JP4765369B2 - Thermosetting resin composition for color filter protective film - Google Patents
Thermosetting resin composition for color filter protective film Download PDFInfo
- Publication number
- JP4765369B2 JP4765369B2 JP2005095961A JP2005095961A JP4765369B2 JP 4765369 B2 JP4765369 B2 JP 4765369B2 JP 2005095961 A JP2005095961 A JP 2005095961A JP 2005095961 A JP2005095961 A JP 2005095961A JP 4765369 B2 JP4765369 B2 JP 4765369B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- color filter
- resin composition
- thermosetting resin
- protective film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000001681 protective effect Effects 0.000 title claims description 70
- 239000011342 resin composition Substances 0.000 title claims description 61
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 57
- -1 carboxylic acid compound Chemical class 0.000 claims description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 38
- 125000003700 epoxy group Chemical group 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 23
- 239000004593 Epoxy Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000001723 curing Methods 0.000 description 37
- 238000000034 method Methods 0.000 description 30
- 239000000243 solution Substances 0.000 description 25
- 239000002253 acid Substances 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 239000000758 substrate Substances 0.000 description 17
- 239000000178 monomer Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010538 cationic polymerization reaction Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 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 4
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 3
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 3
- 150000002921 oxetanes Chemical class 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- JFWFAUHHNYTWOO-UHFFFAOYSA-N 2-[(2-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC=C1COCC1OC1 JFWFAUHHNYTWOO-UHFFFAOYSA-N 0.000 description 2
- OCKQMFDZQUFKRD-UHFFFAOYSA-N 2-[(3-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC(COCC2OC2)=C1 OCKQMFDZQUFKRD-UHFFFAOYSA-N 0.000 description 2
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 0.000 description 2
- VVOGWKBSDTZLCD-UHFFFAOYSA-N 3-ethyl-3-(methoxymethyl)oxetane Chemical compound COCC1(CC)COC1 VVOGWKBSDTZLCD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- MTQOBMDVVPUSLZ-UHFFFAOYSA-N bis[(3-ethyloxetan-3-yl)methyl] cyclohexane-1,4-dicarboxylate Chemical compound CCC1(COC(=O)C2CCC(CC2)C(=O)OCC2(CC)COC2)COC1 MTQOBMDVVPUSLZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 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
- 150000002170 ethers Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000012812 general test Methods 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- HEQBUZNAOJCRSL-UHFFFAOYSA-N iron(ii) chromite Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Fe+3] HEQBUZNAOJCRSL-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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 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
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 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
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 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
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- RSHKWPIEJYAPCL-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(CC)COC1 RSHKWPIEJYAPCL-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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-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
- AJJLBMIIDVIQIA-UHFFFAOYSA-N 2-[1-(2-ethenylphenyl)ethoxymethyl]oxirane Chemical compound C=1C=CC=C(C=C)C=1C(C)OCC1CO1 AJJLBMIIDVIQIA-UHFFFAOYSA-N 0.000 description 1
- GBQNGHNVAOQHBN-UHFFFAOYSA-N 2-[1-(4-ethenylphenyl)ethoxymethyl]oxirane Chemical compound C=1C=C(C=C)C=CC=1C(C)OCC1CO1 GBQNGHNVAOQHBN-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
- XXHDHAPOSIFMIG-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCCOCC(O)OC1=CC=CC=C1 XXHDHAPOSIFMIG-UHFFFAOYSA-N 0.000 description 1
- OBFOSROPNNOGQF-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCCOCCOCCOCC(O)OC1=CC=CC=C1 OBFOSROPNNOGQF-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-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
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
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- ISTJMQSHILQAEC-UHFFFAOYSA-N 2-methyl-3-pentanol Chemical compound CCC(O)C(C)C ISTJMQSHILQAEC-UHFFFAOYSA-N 0.000 description 1
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
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- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Optical Filters (AREA)
- Epoxy Resins (AREA)
Description
本発明は、液晶表示装置（ＬＣＤ）、固体撮像素子（ＣＣＤ）、エレクトロルミネッセンス装置（ＥＬ）、等に用いられるカラーフィルター保護膜用樹脂組成物に関する。さらに詳しくは、可視光領域での透明性、耐熱性、耐薬品性が良好である上で、平坦性に優れるカラーフィルター保護膜を形成し得る、樹脂組成物に関するものである。 The present invention relates to a resin composition for a color filter protective film used for a liquid crystal display device (LCD), a solid-state imaging device (CCD), an electroluminescence device (EL), and the like. More specifically, the present invention relates to a resin composition that can form a color filter protective film excellent in flatness while having good transparency, heat resistance, and chemical resistance in the visible light region.
近年、カラーフィルターの構成材料であるブラックマトリックスが、ＬＣＤ表示モードの多様化、および環境問題により、クロムブラックマトリックスから樹脂ブラックマトリックスに代替されて使用されるケースが増えてきている。従来のクロムブラックマトリックスは膜厚０．１５〜０．２０μｍで基板上に形成されていたのに対し、樹脂ブラックマトリックスでは十分な光学濃度（ＯＤ値）を得るために１．０〜１．５μｍの膜厚が必要になる。カラーフィルターへ適用する際、その厚みのために、樹脂ブラックマトリックスと重なったＲＧＢ画素端部に大きな段差が生じる。ＩＰＳ（Ｉｎ ｐｌａｎｅ Ｓｗｉｔｃｈｉｎｇ）モードのようなカラーフィルターとＴＦＴアレイ基板間のギャップ（液晶層の厚み）精度が要求される高品質ＬＣＤにおいては、この段差が問題となるため、カラーフィルター保護膜で段差を解消する（平坦化する）等の手段が採られている。
近年、液晶表示関連装置はその技術の進歩に相まって、要求性能も高度化しており、材料に対しても、より高度な性能が強く求められるようになってきている。なかでも液晶表示装置の高画質化と高精細化が求められており、前述の段差をより平滑に平坦化するカラーフィルター保護膜が求められている。段差低減率とはカラーフィルター保護膜形成前後のカラーフィルターの段差より算出される値で、平坦化の指標となる。段差低減率の値が高ければ、良好な平坦化能を有するカラーフィルター保護膜となる。
また、カラーフィルター保護膜に求められる性能としては平坦化能のみならず、保護膜を形成する基材であるＲＧＢレジスト層、および保護膜上に蒸着（スパッタ）形成されるＩＴＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）透明電極層との密着性、可視光領域での透明性、耐熱性、および耐薬品性等が挙げられる。
In recent years, a black matrix, which is a constituent material of a color filter, is increasingly used in place of a chrome black matrix instead of a resin black matrix due to diversification of LCD display modes and environmental problems. The conventional chrome black matrix is formed on the substrate with a film thickness of 0.15 to 0.20 μm, whereas the resin black matrix is 1.0 to 1.5 μm to obtain a sufficient optical density (OD value). Is required. When applied to a color filter, due to its thickness, a large step occurs at the end of the RGB pixel that overlaps the resin black matrix. In high-quality LCDs such as the IPS (In Plane Switching) mode where the gap (liquid crystal layer thickness) accuracy between the color filter and the TFT array substrate is required, this step becomes a problem. A measure such as eliminating (flattening) is taken.
In recent years, liquid crystal display-related devices have been required to have advanced performance in conjunction with technological advances, and higher performance has been strongly demanded for materials. In particular, there is a demand for higher image quality and higher definition of liquid crystal display devices, and there is a need for a color filter protective film that flattens the above-mentioned steps more smoothly. The level difference reduction rate is a value calculated from the level difference of the color filter before and after the color filter protective film is formed, and is an index for flattening. If the value of the step reduction ratio is high, the color filter protective film having good planarization ability is obtained.
The performance required for the color filter protective film is not only flattening ability, but also an RGB resist layer, which is a base material for forming the protective film, and ITO (Indium Tin Oxide) formed on the protective film by vapor deposition (sputtering). Examples thereof include adhesion to the transparent electrode layer, transparency in the visible light region, heat resistance, and chemical resistance.
平坦化能を含めた上記性能を満たすべく、これまで数多くの研究がなされてきた。特許文献１には、エポキシ基含有樹脂と多価カルボン酸誘導体を用いたカラーフィルター保護膜用の熱硬化性樹脂組成物が開示されている。また、より高い平坦性を追求し、特許文献２には、エポキシ樹脂としてアクリル型共重合体、カルドエポキシ樹脂、エポキシ基を２個以上有する脂環式エポキシ樹脂、低分子エポキシ化合物を必須成分とするカラーフィルター保護膜用の熱硬化性樹脂組成物が開示されている。しかしながら、これらの従来技術では平坦化能とその他の性能とを両立できているとはいい難く、特に近年求められているような高い平坦化能を達成するには至っていない。
また、特許文献３においては多価オキセタン化合物とカチオン性重合開始剤とオルガノアルコキシドシランを必須成分とするカラーフィルター保護膜用の熱硬化性樹脂組成物が、特許文献４においては多価オキセタン化合物とカルボン酸無水物とオルガノアルコキシシランとエポキシ基含有樹脂を必須成分とするカラーフィルター保護膜用の熱硬化性樹脂組成物が、特許文献５においてはオキセタニル基を有する化合物と金属酸化物粒子を必須成分とするカラーフィルター保護膜用の熱硬化性樹脂組成物が、特許文献６においては多価オキセタン化合物と側鎖に平面構造基を有するエポキシ樹脂とカチオン性重合開始剤を必須成分とするカラーフィルター保護膜用の熱硬化性樹脂組成物が開示されている。
しかし、これらの開示技術によるカラーフィルター保護膜用の熱硬化性樹脂組成物では、全ての保護膜基本性能を満たしながら、近年の高度化要求である段差低減率８０％以上という性能を実現することができない。
Many studies have been made so far in order to satisfy the above performance including the flattening ability. Patent Document 1 discloses a thermosetting resin composition for a color filter protective film using an epoxy group-containing resin and a polyvalent carboxylic acid derivative. In pursuit of higher flatness, Patent Document 2 includes an acrylic copolymer as an epoxy resin, a cardo epoxy resin, an alicyclic epoxy resin having two or more epoxy groups, and a low molecular epoxy compound as essential components. A thermosetting resin composition for a color filter protective film is disclosed. However, it is difficult to say that these conventional techniques can achieve both the flattening ability and other performances, and have not yet achieved the high flattening ability that has been required particularly in recent years.
Patent Document 3 discloses a thermosetting resin composition for a color filter protective film comprising a polyvalent oxetane compound, a cationic polymerization initiator, and an organoalkoxide silane as essential components, and Patent Document 4 discloses a polyvalent oxetane compound and A thermosetting resin composition for a color filter protective film comprising a carboxylic acid anhydride, an organoalkoxysilane, and an epoxy group-containing resin as essential components is disclosed in Patent Document 5 as an essential component comprising a compound having an oxetanyl group and metal oxide particles. The thermosetting resin composition for a color filter protective film is a color filter protection comprising a polyvalent oxetane compound, an epoxy resin having a planar structure group in a side chain, and a cationic polymerization initiator as essential components in Patent Document 6. A thermosetting resin composition for a film is disclosed.
However, the thermosetting resin composition for the color filter protective film according to these disclosed technologies achieves the performance of the step reduction rate of 80% or more, which is a demand for advanced technology in recent years, while satisfying all the basic characteristics of the protective film. I can't.
本発明の第１の目的は、硬化後の保護膜の透明性、鉛筆硬度、耐熱性、耐溶剤性、および保護膜を形成する基材等への密着性等の諸物性に優れながら、良好な高平坦化能を有した熱硬化型樹脂組成物を提供することにある。
また、本発明の第２の目的は、このカラーフィルター保護膜用の熱硬化性樹脂組成物を硬化させた樹脂硬化物の層を有するカラーフィルターを提供することにある。
本発明者らは前記の課題を解決するために鋭意検討を重ねた結果、エポキシ基を有する重合体（Ａ）と、カルボキシル基がビニルエーテルにより潜在化された多価カルボン酸化合物（Ｂ）とを含むカラーフィルター保護膜用の熱硬化性樹脂組成物において、さらに多価オキセタン化合物（Ｃ）を用いることにより、前記の課題を解決しうる熱硬化型樹脂組成物が得られるという知見を得て、本発明を完成するに至った。
The first object of the present invention is excellent in various properties such as transparency of the protective film after curing, pencil hardness, heat resistance, solvent resistance, and adhesion to the substrate forming the protective film, etc. An object of the present invention is to provide a thermosetting resin composition having a high leveling ability.
The second object of the present invention is to provide a color filter having a layer of a cured resin obtained by curing the thermosetting resin composition for the color filter protective film.
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polymer (A) having an epoxy group and a polyvalent carboxylic acid compound (B) in which a carboxyl group is made latent by vinyl ether. In the thermosetting resin composition for the color filter protective film containing, by using a polyvalent oxetane compound (C), the knowledge that a thermosetting resin composition capable of solving the above problems can be obtained is obtained, The present invention has been completed.
すなわち、本発明は、次の〔１〕〜〔３〕である。
〔１〕下記の（Ａ）、（Ｂ）、（Ｃ）成分を、（Ａ）１５〜６５重量％、（Ｂ）１０〜６０重量％、（Ｃ）５〜４５重量％の割合（ただし、全体が１００重量％）で含有することを特徴とするカラーフィルター保護膜用の熱硬化性樹脂組成物。
（Ａ）下記の式（１）で表される構成単位を有し、エポキシ当量が５００ｇ／ｍｏｌ以下であり、ポリスチレン換算の重量平均分子量（Ｍｗ）が３，０００〜１００，０００であるエポキシ基を有する重合体
（Ｂ）炭素数４〜２０で２〜８価のカルボン酸のカルボキシル基を、下記の式（１４）
で表されるビニルエーテルのビニル基と反応させて得られる式（１３）
で表される官能基を２〜８個有する潜在化された多価カルボン酸化合物
（Ｃ）多価オキセタン化合物
That is, the present invention includes the following [1] to [3].
[1] The following components (A), (B), and (C) are mixed in proportions of (A) 15 to 65% by weight, (B) 10 to 60% by weight, and (C) 5 to 45% by weight (however, A thermosetting resin composition for a color filter protective film, comprising 100% by weight as a whole .
(A) An epoxy group having a structural unit represented by the following formula (1), an epoxy equivalent of 500 g / mol or less, and a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 to 100,000. Polymer having
(B) A carboxyl group of a divalent to octavalent carboxylic acid having 4 to 20 carbon atoms is represented by the following formula (14):
Formula (13) obtained by reacting with the vinyl group of vinyl ether represented by
A latent polyvalent carboxylic acid compound (C) having a functional group represented by formula (C): a polyvalent oxetane compound
〔２〕前記の〔１〕に記載のカラーフィルター保護膜用の熱硬化性樹脂組成物を有機溶剤で希釈してなる塗布液。
〔３〕前記の〔１〕に記載の熱硬化性樹脂組成物を硬化させてなる樹脂硬化物の層を有するカラーフィルター。
[2] A coating solution obtained by diluting the thermosetting resin composition for a color filter protective film according to [1] with an organic solvent.
[3] A color filter having a layer of a cured resin obtained by curing the thermosetting resin composition according to [1].
本発明の熱硬化性樹脂組成物は、多価オキセタン化合物（Ｃ）を含有させることで、段差を平滑にする効果に優れ、かつ、可視光線透過率、耐溶剤性、保護膜を形成する基材等への密着性、耐熱性等の諸物性が良好である。この熱硬化性樹脂組成物は液晶表示装置、および固体撮像素子等の用途として、硬化して用いることにより、上記特性を有したカラーフィルター保護膜用の樹脂硬化物を得ることができる。 The thermosetting resin composition of the present invention contains a polyvalent oxetane compound (C), is excellent in the effect of smoothing the steps, and forms a visible light transmittance, solvent resistance, and protective film. Good physical properties such as adhesion to materials and heat resistance. When this thermosetting resin composition is cured and used for applications such as a liquid crystal display device and a solid-state imaging device, a cured resin for a color filter protective film having the above characteristics can be obtained.
以下、本発明についてさらに詳細に説明する。
本発明において、カラーフィルターの保護膜とは、カラーフィルターを有する液晶表示装置、および固体撮像素子の保護膜に用いるものを広く意味し、より詳しくは、ＲＧＢ等のカラーフィルター部分、発光ないしは受光の素子部分、電極部分等に直接に接して、これらを保護する保護膜である。
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物は、下記の（Ａ）、（Ｂ）、（Ｃ）成分を、（Ａ）１５〜６５重量％、（Ｂ）１０〜６０重量％、（Ｃ）５〜４５重量％の割合（ただし、全体が１００重量％）で含有することを特徴とする。
（Ａ）下記の式（１）で表される構成単位を有し、エポキシ当量が５００ｇ／ｍｏｌ以下であり、ポリスチレン換算の重量平均分子量（Ｍｗ）が３，０００〜１００，０００であるエポキシ基を有する重合体
（Ｂ）炭素数４〜２０で２〜８価のカルボン酸のカルボキシル基を、下記の式（１４）
で表されるビニルエーテルのビニル基と反応させて得られる式（１３）
で表される官能基を２〜８個有する潜在化された多価カルボン酸化合物
（Ｃ）多価オキセタン化合物
エポキシ基を有する重合体（Ａ）のエポキシ基のモル濃度をＮＡ、多価オキセタン化合物（Ｃ）のオキセタニル基のモル濃度をＮＢ、および多価カルボン酸化合物より生成されるカルボキシル基のモル濃度ＮＣとするとき、本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物中の（Ａ）、（Ｂ）、（Ｃ）各成分の配合比率は、［ＮＣ／（ＮＡ＋ＮＢ）］が、０．２〜１．６になるように、好ましくは０．４〜１．２になるように配合する。［ＮＣ／（ＮＡ＋ＮＢ）］が０．２未満であると、硬化後に未反応のオキシラン基が多量に残存するため、架橋密度が低くなり、本発明の目的とする効果が得ることが難しい。また、［ＮＣ／（ＮＡ＋ＮＢ）］が１．６を上回ると、硬化後に未反応のカルボキシル基が多量に残存するためカルボキシル基が過剰となり、本発明の目的とする効果を得ることが難しい。
Hereinafter, the present invention will be described in more detail.
In the present invention, the color filter protective film broadly means a liquid crystal display device having a color filter, and a solid film image sensor, and more specifically, a color filter part such as RGB, light emitting or receiving light. It is a protective film that directly contacts and protects the element portion, the electrode portion, and the like.
The thermosetting resin composition for a color filter protective film of the present invention comprises the following components (A), (B), and (C): (A) 15 to 65% by weight, (B) 10 to 60% by weight. (C) It is characterized by containing 5 to 45 weight% (however, the whole is 100 weight%) .
(A) An epoxy group having a structural unit represented by the following formula (1), an epoxy equivalent of 500 g / mol or less, and a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 to 100,000. Polymer having
(B) A carboxyl group of a divalent to octavalent carboxylic acid having 4 to 20 carbon atoms is represented by the following formula (14):
Formula (13) obtained by reacting with the vinyl group of vinyl ether represented by
A latent polyvalent carboxylic acid compound (C) having a functional group represented by the formula (C): a polyvalent oxetane compound: NA, the molar concentration of the epoxy group of the polymer (A) having an epoxy group, NA When the molar concentration of the oxetanyl group in (C) is NB and the molar concentration NC of the carboxyl group produced from the polyvalent carboxylic acid compound, ((in the thermosetting resin composition for a color filter protective film of the present invention) The blending ratio of each component of A), (B), and (C) is such that [NC / (NA + NB)] is 0.2 to 1.6, preferably 0.4 to 1.2. Blend in. When [NC / (NA + NB)] is less than 0.2, a large amount of unreacted oxirane groups remain after curing, resulting in a low crosslinking density, and it is difficult to obtain the intended effect of the present invention. On the other hand, if [NC / (NA + NB)] exceeds 1.6, a large amount of unreacted carboxyl groups remain after curing, resulting in an excess of carboxyl groups, making it difficult to obtain the intended effect of the present invention.
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物の構成成分であるエポキシ基を有する重合体（Ａ）は、好ましい構成単位として、下記の式（１）〜（３）で表される、エポキシ基を含有する構造を例示することができる。 The polymer (A) having an epoxy group, which is a constituent component of the thermosetting resin composition for the color filter protective film of the present invention, is represented by the following formulas (1) to (3) as preferred constituent units. A structure containing an epoxy group can be exemplified.
（ここで、Ｒ１は水素原子または炭素数１〜５のアルキル基、Ｒ２は水素原子または炭素数１〜２のアルキル基を示し、ｐ１＝１〜８の整数を示す。） (Here, R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and p1 = 1 to 8 represents an integer.)
（ここで、Ｒ３は水素原子または炭素数１〜５のアルキル基、Ｒ４は−ＣＨ２Ｏ−基または−ＣＨ２−基、Ｒ５は水素原子または炭素数１〜２のアルキル基を示し、ｑ１＝０〜７の整数を示す。） (Wherein R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 4 represents a —CH 2 O— group or —CH 2 — group, and R 5 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. And q1 represents an integer of 0 to 7.)
（ここで、Ｒ６は水素原子または炭素数１〜５のアルキル基を示し、ｒ１＝１〜８の整数を示す。） (Here, R 6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and an integer of r1 = 1 to 8).
本発明の熱硬化性樹脂組成物の構成成分であるエポキシ基を有する重合体（Ａ）は、その構成単位として、さらに下記の式（４）〜（６）で表される構造を有していてもよい。 The polymer (A) having an epoxy group, which is a constituent component of the thermosetting resin composition of the present invention, further has a structure represented by the following formulas (4) to (6) as its constituent unit. May be.
（ここで、Ｒ７は水素原子または炭素数１〜１２のアルキル基を示し、Ｒ８は水素原子、炭素数１〜１２のアルキル基、主環構成炭素数３〜１２の脂環式炭化水素基、芳香族炭化水素基、アリール基、アリールオキシ基、または芳香族ポリアルキレングリコール残基を示す。） (Here, R 7 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon having 3 to 12 carbon atoms constituting the main ring. Group, aromatic hydrocarbon group, aryl group, aryloxy group, or aromatic polyalkylene glycol residue.)
（ここで、Ｒ９は水素原子または炭素数１〜１２のアルキル基を示し、Ｒ１０は水素原子、炭素数１〜１２のアルキル基、または芳香族炭化水素基を示す。） (Here, R 9 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R 10 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group.)
（ここで、Ｒ１１は、水素原子または炭素数１〜１２のアルキル基、主環構成炭素数３〜１２の脂環式炭化水素基、芳香族炭化水素基を示す。） (Here, R 11 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms constituting the main ring, or an aromatic hydrocarbon group.)
前記の式（１）〜（３）で表される構成単位の構造は、それぞれ下記式（７）〜（９）で表される単量体から誘導される。 The structures of the structural units represented by the above formulas (1) to (3) are derived from monomers represented by the following formulas (7) to (9), respectively.
（ここで、Ｒ１２は水素原子または炭素数１〜５のアルキル基、Ｒ１３は水素原子または炭素数１〜２のアルキル基を示し、ｐ２＝１〜８の整数を示す。） (Here, R 12 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 13 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and p2 = 1 to 8 represents an integer.)
（ここで、Ｒ１４は水素原子または炭素数１〜５のアルキル基、Ｒ１５は−ＣＨ２Ｏ−基または−ＣＨ２−基、Ｒ１６は水素原子または炭素数１〜２のアルキル基を示し、ｑ２＝０〜７の整数を示す。） (Where R 14 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 15 represents a —CH 2 O— group or —CH 2 — group, and R 16 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. And q2 represents an integer of 0 to 7.)
（ここで、Ｒ１７は水素原子または炭素数１〜５のアルキル基を示し、ｒ２＝１〜８の整数を示す。） (Here, R 17 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and an integer of r2 = 1 to 8).
前記の式（７）〜（９）で表される単量体は、エポキシ基を有する重合体（Ａ）中にエポキシ基（エポキシの反応点）を導入するために用いられる。
式（７）において、Ｒ１２，およびＲ１３として好ましいのは、それぞれ独立に水素原子またはメチル基である。式（７）で表される単量体としては、具体的には、グリシジル（メタ）アクリレート、β−メチルグルシジル（メタ）アクリレートを例示することができ、その中ではグリシジルメタクリレート（ＧＭＡ）が入手性の面等から好ましい。
式（８）において、Ｒ１４，およびＲ１６として好ましいのは、それぞれ独立に水素原子またはメチル基であり、Ｒ１５として好ましいのは−ＣＨ２Ｏ−基である。式（８）で表される単量体としては、具体的には、ｏ−ビニルベンジルグリシジルエーテル、ｍ−ビニルベンジルグリシジルエーテル、ｐ−ビニルベンジルグリシジルエーテル，α−メチル−ｏ−ビニルベンジルグリシジルエーテル、α−メチル−ｍ−ビニルベンジルグリシジルエーテル、α−メチル−ｐ−ビニルベンジルグリシジルエーテルを例示することができ、その中ではｏ−ビニルベンジルグリシジルエーテル、ｍ−ビニルベンジルグリシジルエーテル、ｐ−ビニルベンジルグリシジルエーテルが入手性の面等から好ましい。
式（９）において、Ｒ１７として好ましいのは、水素原子またはメチル基である。式（９）で表される単量体としては３，４−エポキシシクロヘキシルメチル（メタ）アクリレートを例示することができる。その中で３，４−エポキシシクロヘキシルメチルメタクリレートが硬度等、熱硬化性樹脂組成物の硬化物の物性の面から好ましい。ここで、（メタ）アクリレートとは、アクリレートまたはメタクリレートのいずれであっても良いことを意味する。
The monomers represented by the formulas (7) to (9) are used for introducing an epoxy group (epoxy reaction point) into the polymer (A) having an epoxy group.
In the formula (7), preferred as R 12 and R 13 are each independently a hydrogen atom or a methyl group. Specific examples of the monomer represented by the formula (7) include glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate. Among them, glycidyl methacrylate (GMA) is used. It is preferable from the viewpoint of availability.
In the formula (8), preferred as R 14 and R 16 are each independently a hydrogen atom or a methyl group, and preferred as R 15 is a —CH 2 O— group. Specific examples of the monomer represented by the formula (8) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and α-methyl-o-vinylbenzyl glycidyl ether. , Α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, among which o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl Glycidyl ether is preferable from the viewpoint of availability.
In the formula (9), R 17 is preferably a hydrogen atom or a methyl group. Examples of the monomer represented by the formula (9) include 3,4-epoxycyclohexylmethyl (meth) acrylate. Among them, 3,4-epoxycyclohexylmethyl methacrylate is preferable from the viewpoint of physical properties of a cured product of the thermosetting resin composition such as hardness. Here, (meth) acrylate means that either acrylate or methacrylate may be used.
また式（４）〜（６）で表される構成単位の構造は、下記式（１０）〜（１２）で表される単量体から誘導される。 Moreover, the structure of the structural unit represented by Formula (4)-(6) is induced | guided | derived from the monomer represented by following formula (10)-(12).
（ここで、Ｒ１８は水素原子または炭素数１〜１２のアルキル基を示し、Ｒ１９は水素原子、炭素数１〜１２のアルキル基、主環構成炭素数３〜１２の脂環式炭化水素基、芳香族炭化水素基、アリール基、アリールオキシ基、または芳香族ポリアルキレングリコール残基を示す。）
式（１０）において、Ｒ１９で表される主環構成炭素数３〜１２の脂環式炭化水素基は、付加的な構造、例えば環内二重結合、炭化水素基の側鎖、スピロ環の側鎖、環内架橋炭化水素基等を含んでいてもよい。
(Here, R 18 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 19 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon having 3 to 12 carbon atoms constituting the main ring. Group, aromatic hydrocarbon group, aryl group, aryloxy group, or aromatic polyalkylene glycol residue.)
In the formula (10), the alicyclic hydrocarbon group having 3 to 12 carbon atoms constituting the main ring represented by R 19 has an additional structure such as an intracyclic double bond, a side chain of a hydrocarbon group, a spiro ring. Side chains, intracyclic bridged hydrocarbon groups, and the like.
（ここで、Ｒ２０は水素原子または炭素数１〜１２のアルキル基を示し、Ｒ２１は水素原子、炭素数１〜１２のアルキル基、または芳香族炭化水素基を示す。） (Here, R 20 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R 21 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group.)
（ここで、Ｒ２２は、水素原子または炭素数１〜１２のアルキル基、主環構成炭素数３〜１２の脂環式炭化水素基、芳香族炭化水素基を示す。）
前記式（１０）〜（１２）で表される単量体を用いることにより、保護膜に充分な硬度、耐熱性および耐薬品性を付与することができる。
前記の式（１０）で表される単量体としては、具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メトキシ化シクロデカトリエンアクリレート、パラ−ｔ−ブチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシテトラエチレングリコール（メタ）アクリレート、フェノキヘキサエチレングリコール（メタ）アクリレート、フェニル（メタ）アクリレート等を例示することができる。ここで、（メタ）アクリレートとは、アクリレートまたはメタクリレートのいずれであっても良いことを意味する。
(Here, R 22 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms constituting the main ring, or an aromatic hydrocarbon group.)
By using the monomers represented by the formulas (10) to (12), sufficient hardness, heat resistance and chemical resistance can be imparted to the protective film.
Specific examples of the monomer represented by the formula (10) include methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxylated cyclodecatriene acrylate, para-t- Butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, Examples thereof include phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, and phenyl (meth) acrylate. Here, (meth) acrylate means that either acrylate or methacrylate may be used.
前記の式（１０）において、Ｒ１８としては好ましいのは水素またはメチル基であり、Ｒ１９としては好ましいのはシクロヘキシル基、またはジシクロペンタニル基である。式（１０）で表される単量体としては、具体的には、シクロヘキシルメタクリレート、およびジシクロペンテニルメタクリレートが硬度、耐熱性等、熱硬化性樹脂組成物の硬化物の物性の面から好ましい。
前記の式（１１）で表される単量体としては、具体的には、エチレン、プロピレン、ビニルシクロヘキサノン、スチレン、ビニルトルエン、ｔ−ブチルスチレン、アリルシクロプロパン、α−メチルスチレン、およびα−エチルスチレン等が挙げられる。
前記の式（１１）において、Ｒ２０としては好ましいのは水素またはメチル基であり、Ｒ２１としては好ましいのはフェニル基である。式（１１）で表される単量体としては、具体的には、スチレンが他種単量体との共重合性、および入手性の面等から好ましい。
In the formula (10), R 18 is preferably hydrogen or a methyl group, and R 19 is preferably a cyclohexyl group or a dicyclopentanyl group. Specifically, as the monomer represented by the formula (10), cyclohexyl methacrylate and dicyclopentenyl methacrylate are preferable from the viewpoint of physical properties of a cured product of the thermosetting resin composition such as hardness and heat resistance.
Specific examples of the monomer represented by the formula (11) include ethylene, propylene, vinylcyclohexanone, styrene, vinyltoluene, t-butylstyrene, allylcyclopropane, α-methylstyrene, and α- Examples include ethyl styrene.
In the formula (11), R 20 is preferably hydrogen or a methyl group, and R 21 is preferably a phenyl group. Specifically, as the monomer represented by the formula (11), styrene is preferable from the viewpoints of copolymerization with other monomers and availability.
前記の式（１２）で表される単量体としては、具体的には、Ｎ−メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−プロピルマレイミド、Ｎ−ブチルマレイミド、Ｎ−シクロヘキシルマレイミド、およびＮ−フェニルマレイミド等が挙げられる。
前記式（１２）において、Ｒ２２としては好ましいのはシクロヘキシル基、およびフェニル基である。式（１２）で表される単量体としては、具体的には、Ｎ−シクロヘキシルマレイミド、およびＮ−フェニルマレイミドが硬度、および耐熱性等、熱硬化性樹脂組成物の硬化物の物性の面から好ましい。
Specific examples of the monomer represented by the formula (12) include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, and N-phenyl. Examples include maleimide.
In the formula (12), R 22 is preferably a cyclohexyl group or a phenyl group. Specific examples of the monomer represented by the formula (12) include N-cyclohexylmaleimide and N-phenylmaleimide having hardness, heat resistance, and other properties of the cured product of the thermosetting resin composition. To preferred.
本発明の熱硬化性樹脂組成物の構成成分であるエポキシ基を有する重合体（Ａ）は、単独重合体であってもよいし、ランダム共重合体であってもよいし、ブロック共重合体であってもよいし、グラフト共重合体であってもよい。また、重合体（Ａ）は、式（１）〜（３）あるいは式（４）〜（６）以外の構成単位を共重合成分として使用してもよい。これらの構成単位の重合体（Ａ）中の割合は、式（１）〜（３）で示される構成単位を１０〜１００重量％と、式（４）〜（６）で示される構成単位のいずれか、あるいは２種類以上を０〜９０重量％とするのが好ましい。式（１）〜（３）の構成単位の割合が上記範囲内にあれば、硬化の反応点が十分となり高い架橋密度を得ることができ、一方、式（４）〜（６）の構成単位の割合が上記範囲内にあれば、嵩高の骨格が多いことにより硬化収縮等を抑制できることが知られている。エポキシ基を有する重合体（Ａ）のポリスチレン換算の重量平均分子量（Ｍｗ）、およびエポキシ当量が上記範囲内にあれば、溶剤揮発後の塗布層のタック（べたつき）の発生を防止でき、また、均一な膜厚を容易に得ることができる。エポキシ基を有する重合体（Ａ）のポリスチレン換算の重量平均分子量（Ｍｗ）が３，０００未満であると、硬化して得られる保護膜に硬度の低下とタック（べたつき）が発生し、エポキシ基を有する重合体（Ａ）のポリスチレン換算の重量平均分子量（Ｍｗ）が１００，０００を上回ると硬化して得られる保護膜の外観が低下するおそれがある。また、エポキシ基を有する重合体のエポキシ当量が５００ｇ／ｍｏｌを上回ると、硬化して得られる保護膜の硬度が低下する。
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物中のエポキシ基を有する重合体（Ａ）の配合割合は、１５〜６５重量％であり、好ましくは１５〜６０重量％、より好ましくは１５〜５５重量％である。エポキシ基を有する重合体（Ａ）の配合割合が１５重量％未満であると、硬化して得られる保護膜の硬度の低下が発生し、６５重量％を上回ると十分な段差低減率が得られない。
The polymer (A) having an epoxy group which is a constituent component of the thermosetting resin composition of the present invention may be a homopolymer, a random copolymer, or a block copolymer. Or a graft copolymer. Moreover, the polymer (A) may use structural units other than the formulas (1) to (3) or the formulas (4) to (6) as a copolymerization component. The proportion of these structural units in the polymer (A) is 10 to 100% by weight of the structural units represented by the formulas (1) to (3) and the structural units represented by the formulas (4) to (6). It is preferable that any one or two or more types be 0 to 90% by weight. If the proportion of the structural units of the formulas (1) to (3) is within the above range, the curing reaction point is sufficient and a high crosslinking density can be obtained, while the structural units of the formulas (4) to (6). If the ratio is within the above range, it is known that curing shrinkage and the like can be suppressed due to a large bulky skeleton. If the polymer (A) having an epoxy group has a polystyrene-equivalent weight average molecular weight (Mw) and an epoxy equivalent within the above range, it is possible to prevent the occurrence of tackiness (stickiness) of the coating layer after solvent volatilization, A uniform film thickness can be easily obtained. When the weight average molecular weight (Mw) in terms of polystyrene of the polymer (A) having an epoxy group is less than 3,000, the protective film obtained by curing causes a decrease in hardness and tack (stickiness). If the polymer (A) having a weight average molecular weight (Mw) in terms of polystyrene exceeds 100,000, the appearance of the protective film obtained by curing may be deteriorated. Moreover, when the epoxy equivalent of the polymer which has an epoxy group exceeds 500 g / mol, the hardness of the protective film obtained by hardening will fall.
The blending ratio of the polymer (A) having an epoxy group in the thermosetting resin composition for the color filter protective film of the present invention is 15 to 65% by weight, preferably 15 to 60% by weight, more preferably. 15 to 55% by weight. When the blending ratio of the polymer (A) having an epoxy group is less than 15% by weight, the hardness of the protective film obtained by curing is lowered, and when it exceeds 65% by weight, a sufficient step reduction rate is obtained. Absent.
エポキシ基を有する重合体（Ａ）は、常法の重合法により共重合することができる。すなわち、共重合の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方法を採ることがことができ、より具体的には重合開始剤の存在下、塊状重合法、溶液重合法、懸濁重合法、乳化重合法等の重合方法を採ることができる。また、共重合の形態も特に制限されず、ランダム共重合、ブロック共重合、グラフト共重合等のいずれでもよい。なかでも、ラジカル重合を溶液重合により行いランダム共重合体を得る重合方法が諸物性の設計が容易なことから好ましい。
重合方法によっては、単量体が多量に残存する場合があるが、この単量体が塗布硬化後の保護膜物性に影響を与える場合には、減圧留去法や再沈殿形成法等によって単量体を除去してもよい。
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物において、エポキシ基を有する重合体（Ａ）は、１種単独で、あるいは２種以上を混合して用いてもよい。
The polymer (A) having an epoxy group can be copolymerized by a conventional polymerization method. That is, the copolymerization method is not particularly limited, and a polymerization method such as radical polymerization or ionic polymerization can be employed. More specifically, in the presence of a polymerization initiator, a bulk polymerization method, a solution polymerization method, a suspension polymerization method can be used. A polymerization method such as a turbid polymerization method or an emulsion polymerization method can be employed. Further, the form of copolymerization is not particularly limited, and any of random copolymerization, block copolymerization, graft copolymerization and the like may be used. Among these, a polymerization method for obtaining a random copolymer by performing radical polymerization by solution polymerization is preferable because various physical properties can be easily designed.
Depending on the polymerization method, a large amount of monomer may remain. However, if this monomer affects the physical properties of the protective film after coating and curing, it can be obtained by a vacuum distillation method or a reprecipitation formation method. The polymer may be removed.
In the thermosetting resin composition for a color filter protective film of the present invention, the polymer (A) having an epoxy group may be used alone or in combination of two or more.
本発明の熱硬化性樹脂組成物に用いる、カルボキシル基がビニルエーテルによりブロック化された多価カルボン酸化合物（Ｂ）は、より具体的には、式（１３）で表される官能基を２個以上有する化合物である。 More specifically, the polyvalent carboxylic acid compound (B) in which the carboxyl group is blocked with vinyl ether used in the thermosetting resin composition of the present invention has two functional groups represented by the formula (13). It is a compound having the above.
（ここで、Ｒ２３は炭素数１〜１８の炭化水素基である。より具体的には、炭素原子１〜１８のアルキル基、アリール基、アルカリール基であって、これらの有機基は適当な置換基を有していてもよい。） (Here, R 23 is a hydrocarbon group having 1 to 18 carbon atoms. More specifically, it is an alkyl group having 1 to 18 carbon atoms, an aryl group, or an alkaryl group, and these organic groups are suitable. May have a substituent.
上記の式（１３）で表される官能基を２個以上有する化合物は、多価カルボン酸のカルボキシル基と下記式（１４）で表されるビニルエーテルのビニル基とを反応させることによって得られる。 The compound having two or more functional groups represented by the above formula (13) can be obtained by reacting a carboxyl group of a polyvalent carboxylic acid with a vinyl group of a vinyl ether represented by the following formula (14).
（ここで、Ｒ２３は式（１３）に同じ）
式（１４）で表されるビニルエーテルの具体例としては、例えばメチルビニルエーテル、エチルビニルエーテル、イソ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、イソ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。
(Where R 23 is the same as in equation (13))
Specific examples of the vinyl ether represented by the formula (14) include, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether. Aliphatic vinyl ether compounds such as
本発明の熱硬化性樹脂組成物に用いる多価カルボン酸化合物（Ｂ）に使用する多価カルボン酸は、炭素数４〜２０で２〜８価のカルボン酸である。具体的には例えば、イタコン酸、マレイン酸、コハク酸、シトラコン酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルテトラヒドロフタル酸、シクロペンタンテトラカルボン酸、シクロヘキサントリカルボン酸等の脂肪族多価カルボン酸；フタル酸、テレフタル酸、イソフタル酸、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、およびこれらの水素化物が挙げられる。 The polyvalent carboxylic acid used for the polyvalent carboxylic acid compound (B) used in the thermosetting resin composition of the present invention is a carboxylic acid having 4 to 20 carbon atoms and 2 to 8 valences. Specific examples thereof include aliphatic polycarboxylic acids such as itaconic acid, maleic acid, succinic acid, citraconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, cyclopentanetetracarboxylic acid, and cyclohexanetricarboxylic acid; Examples include phthalic acid, terephthalic acid, isophthalic acid, merit acid, trimellitic acid, pyromellitic acid, aromatic polycarboxylic acids such as benzophenone tetracarboxylic acid, and hydrides thereof.
通常は、前記の多価カルボン酸と、式（１４）で表されるビニルエーテルとを無触媒で、あるいは酸性リン酸エステル化合物等の酸触媒の存在下で、室温〜１００℃の温度で反応させてカルボキシル基を保護（ブロック）することにより、式（１３）で表される官能基を２個以上有する化合物が得られる。
反応系を均一にし、反応を容易にする目的で有機溶媒を使用することができる。そのような有機溶媒としては、例えば、ベンゼン、トルエン、キシレン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；酢酸イソブチル、二塩基酸ジメチルエステル混合物（商品名ＤＢＥ、デュポン社製）、酢酸３−メトキシブチル等のエステルおよびエーテルエステル類；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、メチルイソアミルケトン等のケトン類；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媒；ジエチレングリコールモノヘキシルエーテル、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。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。
Usually, the polyvalent carboxylic acid is reacted with the vinyl ether represented by the formula (14) without a catalyst or in the presence of an acid catalyst such as an acidic phosphate compound at a temperature of room temperature to 100 ° C. By protecting (blocking) the carboxyl group, a compound having two or more functional groups represented by the formula (13) can be obtained.
An organic solvent can be used for the purpose of making the reaction system uniform and facilitating the reaction. Examples of such an organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as dioxane and tetrahydrofuran; isobutyl acetate, dibasic acid dimethyl ester mixture (trade name DBE, manufactured by DuPont), acetic acid Esters and ether esters such as 3-methoxybutyl; ketones such as methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone, and methyl isoamyl ketone; phosphate esters such as triethyl phosphate and tributyl phosphate; dimethyl sulfoxide, N, N -Aprotic polar solvents such as dimethylformamide; diethylene glycol monohexyl ether, propylene glycol monoethyl ether acetate, ethylene glycol monophenyl ether, dipropylene Recall, diethylene glycol 2-ethylhexyl ether, glycol derivatives such as tetraethylene glycol dimethyl ether. Preferably, propylene glycol monomethyl ether acetate is used.
有機溶剤は、１種単独または２種以上を組み合わせて用いることができる。前記の有機溶媒の使用量は、特に限定されないが、反応原料１００重量部に対して、通常５〜９５重量部、好ましくは２０〜８０重量部である。
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物において、多価カルボン酸化合物（Ｂ）は、１種単独で、あるいは２種以上を混合して用いてもよい。
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物に用いる多価オキセタン化合物（Ｃ）は、より具体的には、式（１５）で表される化合物である。
An organic solvent can be used individually by 1 type or in combination of 2 or more types. Although the usage-amount of the said organic solvent is not specifically limited, It is 5-95 weight part normally with respect to 100 weight part of reaction raw materials, Preferably it is 20-80 weight part.
In the thermosetting resin composition for a color filter protective film of the present invention, the polycarboxylic acid compound (B) may be used alone or in combination of two or more.
More specifically, the polyvalent oxetane compound (C) used in the thermosetting resin composition for the color filter protective film of the present invention is a compound represented by the formula (15).
（ここで、Ｒ２４は、酸素原子もしくは２〜８価のカルボキシル残基またはヒドロキシル残基を有する炭素数１〜１８の有機基であり、Ｒ２５は、炭素数１〜４の分岐を有していてもよい脂肪族アルキル基である。）
多価オキセタン化合物（Ｃ）としては、３−メチル−３−メトキシメチルオキセタンや３−エチル−３−メトキシメチルオキセタン等の、炭素数１〜４の分岐を有していてもよい脂肪族アルキル基を有する３−アルキル−３−ヒドロキシメチルオキセタン類から誘導される、次の（Ｃ１）および（Ｃ２）のオキセタン化合物が挙げられる。
ヒドロキシル化合物と３−アルキル−３−ヒドロキシメチルオキセタン類とのエーテル化物（Ｃ１）、または
カルボキシル化合物と３−アルキル−３−ヒドロキシメチルオキセタン類とのエステル化物（Ｃ２）
(Here, R 24 is an organic group having 1 to 18 carbon atoms having an oxygen atom, a divalent to octavalent carboxyl residue or a hydroxyl residue, and R 25 has a branch having 1 to 4 carbon atoms. It is an aliphatic alkyl group that may be present.)
Examples of the polyvalent oxetane compound (C) include aliphatic alkyl groups which may have 1 to 4 carbon atoms such as 3-methyl-3-methoxymethyloxetane and 3-ethyl-3-methoxymethyloxetane. The following oxetane compounds of (C1) and (C2) derived from 3-alkyl-3-hydroxymethyl oxetanes having:
Etherified product (C1) of hydroxyl compound and 3-alkyl-3-hydroxymethyloxetane, or esterified product (C2) of carboxyl compound and 3-alkyl-3-hydroxymethyloxetane
ヒドロキシル化合物と３−アルキル−３−ヒドロキシメチルオキセタン類とのエーテル化物（Ｃ１）として、例えば、３−アルキル−３−ヒドロキシメチルオキセタン類自体、炭素数２〜８のアルキレン基からなる脂肪族グリコール、炭素数２〜１８の芳香族アルコール、フェノールノボラック樹脂、重合単位が第４級構造で重合度２〜８のポリシロキサン等のヒドロキシル化合物と、３−エチル−３−メトキシメチルオキセタン等のオキセタン類とをエーテル縮合した化合物等が挙げられる。より具体的には例えば、ビス（（３−エチル−３−オキセタニル）メチル）エーテル、１，４−ビス（（（３−エチル−３−オキセタニル）メトキシ）メチル）ベンゼン、１，４−ビス（（（３−エチル−３−オキセタニル）メトキシ）メチル）ベンゼン、４，４’−ビス（（（３−エチル−３−オキセタニル）メトキシ）メチル）ビフェニル、３，３’，５，５’−メチル−４，４’−ビス（（（３−エチル−３−オキセタニル）メトキシ）メチル）ビフェニル、１，４−ビス（（３−エチル−３−オキセタニル）メトキシ）ベンゼン、４，４’−ビス（（３−エチル−３−オキセタニル）メトキシ）ビフェニル、３，３’，５，５’−メチル−４，４’−ビス（（３−エチル−３−オキセタニル）メチル）ビフェニル等が挙げられる。 As an etherified product (C1) of a hydroxyl compound and 3-alkyl-3-hydroxymethyloxetane, for example, 3-alkyl-3-hydroxymethyloxetane itself, an aliphatic glycol comprising an alkylene group having 2 to 8 carbon atoms, An aromatic alcohol having 2 to 18 carbon atoms, a phenol novolac resin, a hydroxyl compound such as polysiloxane having a quaternary structure and a polymerization unit of 2 to 8, and an oxetane such as 3-ethyl-3-methoxymethyloxetane; And the like, and the like. More specifically, for example, bis ((3-ethyl-3-oxetanyl) methyl) ether, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene, 1,4-bis ( ((3-Ethyl-3-oxetanyl) methoxy) methyl) benzene, 4,4′-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) biphenyl, 3,3 ′, 5,5′-methyl -4,4'-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) biphenyl, 1,4-bis ((3-ethyl-3-oxetanyl) methoxy) benzene, 4,4'-bis ( (3-ethyl-3-oxetanyl) methoxy) biphenyl, 3,3 ′, 5,5′-methyl-4,4′-bis ((3-ethyl-3-oxetanyl) methyl) biphenyl and the like.
カルボキシル化合物と３−アルキル−３−ヒドロキシメチルオキセタン類とのエステル化物（Ｃ２）として、例えば、（メタ）アクリル酸、炭酸、アジピン酸、テレフタル酸、シクロヘキサンジカルボン酸等のカルボキシル化合物と、３−エチル−３−メトキシメチルオキセタン等のオキセタン類をエステル化した化合物等が挙げられ、より具体的には例えば、（３−エチル−３−オキセタニル）メチルメタクリレート、ビス（（３−エチル−３−オキセタニル）メチル）カーボネート、ビス（（３−エチル−３−オキセタニル）メチル）アジペート、ビス（（３−エチル−３−オキセタニル）メチル）ベンゼン−１，４−ジカルボキシレート、ビス（（３−エチル−３−オキセタニル）メチル）シクロヘキサン−１，４−ジカルボキシレート等が挙げられる。
これらの、多価オキセタン化合物（Ｃ）の中でも、１，４−ビス（（（３−エチル−３−オキセタニル）メトキシ）メチル）ベンゼン、およびビス（１−エチル（３−オキセタニル））メチルエーテルが、光線透過率等、硬化して得られる保護膜の物性の面から好ましい。
Examples of esterified products (C2) of carboxyl compounds and 3-alkyl-3-hydroxymethyloxetanes include carboxyl compounds such as (meth) acrylic acid, carbonic acid, adipic acid, terephthalic acid, cyclohexanedicarboxylic acid, and 3-ethyl Examples thereof include compounds obtained by esterifying oxetanes such as -3-methoxymethyloxetane, and more specifically, for example, (3-ethyl-3-oxetanyl) methyl methacrylate, bis ((3-ethyl-3-oxetanyl) Methyl) carbonate, bis ((3-ethyl-3-oxetanyl) methyl) adipate, bis ((3-ethyl-3-oxetanyl) methyl) benzene-1,4-dicarboxylate, bis ((3-ethyl-3 -Oxetanyl) methyl) cyclohexane-1,4-dicarboxylate Etc. The.
Among these polyvalent oxetane compounds (C), 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene and bis (1-ethyl (3-oxetanyl)) methyl ether are From the viewpoint of physical properties of a protective film obtained by curing, such as light transmittance.
多価オキセタン化合物（Ｃ）のポリスチレン換算の重量平均分子量（Ｍｗ）は、通常１５０〜３０００、好ましくは１７５〜２５００、より好ましくは２００〜２０００である。多価オキセタン化合物（Ｃ）のポリスチレン換算の重量平均分子量（Ｍｗ）が１５０未満であると耐熱性、硬度の低下が発生し、３０００を上回ると目的の段差低減率が得ることが難しい。 The polystyrene equivalent weight average molecular weight (Mw) of the polyvalent oxetane compound (C) is usually 150 to 3000, preferably 175 to 2500, and more preferably 200 to 2000. If the weight average molecular weight (Mw) in terms of polystyrene of the polyvalent oxetane compound (C) is less than 150, heat resistance and hardness are reduced. If it exceeds 3000, it is difficult to obtain the desired step reduction ratio.
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物中の多価オキセタン化合物（Ｃ）の配合割合は、５〜４５重量％であり、好ましくは１０〜４０重量％、より好ましくは１４〜３５重量％である。多価オキセタン化合物（Ｃ）の配合割合が５重量％未満であると十分な段差低減率を得ることができず、４５重量％を上回ると、硬化して得られる保護膜の硬度の低下が発生する。
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物において、多価オキセタン化合物（Ｃ）は、１種単独で、あるいは２種以上を混合して用いてもよい。
The blending ratio of the polyvalent oxetane compound (C) in the thermosetting resin composition for the color filter protective film of the present invention is 5 to 45% by weight, preferably 10 to 40% by weight, more preferably 14 to 35% by weight. If the blending ratio of the polyvalent oxetane compound (C) is less than 5% by weight, a sufficient step reduction ratio cannot be obtained, and if it exceeds 45% by weight, the hardness of the protective film obtained by curing is reduced. To do.
In the thermosetting resin composition for a color filter protective film of the present invention, the polyvalent oxetane compound (C) may be used alone or in combination of two or more.
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には、本発明の熱硬化性樹脂組成物を硬化させてなる樹脂硬化物の無色透明性を損なわない範囲において、硬化促進剤を適宜使用することもできる。添加しうる硬化促進剤としては、例えば、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、アルミニウムアセチルアセトン錯体等の有機金属化合物類；テトラエチルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド等の４級アンモニウム塩類；三フッ化ホウ素、トリフェニルボレート等のホウ素化合物；塩化亜鉛、塩化第二錫等の金属ハロゲン化物が挙げられる。さらには他の硬化促進剤として、高融点イミダゾール化合物、ジシアンジアミド、アミン等エポキシ樹脂等に付加したアミン付加型促進剤等の高融点分散型潜在性促進剤；イミダゾール系、リン系、ホスフィン系促進剤の表面をポリマーで被覆したマイクロカプセル型潜在性促進剤；アミン塩型潜在性硬化促進剤、ルイス酸塩、ブレンステッド酸塩等の高温解離型の熱カチオン重合型の潜在性硬化促進剤等に代表される潜在性硬化促進剤も使用することができる。
硬化促進剤は、硬化物の液晶非汚染性等の観点から、ハロゲンフリーの酸性触媒であることが好ましい。さらに、樹脂組成物の保存安定性の観点を加味すると、ハロゲンフリーの酸性触媒のなかでも、具体的にはルイス酸塩高温解離型の潜在性硬化促進剤がより好ましく、市販品としてはノフキュアーＬＣ−１およびノフキュアーＬＣ−２（いずれも商品名、日本油脂（株）製）が挙げられる。
これらの硬化促進剤は１種単独で、あるいは２種以上を適宜組み合わせて使用することができる。
前記の硬化促進剤は、エポキシ基を有する重合体（Ａ）と、カルボキシル基がビニルエーテルにより潜在化された多価カルボン酸化合物（Ｂ）と、多価オキセタン化合物（Ｃ）の合計１００重量部に対して、通常０．０１〜１０重量部の割合で配合される。
In the thermosetting resin composition for a color filter protective film of the present invention, a curing accelerator is appropriately used as long as the colorless transparency of the cured resin obtained by curing the thermosetting resin composition of the present invention is not impaired. You can also Examples of the curing accelerator that can be added include tertiary amines such as benzyldimethylamine, tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine; 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl- Imidazoles such as 4-methylimidazole and 1-benzyl-2-methylimidazole; Organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; Quaternary compounds such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide Phosphonium salts; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complex; Tetraethylammoni Arm bromide, quaternary ammonium salts such as tetrabutylammonium bromide; boron trifluoride, boron compounds such as triphenyl borate; zinc chloride, metal halides such as stannic chloride. Furthermore, as other curing accelerators, high melting point dispersion type latent accelerators such as amine addition type accelerators added to epoxy resins such as high melting point imidazole compounds, dicyandiamide, amines, etc .; imidazole type, phosphorus type, phosphine type accelerators Microcapsule type latent accelerator with polymer surface coated; amine salt type latent curing accelerator, high temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt, Bronsted acid salt, etc. Representative latent curing accelerators can also be used.
The curing accelerator is preferably a halogen-free acidic catalyst from the viewpoint of liquid crystal non-contamination of the cured product. Furthermore, in view of the storage stability of the resin composition, among the halogen-free acidic catalysts, specifically, a Lewis acid salt high-temperature dissociation type latent curing accelerator is more preferable. -1 and Nocure LC-2 (both are trade names, manufactured by NOF Corporation).
These curing accelerators can be used singly or in appropriate combination of two or more.
The curing accelerator is a total of 100 parts by weight of the polymer (A) having an epoxy group, the polyvalent carboxylic acid compound (B) having a carboxyl group made latent by vinyl ether, and the polyvalent oxetane compound (C). On the other hand, it is normally blended at a ratio of 0.01 to 10 parts by weight.
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、有機溶剤、炭酸ガス発生防止剤、可撓性付与剤、酸化防止剤、可塑剤、滑剤、カップリング剤、無機充填材、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。 In the thermosetting resin composition of the present invention, an organic solvent, a carbon dioxide gas generation inhibitor, a flexibility imparting agent, an antioxidant, a plasticizer, and a lubricant are included as long as the curing of the present invention is not impaired. , Coupling agents, inorganic fillers, surface treatment agents, flame retardants, antistatic agents, colorants, leveling agents, ion trap agents, slidability improvers, various rubbers, organic polymer beads, glass beads, glass fibers, etc. Impact modifiers such as inorganic fillers, thixotropic agents, surfactants, surface tension reducing agents, antifoaming agents, anti-settling agents, light diffusing agents, ultraviolet absorbers, antioxidants, mold release agents, fluorescence Additives such as an agent and a conductive filler can be blended.
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、さらに有機溶剤を添加し希釈し塗布液となして、使用してもよい。すなわち、本発明の塗布液において、有機溶剤の添加量としては、本発明の熱硬化性樹脂組成物１００重量部に対して、５〜２０００重量部、好ましくは１０〜９００重量部である。
前記の有機溶剤としては、例えば、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、３−メトキシブチルアセテート、３−エトキシエチルプロピオネート、メチル−β−メトキシイソブチレート、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、二塩基酸ジメチルエステル混合物（商品名ＤＢＥ、デュポン社製）、シクロヘキサノンなどを例示できる。これらの中でも塗布性の点から、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好ましく挙げられる。
これらの有機溶剤は１種単独で、あるいは２種以上を適宜組み合わせて使用することができる。
The thermosetting resin composition for a color filter protective film of the present invention may be used after further diluting by adding an organic solvent to form a coating solution. That is, in the coating liquid of the present invention, the addition amount of the organic solvent is 5 to 2000 parts by weight, preferably 10 to 900 parts by weight, with respect to 100 parts by weight of the thermosetting resin composition of the present invention.
Examples of the organic solvent include diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-ethoxyethyl propionate, methyl-β-methoxyisobutyrate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl. Examples include ether acetate, propylene glycol monoethyl ether acetate, dibasic acid dimethyl ester mixture (trade name DBE, manufactured by DuPont), and cyclohexanone. Among these, propylene glycol monomethyl ether acetate is preferably mentioned from the viewpoint of applicability.
These organic solvents can be used individually by 1 type or in combination of 2 or more types as appropriate.
エポキシ基を有する重合体（Ａ）をはじめとする各材料を溶剤に溶解、分散する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解して熱硬化性樹脂組成物を調製してもよいし、必要に応じて各成分を適宜２つ以上の溶液としておいて、使用時にこれらの溶液を混合して熱硬化性樹脂組成物として調製してもよい。
混合は、撹拌翼を取り付けたモーターやマグネットスターラーの撹拌子で撹拌を行ってもよいし、または各成分をガロン容器等に配合してから容器ごとミックスローターで回転させて行ってもよい。
ただし、カルボキシル基がビニルエーテルにより潜在化された多価カルボン酸化合物（Ｂ）の使用に当たっては、溶剤の液温が高すぎると、カラーフィルター保護膜用の熱硬化性樹脂組成物を調製している段階でカルボキシル基がビニルエーテルにより潜在化された多価カルボン酸化合物（Ｂ）の保護基が外れてカルボキシル基が再生してしまうので、溶剤の液温は化合物のカルボキシル基が再生しない程度の温度、通常は２０〜３０℃程度の温度で調整する。
There are no particular restrictions on the order of input and working conditions when each material including the polymer (A) having an epoxy group is dissolved and dispersed in a solvent. For example, the thermosetting resin composition may be prepared by dissolving all the components in a solvent at the same time, or if necessary, each component is appropriately made into two or more solutions, and these solutions are mixed at the time of use. It may be prepared as a thermosetting resin composition.
Mixing may be performed with a motor equipped with a stirring blade or a stirring bar of a magnetic stirrer, or may be performed by mixing each component in a gallon container or the like and then rotating the whole container with a mix rotor.
However, when the polyvalent carboxylic acid compound (B) in which the carboxyl group is latentized with vinyl ether is used, if the solvent temperature is too high, a thermosetting resin composition for a color filter protective film is prepared. Since the protecting group of the polyvalent carboxylic acid compound (B) in which the carboxyl group is latentized with vinyl ether at the stage is removed and the carboxyl group is regenerated, the liquid temperature of the solvent is such that the carboxyl group of the compound is not regenerated, Usually, it adjusts at the temperature of about 20-30 degreeC.
このようにして得られる本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物は、カルボキシル基がビニルエーテルにより潜在化された多価カルボン酸化合物（Ｂ）およびオキセタン含有化合物（Ｃ）を使用することで高固形分濃度ながら低粘度である。また、オキセタン含有化合物（Ｃ）を使用したカラーフィルター保護膜用の熱硬化性樹脂組成物は、加熱時の硬化速度を遅延することにより流動性が維持される時間を延長することができるので、保護膜としての良好な平坦化能が得られる。
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物を塗布する方法には、特に制限はなく、スピンコーターによる回転塗布法、浸漬法、スプレー法、ロールコーター法、スクリーン印刷法、オフセット印刷法、スリットコーター法、ダイコート法等により、基材に塗布することができる。
スピンコーターによる回転塗布法を使用する場合、回転数は通常３００〜１５００ｒｐｍの範囲内で設定するとよい。一般的に、カラーフィルター保護膜用の熱硬化性樹脂組成物を硬化させて得られる保護膜は、硬化終了後で０．５〜５．０μｍ程度の厚さで形成する。
The thermosetting resin composition for a color filter protective film of the present invention thus obtained uses a polyvalent carboxylic acid compound (B) and an oxetane-containing compound (C) in which the carboxyl group is made latent by vinyl ether. Therefore, it has a low viscosity with a high solid content concentration. Moreover, since the thermosetting resin composition for a color filter protective film using the oxetane-containing compound (C) can extend the time during which fluidity is maintained by delaying the curing rate during heating, Good planarization ability as a protective film can be obtained.
The method for applying the thermosetting resin composition for the color filter protective film of the present invention is not particularly limited, and is a spin coating method using a spin coater, a dipping method, a spray method, a roll coater method, a screen printing method, an offset printing method. It can be applied to a substrate by the method, slit coater method, die coating method or the like.
When the spin coating method using a spin coater is used, the rotation speed is usually set within a range of 300 to 1500 rpm. Generally, a protective film obtained by curing a thermosetting resin composition for a color filter protective film is formed with a thickness of about 0.5 to 5.0 μm after the completion of curing.
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物の反応方法（硬化方法）には、特に制限はなく、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。硬化温度、および硬化時間は、８０℃〜２５０℃で３０秒〜１０時間の範囲が好ましい。硬化物の内部応力を低減したい場合は、８０〜１２０℃、０．５時間〜５時間の条件で前硬化した後、１２０〜１８０℃、０．１時間〜５時間の条件で後硬化することが好ましい。短時間硬化を目的とする場合は１５０〜２５０℃、３０秒〜１時間の条件で硬化することが好ましい。
本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物により形成される保護膜は、透明性、鉛筆硬度、耐熱性、耐溶剤性、密着性、および平坦化能に優れているため、各種基材の表面コーティング剤、装飾材料等の用途に使用すると有用である。特に、アクリル樹脂、ポリビニルアルコール、ゼラチン等の種々バインダー樹脂を染料による染色や、顔料分散による着色により作製したカラーフィルターの表面に使用する保護膜として使用すると有用である。本発明のカラーフィルター保護膜用の熱硬化性樹脂組成物の層を有するカラーフィルターは、液晶表示装置や固体撮像素子に好適に使用することができる。
There is no restriction | limiting in particular in the reaction method (curing method) of the thermosetting resin composition for color filter protective films of this invention, Adopting hardening apparatuses, such as a closed-type hardening furnace and a tunnel furnace in which continuous hardening is possible. Can do. 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. The curing temperature and the curing time are preferably in the range of 80 ° C. to 250 ° C. and 30 seconds to 10 hours. If you want to reduce the internal stress of the cured product, after pre-curing under conditions of 80-120 ° C, 0.5 hours to 5 hours, post-curing under conditions of 120-180 ° C, 0.1 hours to 5 hours Is preferred. When aiming at short-time curing, curing is preferably performed under conditions of 150 to 250 ° C. and 30 seconds to 1 hour.
The protective film formed by the thermosetting resin composition for the color filter protective film of the present invention is excellent in transparency, pencil hardness, heat resistance, solvent resistance, adhesion, and planarization ability. It is useful when used in applications such as surface coating agents for base materials and decorative materials. In particular, it is useful to use various binder resins such as acrylic resin, polyvinyl alcohol, gelatin and the like as a protective film used on the surface of a color filter prepared by dyeing with a dye or coloring by pigment dispersion. The color filter having the layer of the thermosetting resin composition for the color filter protective film of the present invention can be suitably used for a liquid crystal display device or a solid-state imaging device.
以下に実施例および比較例を挙げて本発明をさらに具体的に説明する。なお、以下特に断りのない限り、「部」とは重量部を示す。
材料の調製に用いた測定方法、試験方法を次に示す。
＜重量平均分子量＞
重量平均分子量（Ｍｗ）は、東ソー（株）製ゲルパミエーションクロマトグラフィー装置ＨＬＣ−８２２０ＧＰＣを用い、カラムとして昭和電工（株）製ＳＨＯＤＥＸ Ｋ−８０１を用い、テトラヒドロフラン（ＴＨＦ）を溶離液とし、示差走査屈折率検出器により測定してポリスチレン換算により求めた。
＜固形分＞
固形分は、溶液１ｇを精秤し、恒温機で１７０℃で１時間乾燥後に乾燥前後の重量変化から算出した残存率に基づく。
＜粘度＞
粘度は、循環式恒温水浴を装備した東機産業（株）製Ｂ型粘度計を用いて、温度２０℃で測定した。
＜エポキシ当量＞
エポキシ当量は、ＪＩＳ Ｋ ７２３６：２００１「エポキシ樹脂のエポキシ当量の求め方」によって規定される方法によって測定した。
＜全酸当量＞
全酸当量は、ＪＩＳ Ｋ ００７０：１９９２「化学製品の酸価、けん化価、エステル価、よう素価、水酸基価及び不けん化物の試験方法」の加水分解酸価測定によって測定した。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following, “part” means part by weight unless otherwise specified.
The measurement method and test method used for preparing the materials are shown below.
<Weight average molecular weight>
The weight average molecular weight (Mw) is a differential using a gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation, SHODEX K-801 manufactured by Showa Denko KK as a column, tetrahydrofuran (THF) as an eluent, and a differential. It measured with the scanning refractive index detector and calculated | required by polystyrene conversion.
<Solid content>
The solid content is based on the residual rate calculated from the change in weight before and after drying after precisely weighing 1 g of the solution and drying it at 170 ° C. for 1 hour with a thermostat.
<Viscosity>
The viscosity was measured at a temperature of 20 ° C. using a B-type viscometer manufactured by Toki Sangyo Co., Ltd. equipped with a circulating constant temperature water bath.
<Epoxy equivalent>
The epoxy equivalent was measured by a method defined by JIS K 7236: 2001 “How to Determine Epoxy Equivalent of Epoxy Resin”.
<Total acid equivalent>
The total acid equivalent was measured by hydrolysis acid value measurement according to JIS K 0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”.
熱硬化性樹脂組成物の硬化物の試験方法は以下の通りである。
＜４００ｎｍ光線透過率＞
ガラス基板をリファレンスとして、４００ｎｍ光線透過率を測定した。４００ｎｍ光線透過率が９５％以上の時に良好と判定した。
＜鉛筆硬度＞
ＪＩＳ Ｋ ５６００−５−４：１９９９「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）」のうち、手掻き法で３Ｈ以上の鉛筆硬度を示す時に良好と判定した。
The test method for the cured product of the thermosetting resin composition is as follows.
<400 nm light transmittance>
The light transmittance of 400 nm was measured using a glass substrate as a reference. When the light transmittance at 400 nm was 95% or more, it was determined to be good.
<Pencil hardness>
Of JIS K 5600-5-4: 1999 "General test methods for paints-Part 5: Mechanical properties of coating films-Section 4: Scratch hardness (pencil method)" It was determined to be good when indicated.
＜耐熱性試験＞
保護膜を塗布したガラス基板を２３０℃と２５０℃の２水準の温度で１時間放置後の保護膜の４００ｎｍ光線透過率が９５％以上で、および当該放置前後の色差が０．３以下の時に良好と判定した。なお、色差はＣＩＥ（国際照明委員会）によって１９７６年に定められたΔＥａｂの色差式によって求めた。実際の測定は、分光測色計（ミノルタ（株）製分光測色計ＣＭ−３５００ｄ）によって行った。
＜耐溶剤性試験＞
保護膜を設けたガラス基板を、イソプロピパノール、Ｎ−メチルピロリドンおよびγ−ブチロラクトンの３種の各々の溶剤に液温４０℃で１時間浸漬した後に保護膜の膜厚を測定して算出される膜厚減少が、いずれの溶剤に浸漬した場合でも１０％以下である時に良好と判定した。
<Heat resistance test>
When the glass substrate coated with the protective film has been left at 230 ° C. and 250 ° C. for two hours at 400 ° C. and the 400 nm light transmittance is 95% or more, and the color difference before and after being left is 0.3 or less It was determined to be good. The color difference was determined by the ΔEab color difference formula established in 1976 by the CIE (International Commission on Illumination). Actual measurement was performed with a spectrocolorimeter (Spectrocolorimeter CM-3500d manufactured by Minolta Co., Ltd.).
<Solvent resistance test>
It is calculated by immersing a glass substrate provided with a protective film in each of the three solvents of isopropylpropanol, N-methylpyrrolidone and γ-butyrolactone at a liquid temperature of 40 ° C. for 1 hour and then measuring the thickness of the protective film. When the film thickness reduction was 10% or less even when immersed in any solvent, the film was judged to be good.
＜耐温純水試験後密着性＞
保護膜を設けたガラス基板を８０℃の純水に１時間浸漬後にＪＩＳ Ｋ 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）」試験法を行った結果が、同法における分類０〜１のときに良好と判定した。
＜段差低減率＞
透明ガラス基板上に光硬化性レジストを用いて、常法によりストライプ状の凹凸をガラス基板に作製した（ストライプ幅；５０μｍ）。この基板の表面の凹凸（段差）を微細形状測定機（（株）小坂研究所製；商標；サーフコーダー ＥＴ４００）によって測定した結果、２．０μｍであった。この凹凸基板上に保護膜を設けた基板の表面の凹凸を同測定機によって計測し、段差低減率を算出し、８０％以上であるときに良好と判定した。
段差低減率は、次式から算出される。
段差低減率（％）＝｛（カラーフィルター保護膜形成前のカラーフィルターの段差−カラーフィルター保護膜形成後のカラーフィルターの段差）／カラーフィルター保護膜形成前のカラーフィルターの段差｝×１００
<Adhesion after heat-resistant pure water test>
A glass substrate provided with a protective film is immersed in pure water at 80 ° C. for 1 hour, and then JIS K 5600-5-6: 1999 “General Test Method for Paint—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesiveness (Cross-cut method) "The test method was determined to be good when the classification was 0 to 1 in the method.
<Step reduction ratio>
Using a photocurable resist on a transparent glass substrate, stripe-shaped irregularities were formed on the glass substrate by a conventional method (stripe width; 50 μm). As a result of measuring the unevenness (step) on the surface of the substrate with a fine shape measuring instrument (manufactured by Kosaka Laboratory Ltd .; trademark: Surfcoder ET400), it was 2.0 μm. The unevenness on the surface of the substrate provided with a protective film on the uneven substrate was measured by the same measuring machine, and the step reduction rate was calculated, and judged to be good when it was 80% or more.
The step reduction rate is calculated from the following equation.
Step reduction ratio (%) = {(step of color filter before forming color filter protective film−step of color filter after forming color filter protective film) / step of color filter before forming color filter protective film} × 100
重合例１
＜重合体（ａ−１）の重合＞
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（以下、ＰＭＡと略記する）を１６０ｇ仕込み、攪拌しながら加熱して７８℃に昇温した。次いで、７８℃の温度でグリシジルメタクリレート（以下、ＧＭＡと略記する）１１４ｇ、シクロヘキシルメタクリレート８６ｇ、日本油脂（株）製の過酸化物系重合開始剤「パーヘキシルＯ（；商品名、純度９２．５％）」（以下、ＰＨＯと略記する）７ｇ、およびＰＭＡ３３ｇ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。滴下終了後、９８℃に昇温し温度を７時間維持した後、反応を終了した。重量平均分子量（Ｍｗ）５５，０００、固形分５２％、粘度３８Ｐａ・ｓ（２０℃）および溶液のエポキシ当量５２０ｇ／ｍｏｌのエポキシ基を有する重合体の溶液（エポキシ基を有する重合体のエポキシ当量２６０ｇ／ｍｏｌ）を得た。
Polymerization example 1
<Polymerization of polymer (a-1)>
A 500 mL four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel was charged with 160 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PMA) and heated to 78 ° C. while stirring. Warm up. Next, at a temperature of 78 ° C., 114 g of glycidyl methacrylate (hereinafter abbreviated as GMA), 86 g of cyclohexyl methacrylate, a peroxide polymerization initiator “Perhexyl O” (trade name, purity 92.5%) manufactured by NOF Corporation. ) "(Hereinafter abbreviated as PHO) and PMA (33 g), which were previously mixed uniformly (dropping component), were dropped at a constant rate from a dropping funnel over 2 hours. After completion of dropping, the temperature was raised to 98 ° C. and the temperature was maintained for 7 hours, and then the reaction was terminated. Weight average molecular weight (Mw) 55,000, solid content 52%, viscosity 38 Pa · s (20 ° C.), and solution of polymer having epoxy group of 520 g / mol of epoxy equivalent (epoxy equivalent of polymer having epoxy group) 260 g / mol).
＜重合体（ａ−２〜ａ−６）の重合＞
重合体（ａ−１）と同様に重合体（ａ−２〜ａ−６）を得た。各原料の仕込み比、滴下温度、重量平均分子量、固形分、粘度、およびエポキシ当量を、重合例（ａ−１）と合わせて、表１に示した。
<Polymerization of polymer (a-2 to a-6)>
Polymers (a-2 to a-6) were obtained in the same manner as the polymer (a-1). The charge ratio, dropping temperature, weight average molecular weight, solid content, viscosity, and epoxy equivalent of each raw material are shown in Table 1 together with the polymerization example (a-1).
なお、表中の略号は以下の通りである。
＊１：ジシクロペンタニルメタクリレート
＊２：スチレン
＜重合体（ａ−７）の重合＞
温度計、還流冷却器、攪拌機を備えた容量５００ｍＬの３つ口フラスコに、ビニルトリメトキシシランを１６９ｇ、プロピレングリコールモノメチルエーテルアセテート２１０ｇを仕込み攪拌した。次いで、蒸留水６２ｇ、シュウ酸０．０５０ｇを加え１２０℃に昇温した。反応によって生成するメタノール、および水を留去しながら、１２０℃で２時間攪拌した後、反応を終了した。
The abbreviations in the table are as follows.
* 1: Dicyclopentanyl methacrylate * 2: Styrene <Polymerization of polymer (a-7)>
In a 500 mL three-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, 169 g of vinyltrimethoxysilane and 210 g of propylene glycol monomethyl ether acetate were charged and stirred. Next, 62 g of distilled water and 0.050 g of oxalic acid were added and the temperature was raised to 120 ° C. The reaction was completed after stirring at 120 ° C. for 2 hours while distilling off methanol and water produced by the reaction.
合成例１
＜カルボキシル基がビニルエーテルにより潜在化された多価カルボン酸化合物（Ｂ−１）の合成＞
温度計、還流冷却器、攪拌機、滴下ロートを備えた４つ口フラスコに、ＰＭＡ２７ｇ、三菱瓦斯化学（株）製トリメリット酸（以下、ＴＭＡと略記する）２７ｇ、ｎ−プロピルビニルエーテル４６ｇを仕込み、攪拌しながら加熱し７０℃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０．６４ｍｇＫＯＨ／ｇの潜在化された多価カルボン酸化合物の溶液（ｂ−１）が得られた。なお、溶液の酸価は０．１ＮのＫＯＨエタノール溶液で滴定し、算出した。また、化合物（Ｂ−１）の全酸当量は、ＪＩＳ Ｋ００７０：１９９２「化学製品の酸価、けん化、エステル価、よう素価、水酸基価、および不けん化物の試験方法」の加水分解酸価測定（全酸価測定）に基づき測定し、２６０ｍｇＫＯＨ／ｇであった。
Synthesis example 1
<Synthesis of polyvalent carboxylic acid compound (B-1) in which carboxyl group is made latent by vinyl ether>
A four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel was charged with 27 g of PMA, 27 g of trimellitic acid (hereinafter abbreviated as TMA) manufactured by Mitsubishi Gas Chemical Co., Ltd., and 46 g of n-propyl vinyl ether. The mixture was heated with stirring and heated to 70 ° 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 latent polyvalent carboxylic acid compound having an acid value of 0.64 mgKOH / g of the solution was terminated. A solution (b-1) was obtained. The acid value of the solution was calculated by titration with a 0.1N KOH ethanol solution. The total acid equivalent weight of the compound (B-1) is the hydrolysis acid value of JIS K0070: 1992 “Testing method for acid value, saponification, ester value, iodine value, hydroxyl value, and unsaponified product of chemical products”. Based on measurement (total acid value measurement), it was 260 mgKOH / g.
合成例２
＜カルボキシル基がビニルエーテルにより潜在化された多価カルボン酸化合物（Ｂ−２）の合成＞
温度計、還流冷却器、攪拌機、滴下ロートを備えた４つ口フラスコに、ＰＭＡ３３ｇ、三菱瓦斯化学（株）製シクロヘキサン−１，２，４−トリカルボン酸（以下、ＣＨＴＡと略記する）２７ｇ、およびｎ−プロピルビニルエーテル４０ｇ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１．２３ｍｇＫＯＨ／ｇのブロック化カルボン酸化合物溶液（ｂ−２）が得られた。なお、溶液の酸価は０．１ＮのＫＯＨエタノール溶液で滴定し、算出した。また、化合物（Ｂ−２）の全酸当量は、化合物（Ｂ−１）と同様の方法で測定し、２７０ｍｇＫＯＨ／ｇであった。
Synthesis example 2
<Synthesis of polyvalent carboxylic acid compound (B-2) in which carboxyl group is latentized by vinyl ether>
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel, 33 g of PMA, 27 g of cyclohexane-1,2,4-tricarboxylic acid (hereinafter abbreviated as CHTA) manufactured by Mitsubishi Gas Chemical Co., Ltd., and 40 g of n-propyl vinyl ether 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 blocked carboxylic acid compound solution (b-2) having an acid value of 1.23 mgKOH / g of the solution was obtained. )was gotten. The acid value of the solution was calculated by titration with a 0.1N KOH ethanol solution. Moreover, the total acid equivalent of compound (B-2) was measured by the same method as for compound (B-1), and was 270 mgKOH / g.
実施例１〜６
表２に示す配合割合で溶解混合したカラーフィルター保護膜用の熱硬化性樹脂組成物の溶液を、孔径０．２μｍのメンブランフィルターで濾過した後、スピンコーターを用いてガラス基板（日本電気硝子（株）製、商品名「ＯＡ−１０」無アルカリガラス）、および前記凹凸基板上に８００ｒｐｍで回転塗布した。塗布後、ガラス基板、および凹凸基板を８０℃のクリーンオーブン中にて５分間乾燥処理後、２３０℃のクリーンオーブン中にて３０分間処理し、塗膜を硬化させた。得られた膜状の熱硬化性樹脂組成物の硬化物について、４００ｎｍ光線透過率、鉛筆硬度、耐熱性試験（２３０℃×１ｈ．）、耐熱性試験（２５０℃×１ｈ．）、耐溶剤性試験、耐温純水試験後密着性、および段差低減率の各試験を行った。結果を表２に併せて示す。
Examples 1-6
After the solution of the thermosetting resin composition for the color filter protective film dissolved and mixed at the blending ratio shown in Table 2 is filtered through a membrane filter having a pore diameter of 0.2 μm, a glass substrate (Nippon Electric Glass ( Co., Ltd., trade name “OA-10” non-alkali glass) and the uneven substrate were spin-coated at 800 rpm. After coating, the glass substrate and the concavo-convex substrate were dried in a clean oven at 80 ° C. for 5 minutes and then treated in a clean oven at 230 ° C. for 30 minutes to cure the coating film. About the cured | curing material of the obtained film-form thermosetting resin composition, 400 nm light transmittance, pencil hardness, a heat resistance test (230 degreeC x 1 h.), A heat resistance test (250 degreeC x 1 h.), Solvent resistance Each test of a test, adhesion after a heat-resistant pure water test, and a level | step difference reduction rate was done. The results are also shown in Table 2.
比較例１〜７
表３に示す配合割合で溶解混合したカラーフィルター保護膜用の熱硬化性樹脂組成物の溶液から、実施例と全く同じ方法によって熱硬化性樹脂組成物の硬化物を得、硬化物について同じ試験を行った。結果を表３に併せて示す。
なお、実施例および比較例の全ての場合において、得られた塗膜の表面は極めて平滑であり、ピンホール等は全く見られなかった。膜厚は２．０〜２．５μｍであった。
Comparative Examples 1-7
A cured product of the thermosetting resin composition was obtained from the solution of the thermosetting resin composition for the color filter protective film dissolved and mixed at the blending ratio shown in Table 3 by the same method as in the examples, and the same test was performed on the cured product Went. The results are also shown in Table 3.
In all cases of Examples and Comparative Examples, the surface of the obtained coating film was extremely smooth, and no pinholes were observed. The film thickness was 2.0 to 2.5 μm.
※１）記載の（Ａ）成分（エポキシ基含有樹脂）、（Ｂ）成分（ブロック化された多価カルボン酸）、およびａ−７（重合例７の樹脂）と溶剤のプロピレングリコールモノメチルエーテルアセテート（ＰＭＡ）の各成分は、重合例１〜７、および合成例１, および２で得られた溶液として配合した。
※２）固形分濃度は、全成分に対しての、希釈溶剤を除いた成分の小計の百分率である。
また、表２、３における略号、および名称は次のものを示す。
ａ−１：重合例１で得られたエポキシ基を有する重合体の溶液、エポキシ当量５２０ｇ／ｍｏｌ。
ａ−２：重合例２で得られたエポキシ基を有する重合体の溶液、エポキシ当量５１０ｇ／ｍｏｌ。
ａ−３：重合例３で得られたエポキシ基を有する重合体の溶液、エポキシ当量５２０ｇ／ｍｏｌ。
ａ−４：重合例４で得られたエポキシ基を有する重合体の溶液、エポキシ当量５１０ｇ／ｍｏｌ。
ａ−５：重合例５で得られたエポキシ基を有する重合体の溶液、エポキシ当量５１０ｇ／ｍｏｌ。
ａ−６：重合例６で得られたエポキシ基を有する重合体の溶液、エポキシ当量１０００ｇ／ｍｏｌ。
ａ−７：重合例７で得られた加水分解縮合物。
ｂ−１：合成例１で得られたブロック化されたカルボキシル基を２個以上有する硬化剤溶液、全酸当量２６０ｇ／ｍｏｌ。
ｂ−２：合成例２で得られたブロック化されたカルボキシル基を２個以上有する硬化剤溶液、全酸当量２７０ｇ／ｍｏｌ。
ｃ−１：１，４−ビス（（（３−エチル−３−オキセタニル）メトキシ）メチル）ベンゼン、東亜合成（株）製、商品名「ＯＸＴ−１２１」。
ｃ−２：ビス（（３−エチル−３−オキセタニル）メチル）エーテル、東亜合成（株）製、商品名「ＯＸＴ−２２１」。
ｃ−３：ビス（（３−エチル−３−オキセタニル）メチル）シクロヘキサン−１，４−ジカルボキシレート。
ＫＢＭ−４０３：シランカップリング剤、γ−グリシドキシプロピルトリメトキシシラン、信越化学工業（株）製。
ＬＣ−１：熱潜在性触媒、日本油脂（株）製。
Ｒ−８：表面張力低下剤、大日本インキ化学工業（株）製、商品名「メガファックＲ−８」。
ＰＭＡ：溶剤、プロピレングリコールモノメチルエーテルアセテート、（株）クラレ製。
Ｅｐ８２７：ビスフェノールＡ型エポキシ樹脂、ジャパンエポキシレジン（株）製、商品名「エピコート８２７」（エポキシ当量１８５ｇ／ｍｏｌ）。
* 1) Component (A) (epoxy group-containing resin), component (B) (blocked polyvalent carboxylic acid), and a-7 (resin of polymerization example 7) and solvent propylene glycol monomethyl ether acetate Each component of (PMA) was blended as a solution obtained in Polymerization Examples 1 to 7 and Synthesis Examples 1 and 2.
* 2) The solid content concentration is the percentage of the total of the components excluding the diluting solvent with respect to the total components.
The abbreviations and names in Tables 2 and 3 indicate the following.
a-1: Polymer solution having an epoxy group obtained in Polymerization Example 1, epoxy equivalent of 520 g / mol.
a-2: Polymer solution having an epoxy group obtained in Polymerization Example 2, epoxy equivalent 510 g / mol.
a-3: Polymer solution having an epoxy group obtained in Polymerization Example 3, epoxy equivalent of 520 g / mol.
a-4: A solution of the polymer having an epoxy group obtained in Polymerization Example 4, an epoxy equivalent of 510 g / mol.
a-5: Polymer solution having an epoxy group obtained in Polymerization Example 5, epoxy equivalent 510 g / mol.
a-6: A solution of the polymer having an epoxy group obtained in Polymerization Example 6, an epoxy equivalent of 1000 g / mol.
a-7: Hydrolysis condensate obtained in Polymerization Example 7.
b-1: Curing agent solution having two or more blocked carboxyl groups obtained in Synthesis Example 1, total acid equivalent of 260 g / mol.
b-2: Hardener solution having two or more blocked carboxyl groups obtained in Synthesis Example 2, total acid equivalent of 270 g / mol.
c-1: 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene, manufactured by Toa Gosei Co., Ltd., trade name “OXT-121”.
c-2: Bis ((3-ethyl-3-oxetanyl) methyl) ether, manufactured by Toa Gosei Co., Ltd., trade name “OXT-221”.
c-3: Bis ((3-ethyl-3-oxetanyl) methyl) cyclohexane-1,4-dicarboxylate.
KBM-403: Silane coupling agent, γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
LC-1: Thermal latent catalyst, manufactured by NOF Corporation.
R-8: Surface tension reducing agent, manufactured by Dainippon Ink & Chemicals, Inc., trade name “Megafac R-8”.
PMA: Solvent, propylene glycol monomethyl ether acetate, manufactured by Kuraray Co., Ltd.
Ep827: Bisphenol A type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., trade name “Epicoat 827” (epoxy equivalent 185 g / mol).
表２の結果より、本発明の樹脂組成物を用いた実施例１〜６の場合は、得られた熱硬化性樹脂組成物の硬化が、透明性、鉛筆硬度、耐熱性、耐溶剤性、密着性等の一般的性能を十分満足しながら、段差低減率の性能が格段に優れており、本発明の目的の効果が申し分なく得られていることがわかる。
これに対して、表３において比較例１〜３は、本発明に用いる多価オキセタン化合物を用いていないため、段差低減率の性能において本発明の目的の効果が得られていない。また、比較例４〜６は、本発明に用いるエポキシ基を有する重合体とは異なるエポキシ基を有する重合体を用いているため、鉛筆硬度、段差低減率の性能に問題があり、本発明の目的の効果が得られていない。比較例７は、オキセタニル基含有樹脂、およびエポキシ基含有樹脂のカチオン重合が優先的に進行し、硬化物の架橋部分が全てエーテル結合となっているため、耐温純水試験後密着性の性能に問題があり、本発明の目的の効果が得られていない。
From the results of Table 2, in the case of Examples 1 to 6 using the resin composition of the present invention, curing of the obtained thermosetting resin composition is transparency, pencil hardness, heat resistance, solvent resistance, It can be seen that the performance of the step reduction ratio is remarkably excellent while sufficiently satisfying general performance such as adhesion and the effect of the object of the present invention is obtained satisfactorily.
On the other hand, in Table 3, Comparative Examples 1 to 3 do not use the polyvalent oxetane compound used in the present invention, and thus the effect of the present invention is not obtained in the performance of the step reduction rate. Moreover, since Comparative Examples 4 to 6 use a polymer having an epoxy group different from the polymer having an epoxy group used in the present invention, there is a problem in the performance of pencil hardness and step reduction ratio. The desired effect is not obtained. In Comparative Example 7, since the cationic polymerization of the oxetanyl group-containing resin and the epoxy group-containing resin proceeds preferentially and all the cross-linked parts of the cured product are ether bonds, there is a problem in the adhesion performance after the heat resistance pure water test. Therefore, the object effect of the present invention is not obtained.
Claims (3)
（Ａ）下記の式（１）で表される構成単位を有し、エポキシ当量が５００ｇ／ｍｏｌ以下であり、ポリスチレン換算の重量平均分子量（Ｍｗ）が３，０００〜１００，０００であるエポキシ基を有する重合体
（Ｂ）炭素数４〜２０で２〜８価のカルボン酸のカルボキシル基を、下記の式（１４）
で表されるビニルエーテルのビニル基と反応させて得られる式（１３）
で表される官能基を２〜８個有する潜在化された多価カルボン酸化合物
（Ｃ）多価オキセタン化合物 The following components (A), (B), and (C) are mixed in a proportion of (A) 15 to 65% by weight, (B) 10 to 60% by weight, and (C) 5 to 45% by weight (however, the total is 100 A thermosetting resin composition for a color filter protective film, characterized by comprising:
(A) An epoxy group having a structural unit represented by the following formula (1 ), having an epoxy equivalent of 500 g / mol or less, and a polystyrene-equivalent weight average molecular weight (Mw) of 3,000 to 100,000. Polymer having
( B) A carboxyl group of a divalent to octavalent carboxylic acid having 4 to 20 carbon atoms is represented by the following formula (14):
Formula (13) obtained by reacting with the vinyl group of vinyl ether represented by
A latent polyvalent carboxylic acid compound (C) having a functional group represented by formula (C): a polyvalent oxetane compound
The color filter which has the layer of the resin cured material formed by hardening | curing the thermosetting resin composition for color filter protective films of Claim 1.
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