）、ＩＲＧＡＮＯＸ５０５７（同）、ＩＲＧＡＮＯＸ５６５（同）、ＩＲＧＡＭＯＤ２９５（同）等のヒンダードフェノール系酸化防止剤などが挙げられる。
<(F) Antioxidant>
As antioxidants, IRGANOX1010 (BASF), IRGANOX1035 (same), IRGANOX1076 (same), IRGANOX1098 (same), IRGANOX1135 (same), IRGANOX1330 (same), IRGANOX1726 (same), IRGANOX1425WL (same), IRGANOX1520L (same) , IRGANOX245 (same), IRGANOX259 (same), IRGANOX3114 (same), IRGANOX5057 (same), IRGANOX565 (same), IRGAMOD295 (same), hindered phenolic antioxidants, etc. are mentioned.
＜（Ｇ）触媒＞
触媒としては、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>
Catalysts include tertiary amines such as benzyldimethylamine tris (dimethylaminomethyl) phenol and dimethylcyclohexylamine; 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl Imidazoles such as 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-diazabicyclo [5.4.0] Diazabicycloalkenes such as undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate, zirconium octylate, and aluminum acetylacetonate complex It is done.
＜（Ｈ）安定剤＞
安定剤は、［００２４］に記載の過剰のビニルエーテルのことを指し、（Ｂ）多価カルボン酸ヘミアセタールエステルの収率向上の目的で添加される。具体的には、［００２３］に記載のビニルエーテルが挙げられる。
<(H) Stabilizer>
The stabilizer refers to the excess vinyl ether described in [0024], and is added for the purpose of improving the yield of (B) polycarboxylic acid hemiacetal ester. Specific examples include vinyl ethers described in [0023].
＜（Ｉ）有機溶剤＞
有機溶剤は、熱硬化性樹脂組成物の粘度等を調整する目的で添加される。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、プロピレングリコールジアセテート、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。
<(I) Organic solvent>
The organic solvent is added for the purpose of adjusting the viscosity and the like of the thermosetting resin composition. 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, propylene glycol diacetate, ethylene glycol monophenyl ether , Diethylene glycol Monophenyl ether, dipropylene glycol, diethylene glycol 2-ethylhexyl ether, glycol derivatives such as tetraethylene glycol dimethyl ether. More preferably, propylene glycol monomethyl ether acetate is used.
（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、インクジェット法、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 an ink jet 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. Moreover, 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、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９２．０重量部仕込み、攪拌しながら加熱して８０℃に昇温した。次いで、８０℃の温度で３、４−エポキシシクロヘキシルメチルメタクリレート（Ｍ−１００）７８．５重量部、スチレン（Ｓｔ）２１．５重量部、日油（株）製の過酸化物系重合開始剤「パーヘキシルＯ（ＰＨＯ）」３．２重量部、およびＰＧＭＥＡ４．８重量部を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。その後、８０℃の温度を５時間維持し、重量平均分子量（Ｍｗ）５０，８００のエポキシ基を有する重合体（Ａ−１）の５０％ＰＧＭＥＡ溶液を得た。
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>
92.0 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was charged into a 500 mL four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel and heated to 80 ° C. while stirring. did. Next, 78.5 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (M-100), 21.5 parts by weight of styrene (St) at a temperature of 80 ° C., a peroxide polymerization initiator manufactured by NOF Corporation. A mixture obtained by uniformly mixing 3.2 parts by weight of “perhexyl O (PHO)” and 4.8 parts by weight of PGMEA in advance (dropping component) was dropped at a constant rate from a dropping funnel over 2 hours. Then, the temperature of 80 degreeC was maintained for 5 hours, and the 50% PGMEA solution of the polymer (A-1) which has an epoxy group of weight average molecular weight (Mw) 50,800 was obtained.
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.
＜重合例２〜８：エポキシ基またはオキセタニル基を有する重合体（Ａ−２〜Ａ−８）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−８の重合体を得た。各原料の仕込み量、反応温度、重量平均分子量を表１に示す。なお、表１中の略号は次の通りである。
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
ＧＭＡ：グリシジルメタクリレート
ＢＭＡ：ブチルメタクリレート
ＢＡ： ブチルアクリレート
ＣＨＭＩ：シクロヘキシルマレイミド
ＭＰＳ：メタクリロキシプロピルトリメトキシシラン
ＣＨＭＡ：シクロヘキシルメタクリレート
<Polymerization Examples 2 to 8: Synthesis of Polymer (A-2 to A-8) 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-8 were obtained in the same manner as in Polymerization Example 1. Table 1 shows the charged amount, reaction temperature, and weight average molecular weight of each raw material. The abbreviations in Table 1 are as follows.
OXE-30: Methacrylic acid 3-methyl-3-oxetane-ylmethyl ester
GMA: glycidyl methacrylate BMA: butyl methacrylate BA: butyl acrylate CHMI: cyclohexyl maleimide MPS: methacryloxypropyltrimethoxysilane CHMA: cyclohexyl methacrylate
＜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）２６．８重量部、多価カルボン酸としてトリメリット酸（ＴＭＡ）２６．９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）４６．３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０．６ｍｇＫＯＨ／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, a reflux condenser, and a stirrer, 26.8 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, 26.9 parts by weight of trimellitic acid (TMA) as a polyvalent carboxylic acid, As vinyl ether, 46.3 parts by weight of n-propyl vinyl ether (nPr-VE) was charged, heated with stirring and heated to 80 ° C. Next, stirring was continued while maintaining the temperature, and the reaction was terminated when the acid value of the mixture became 2.0 mgKOH / g or less, and the polycarboxylic acid hemiacetal ester (B- A 60% PGMEA solution of 1) was obtained.
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.
＜合成例２〜５：多価カルボン酸ヘミアセタールエステル（Ｂ−２〜Ｂ−５）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−５の反応物を得た。各原料の仕込み量、反応温度、酸価を表２に示す。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
ｉＰｒ−ＶＥ：ｉ−プロピルビニルエーテル
ＭＥＫ： メチルエチルケトン
<Synthesis Examples 2 to 5: Synthesis of polyvalent carboxylic acid hemiacetal ester (B-2 to B-5)>
The raw materials shown in Table 2 were mixed under the conditions shown in Table 2, and the reactants B-2 to B-5 were obtained in the same manner as in Synthesis Example 1. Table 2 shows the charged amount, reaction temperature, and acid value of each raw material. The abbreviations in Table 2 are as follows.
CHTA: 1,2,4-cyclohexanetricarboxylic acid iPr-VE: i-propyl vinyl ether MEK: methyl ethyl ketone
＜実施例１〜７、比較例１〜８＞
表３に示す配合量で溶解混合した実施例１〜７および表４に示す配合量で溶解混合した比較例１〜８のカラーフィルター保護膜用樹脂組成物は、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。得られたカラーフィルター保護膜用樹脂組成物の塗工液を、スピンコーター（型式１Ｈ−ＤＸ−２、ミカサ（株）製）により１０ｃｍ角の石英ガラスもしくは無アルカリガラス基板上に回転塗布した。塗布後、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の硬化膜を得た。
<Examples 1-7, Comparative Examples 1-8>
The resin compositions for color filter protective films of Examples 1 to 7 dissolved and mixed in the amounts shown in Table 3 and Comparative Examples 1 to 8 dissolved and mixed in the amounts shown in Table 4 are membrane filters (material: PE, pore size) : 0.2 μm), and further filtered through a hollow filter (material: PP, pore diameter: 0.02 μm). The obtained coating solution of the resin composition for a color filter protective film was spin-coated on a 10 cm square quartz glass or non-alkali glass substrate by a spin coater (model 1H-DX-2, manufactured by Mikasa Co., Ltd.). After coating, the substrate was dried in a clean oven at 90 ° C. for 2 minutes and then heated in a clean oven at 230 ° C. for 30 minutes to obtain a cured film having a thickness of 1.5 μm.
各実施例で使用した（Ｃ１）成分及び比較例で使用したナフチル基非含有フルオレン型エポキシ化合物（（Ｃ１’）成分）は、次の通りである。
（Ｃ１−１）
（Ｃ１−２）
（Ｃ１−３）
（Ｃ１−４）
ナフチル基含有フルオレン型エポキシ化合物（大阪ガスケミカル（株）製、商品名：「ＯＧＳＯＬ ＣＧ−５００」、エポキシ当量３１１ ｇ／ｅｑ）
（Ｃ１’−５）
（Ｃ１’−６）
（Ｃ１’−７）
ナフチル基非含有フルオレン型エポキシ化合物（新日鉄住金化学（株）製、商品名「ＥＳＦ−３００」、エポキシ当量 ２３１ ｇ／ｅｐ）
The (C1) component used in each example and the naphthyl group-free fluorene type epoxy compound ((C1 ′) component) used in the comparative examples are as follows.
(C1-1)
(C1-2)
(C1-3)
(C1-4)
Naphthyl group-containing fluorene type epoxy compound (manufactured by Osaka Gas Chemical Co., Ltd., trade name: “OGSOL CG-500”, epoxy equivalent 311 g / eq)
(C1'-5)
(C1'-6)
(C1'-7)
Naphthyl group-free fluorene type epoxy compound (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name “ESF-300”, epoxy equivalent 231 g / ep)
また、その他の成分として表３および表４に示すものは、次の通りである。
（Ｃ２成分）
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、脂環式型エポキシ化合物（（株）ダイセル製、商品名：「セロキサイド２０２１Ｐ」、エポキシ当量１３０ｇ／ｅｑ）
ＶＧ３１０１Ｌ：グリシジルエ−テル型エポキシ化合物（（株）プリンテック製、商品名：「テクモアＶＧ３１０１Ｌ」、エポキシ当量２１０ｇ／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、脂環式型エポキシ化合物（（株）ダイセル製、商品名：「ＥＨＰＥ−３１５０」、エポキシ当量１７６ｇ／ｅｑ）
Ｅｐ−１５７：ビスフェノールＡノボラック型エポキシ化合物（三菱化学（株）製、商品名：「ｊＥＲ １５７Ｓ７０」、エポキシ当量２１０ｇ／ｅｑ）
ＥＯＣＮ−１０２０：クレゾールノボラック型エポキシ化合物（日本化薬（株）製、商品名：「ＥＯＣＮ−１０２０」、エポキシ当量２００ｇ／ｅｑ）
ＨＰ−５０００：ナフチル基含有エポキシ化合物（ＤＩＣ（株）製、商品名「ＥＰＩＣＲＯＮ ＨＰ−５０００」、エポキシ当量２５０ｇ／ｅｑ）
The other components shown in Tables 3 and 4 are as follows.
(C2 component)
CEL-2021P: 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, alicyclic epoxy compound (manufactured by Daicel Corporation, trade name: “Celoxide 2021P”, epoxy equivalent 130 g / eq)
VG3101L: Glycidyl ether type epoxy compound (manufactured by Printec Co., Ltd., trade name: “Techmore VG3101L”, epoxy equivalent 210 g / eq)
EHPE-3150: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, alicyclic epoxy compound (trade name, manufactured by Daicel Corporation) : “EHPE-3150”, epoxy equivalent 176 g / eq)
Ep-157: Bisphenol A novolak-type epoxy compound (Mitsubishi Chemical Corporation, trade name: “jER 157S70”, epoxy equivalent 210 g / eq)
EOCN-1020: Cresol novolak type epoxy compound (manufactured by Nippon Kayaku Co., Ltd., trade name: “EOCN-1020”, epoxy equivalent 200 g / eq)
HP-5000: naphthyl group-containing epoxy compound (manufactured by DIC Corporation, trade name “EPICRON HP-5000”, epoxy equivalent 250 g / eq)
（Ｄ成分）
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」）
Ｆ−５５９：フッ素系レベリング剤（ＤＩＣ（株）製、商品名：「メガファックＦ−５５９」）
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」）
ＦＴＸ−２１８：フッ素系レベリング剤（（株）ネオス製、商品名：「ＦＴＸ−２１８」）
Ｆ−５５４：フッ素系レベリング剤（ＤＩＣ（株）製、商品名：「メガファックＦ−５５４」）
Ｆ−４７７：フッ素系レベリング剤（ＤＩＣ（株）製、商品名：「メガファックＦ−４７７」）
(D component)
BYK-307: Silicone leveling agent (BIC Chemie Japan Co., Ltd., trade name: “BYK-307”)
F-559: Fluorine-based leveling agent (manufactured by DIC Corporation, trade name: “Megafuck F-559”)
602A: Fluorine leveling agent (manufactured by Neos Co., Ltd., trade name: “Furgent 602A”)
FTX-218: Fluorine-based leveling agent (trade name: “FTX-218”, manufactured by Neos Co., Ltd.)
F-554: Fluorine-based leveling agent (manufactured by DIC Corporation, trade name: “Megafac F-554”)
F-477: Fluorine-based leveling agent (manufactured by DIC Corporation, trade name: “Megafuck F-477”)
（Ｅ成分）
Ｚ−６０４０：３−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング（株）製、商品名：「Ｚ−６０４０」）
Ｘ−４１−１０５９Ａ：シラン化合物（信越化学（株）製、商品名：「Ｘ−４１−１０５９Ａ」）
Ｘ−４１−１０５３： シラン化合物（信越化学（株）製、商品名：「Ｘ−４１−１０５３」）
(E component)
Z-6040: 3-glycidoxypropyltrimethoxysilane (made by Toray Dow Corning Co., Ltd., trade name: “Z-6040”)
X-41-1059A: Silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “X-41-1059A”)
X-41-1053: Silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “X-41-1053”)
（Ｆ成分）
ＩＲＧＡＮＯＸ−１０１０：ヒンダードフェノール系酸化防止剤（ＢＡＳＦ製、商品名：「ＩＲＧＡＮＯＸ−１０１０」）
(F component)
IRGANOX-1010: hindered phenolic antioxidant (manufactured by BASF, trade name: “IRGANOX-1010”)
（Ｇ成分）
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）」
(G component)
ZrOct: Zirconyl 2-ethylhexylate (manufactured by Nippon Chemical Industry Co., Ltd., trade name “Nikka Octix Zirconium 10% (K)”
（Ｈ成分）
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
(H component)
nPr-VE: n-propyl vinyl ether iPr-VE: i-propyl vinyl ether
（Ｉ成分）
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
ＭＭＢＡ：３−メトキシ−３−メチル−１−ブチルアセテート
ＥＤＭ：ジエチレングリコールメチルエチルエーテル
ＥＥＰ：エチルエトキシプロピオネート
ＰＧＤＡ：プロピレングリコールジアセテート
(I component)
PGMEA: Propylene glycol monomethyl ether acetate MMBA: 3-Methoxy-3-methyl-1-butyl acetate EDM: Diethylene glycol methyl ethyl ether EEP: Ethyl ethoxypropionate PGDA: Propylene glycol diacetate
得られた硬化膜のＵＶ吸収性、透明性、鉛筆硬度、密着性（クロスカット試験）および塗工液の保存安定性の物性評価を、次のようにして行った。その結果も表３および表４に示す。
＜ＵＶ吸収性および透明性＞
ＵＶ吸収性および透明性は透過率測定にて評価した。硬化膜を形成した石英ガラス基板を、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２００〜８００ｎｍまでスキャンし、光線透過率を測定した。なお、両性能は下記波長の透過率から評価した。
ＵＶ吸収性：２５４ｎｍの透過率
透明性：３８０〜５００ｎｍの平均透過率
本発明の目的に供するには、ＵＶ吸収性が１．００％未満、透明性が９６．０％以上である必要がある。
The obtained cured film was evaluated for physical properties of UV absorption, transparency, pencil hardness, adhesion (cross-cut test) and storage stability of the coating liquid as follows. The results are also shown in Tables 3 and 4.
<UV absorption and transparency>
UV absorption and transparency were evaluated by measuring transmittance. The quartz glass substrate on which the cured film was formed was scanned to a wavelength of 200 to 800 nm using an ultraviolet-visible light spectrophotometer (model UV-3700, manufactured by Shimadzu Corporation), and the light transmittance was measured. Both performances were evaluated from transmittance at the following wavelengths.
UV absorptivity: 254 nm transmittance Transparency: 380 to 500 nm average transmittance For the purpose of the present invention, the UV absorptivity must be less than 1.00% and the transparency must be 96.0% or more. .
＜鉛筆硬度＞
硬化膜を形成した無アルカリガラス基板をＪＩＳＫ５６００−５−４：１９９９「塗料一般試験方法−第５部：塗膜の機械的性質−第４節：引っかき硬度（鉛筆法）」に準拠した方法で評価した。本発明の目的に供するには、３Ｈ以上が必要である。
<Pencil hardness>
A non-alkali glass substrate on which a cured film is formed is a method in accordance with JIS K5600-5-4: 1999 “Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 4: Scratch Hardness (Pencil Method)”. evaluated. For the purpose of the present invention, 3H or more is required.
＜密着性：クロスカット試験＞
硬化膜を形成した無アルカリガラス基板をプレッシャークッカー試験（ＰＣＴ）に通した後、ＪＩＳＫ ５６００−５−６：１９９９「塗料一般試験方法−第５部：塗膜の機械的性質−第６節：付着性（クロスカット法）」に準拠した方法で密着性を評価した。ＰＣＴは、温度１２０℃、相対湿度１００％、気圧２気圧、試験時間６時間にて試験を行った。本発明の目的に供するには、１００／１００が必要である。
<Adhesion: cross-cut test>
After passing the alkali-free glass substrate on which the cured film is formed through a pressure cooker test (PCT), JISK 5600-5-6: 1999 “Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesion was evaluated by a method based on “Adhesiveness (Crosscutting Method)”. PCT was tested at a temperature of 120 ° C., a relative humidity of 100%, an atmospheric pressure of 2 atmospheres, and a test time of 6 hours. 100/100 is required to serve the purpose of the present invention.
＜保存安定性＞
熱硬化性樹脂組成物の塗工液を密閉容器中に５℃で放置し、測定温度２５℃での粘度が塗工液調製直後の粘度の２倍になるまでの期間（日）を計測した。本発明の目的に供するには、１８０日以上の必要がある。
<Storage stability>
The coating solution of the thermosetting resin composition was allowed to stand in a sealed container at 5 ° C., and the period (day) until the viscosity at the measurement temperature of 25 ° C. was twice the viscosity immediately after preparation of the coating solution was measured. . In order to serve the object of the present invention, it takes 180 days or more.
表３の結果から、実施例１〜７では、（Ａ）成分、（Ｂ）成分、及び特定の（Ｃ１）成分を適量含有していることで、ＵＶ吸収性、透明性、鉛筆硬度、密着性、及び保存安定性に優れる保護膜となっていた。 From the result of Table 3, in Examples 1-7, (A) component, (B) component, and the specific (C1) component are contained by appropriate amount, UV absorptivity, transparency, pencil hardness, adhesion And a protective film excellent in storage stability.
一方、表４の結果から、比較例１〜４では、ナフチル基を含有しないフルオレン型エポキシ化合物を使用したため、ＵＶ吸収性が劣っていた。中でも、比較例２はナフチル基を含有しないフルオレン型エポキシ化合物の含有量が多すぎるため、透明性も劣っていた。また、比較例５〜６は、フルオレン骨格を有さないナフチル基含有エポキシ化合物を使用したため、ＵＶ吸収性が劣っていた。また、比較例７では（Ｃ１）成分の含有量が多すぎるため、透明性が劣っていた。逆に、比較例８は（Ｃ１）成分の含有量が少なすぎるため、ＵＶ吸収性が劣っていた。
On the other hand, from the results of Table 4, in Comparative Examples 1 to 4, since a fluorene type epoxy compound not containing a naphthyl group was used, the UV absorption was inferior. Especially, since the comparative example 2 has too much content of the fluorene type epoxy compound which does not contain a naphthyl group, transparency was also inferior. Moreover, since Comparative Examples 5-6 used the naphthyl group containing epoxy compound which does not have a fluorene skeleton, UV absorption was inferior. Moreover, in comparative example 7, since there was too much content of (C1) component, transparency was inferior. Conversely, Comparative Example 8 was inferior in UV absorption because the content of the component (C1) was too small.
Claims (4)
前記（Ａ）成分〜前記（Ｃ）成分の合計１００重量部中に、前記（Ａ）成分を２０〜８０重量部、前記（Ｂ）成分を５〜４５重量部、及び前記（Ｃ）成分として少なくとも（Ｃ１）下記一般式（１）の構造を有するナフチル基含有フルオレン型エポキシ化合物を２〜３５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
（Ａは炭素数が２〜３のアルキレン基を示し、ｎは０〜１の整数である。） A thermosetting resin composition comprising the following component (A) and component (B), and (C) an epoxy compound,
In a total of 100 parts by weight of the component (A) to the component (C), the component (A) is 20 to 80 parts by weight, the component (B) is 5 to 45 parts by weight, and the component (C). A thermosetting resin composition comprising 2 to 35 parts by weight of at least (C1) a naphthyl group-containing fluorene type epoxy compound having a structure represented by the following general formula (1).
(A) Component: (a1) Weight average molecular weight 3 consisting of a monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group, and a monomer having a carbon-carbon unsaturated bond other than (a2) and (a1) Polymer having an epoxy group or oxetanyl group of 1,000 to 100,000 (B) component: a polyvalent carboxylic acid hemiacetal ester in which a carboxyl group of a polyvalent carboxylic acid compound is blocked as a hemiacetal ester by a vinyl ether compound
(A represents an alkylene group having 2 to 3 carbon atoms, and n is an integer of 0 to 1.)
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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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018073652A3 (en) * | 2016-10-21 | 2018-06-07 | Toray Industries, Inc. | Epoxy resin compositions and fiber-reinforced composite materials prepared therefrom |
| CN109467941A (en) * | 2017-09-07 | 2019-03-15 | 信越化学工业株式会社 | Resin combination, resin film, semiconductor layer stack, the manufacturing method of the manufacturing method of semiconductor layer stack and semiconductor device |
| CN109976090A (en) * | 2017-12-28 | 2019-07-05 | 日铁化学材料株式会社 | Thermosetting composition, cured film and display device |
| WO2024090531A1 (en) * | 2022-10-28 | 2024-05-02 | 日産化学株式会社 | Cation-curable composition |
| JP7493301B2 (en) | 2017-12-28 | 2024-05-31 | 日鉄ケミカル＆マテリアル株式会社 | Thermosetting composition, cured film and display device |
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| JP2015007687A (en) * | 2013-06-25 | 2015-01-15 | 日油株式会社 | Thermosetting resin composition for color filter protective film and color filter having the cured film |
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| JP2015007687A (en) * | 2013-06-25 | 2015-01-15 | 日油株式会社 | Thermosetting resin composition for color filter protective film and color filter having the cured film |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018073652A3 (en) * | 2016-10-21 | 2018-06-07 | Toray Industries, Inc. | Epoxy resin compositions and fiber-reinforced composite materials prepared therefrom |
| CN109890866A (en) * | 2016-10-21 | 2019-06-14 | 东丽株式会社 | Composition epoxy resin and fibre reinforced composites prepared therefrom |
| US10829633B2 (en) | 2016-10-21 | 2020-11-10 | Toray Industries, Inc. | Epoxy resin compositions and fiber-reinforced composite materials prepared therefrom |
| CN109890866B (en) * | 2016-10-21 | 2021-11-12 | 东丽株式会社 | Epoxy resin composition and fiber-reinforced composite material prepared therefrom |
| CN109467941A (en) * | 2017-09-07 | 2019-03-15 | 信越化学工业株式会社 | Resin combination, resin film, semiconductor layer stack, the manufacturing method of the manufacturing method of semiconductor layer stack and semiconductor device |
| CN109467941B (en) * | 2017-09-07 | 2022-02-11 | 信越化学工业株式会社 | Resin composition, resin film, semiconductor laminate, method for producing semiconductor laminate, and method for producing semiconductor device |
| CN109976090A (en) * | 2017-12-28 | 2019-07-05 | 日铁化学材料株式会社 | Thermosetting composition, cured film and display device |
| JP2019119765A (en) * | 2017-12-28 | 2019-07-22 | 日鉄ケミカル＆マテリアル株式会社 | Thermosetting composition, cured film and display device |
| JP7493301B2 (en) | 2017-12-28 | 2024-05-31 | 日鉄ケミカル＆マテリアル株式会社 | Thermosetting composition, cured film and display device |
| WO2024090531A1 (en) * | 2022-10-28 | 2024-05-02 | 日産化学株式会社 | Cation-curable composition |
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