KR102307921B1 - Polymer composition, photosensitive resin composition and color filter - Google Patents
Polymer composition, photosensitive resin composition and color filter Download PDFInfo
- Publication number
- KR102307921B1 KR102307921B1 KR1020207011985A KR20207011985A KR102307921B1 KR 102307921 B1 KR102307921 B1 KR 102307921B1 KR 1020207011985 A KR1020207011985 A KR 1020207011985A KR 20207011985 A KR20207011985 A KR 20207011985A KR 102307921 B1 KR102307921 B1 KR 102307921B1
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylic acid
- polymer
- acid
- photosensitive resin
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 127
- 239000011342 resin composition Substances 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims description 48
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000002253 acid Substances 0.000 claims abstract description 69
- 239000002904 solvent Substances 0.000 claims abstract description 63
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 23
- 238000004040 coloring Methods 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000003086 colorant Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 59
- 229940048053 acrylate Drugs 0.000 description 59
- 239000000758 substrate Substances 0.000 description 33
- 239000000178 monomer Substances 0.000 description 32
- -1 2-ethylhexyl Chemical group 0.000 description 28
- 239000007870 radical polymerization initiator Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000049 pigment Substances 0.000 description 21
- 239000003513 alkali Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 17
- 238000004383 yellowing Methods 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- 229940114077 acrylic acid Drugs 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000007519 polyprotic acids Polymers 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 5
- 239000007809 chemical reaction catalyst Substances 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 4
- WLTSXAIICPDFKI-UHFFFAOYSA-N 3-dodecene Chemical compound CCCCCCCCC=CCC WLTSXAIICPDFKI-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000980 acid dye Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- BEQIIZJSZSVJJK-UHFFFAOYSA-M chembl2028372 Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1N=NC1=C(O)C=CC2=CC=CC=C12 BEQIIZJSZSVJJK-UHFFFAOYSA-M 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 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
- PHWXYKUZSUKPCM-ALCCZGGFSA-N (z)-2-pentan-3-ylbut-2-enedioic acid Chemical compound CCC(CC)C(\C(O)=O)=C\C(O)=O PHWXYKUZSUKPCM-ALCCZGGFSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- FMZITCJWMYHQFG-UHFFFAOYSA-N 1,2,3,4,4a,5,8,8a-octahydro-2-methyl-1,4:5,8-dimethanonaphthalene Chemical compound C1C(C23)C=CC1C3C1CC2CC1C FMZITCJWMYHQFG-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
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- Polymerisation Methods In General (AREA)
Abstract
특정 구성 단위를 갖고 또한 산가 (mgKOH/g) 가 상이한 2 종 이상의 (메트)아크릴산계 중합체와, 용제와, 반응성 희석제와, 광 중합 개시제를 포함하는 감광성 수지 조성물로서, 상기 감광성 수지 조성물은, 상기 2 종 이상의 (메트)아크릴산계 중합체 중, 최대 산가를 갖는 (메트)아크릴산계 중합체 (a) 의 산가를 1 로 한 경우에, 0.01 배 ∼ 0.50 배의 산가를 갖는 (메트)아크릴산계 중합체 (b) 를 포함하고, 상기 (메트)아크릴산계 중합체 (a) 의 중량 평균 분자량이 1,000 ∼ 10,000 이며, 또한 상기 (메트)아크릴산계 중합체 (b) 에 대한 상기 (메트)아크릴산계 중합체 (a) 의 질량비 [(a)/(b)] 가 0.01 ∼ 0.50 인 감광성 수지 조성물.A photosensitive resin composition comprising two or more (meth)acrylic acid-based polymers having specific structural units and having different acid values (mgKOH/g), a solvent, a reactive diluent, and a photoinitiator, wherein the photosensitive resin composition comprises: Among the two or more types of (meth)acrylic acid-based polymers, when the (meth)acrylic acid-based polymer (a) having the largest acid value has an acid value of 1, (meth)acrylic acid-based polymer (b) having an acid value of 0.01 to 0.50 times ), the weight average molecular weight of the (meth)acrylic acid-based polymer (a) is 1,000 to 10,000, and the mass ratio of the (meth)acrylic acid-based polymer (a) to the (meth)acrylic acid-based polymer (b) The photosensitive resin composition whose [(a)/(b)] is 0.01-0.50.
Description
본 발명은, 중합체 조성물, 이 중합체 조성물을 포함하는 감광성 수지 조성물 및 이 감광성 수지 조성물을 사용하여 제조되는 컬러 필터에 관한 것이다.This invention relates to a polymer composition, the photosensitive resin composition containing this polymer composition, and the color filter manufactured using this photosensitive resin composition.
최근, 자원 절약 및 에너지 절약의 관점에서, 각종 코팅, 인쇄, 도료, 접착제 등의 분야에 있어서, 자외선, 전자선 등의 활성 에너지선에 의해 경화 가능한 감광성 수지 조성물이 널리 사용되고 있다. 또, 프린트 배선 기판 등의 전자 재료의 분야에 있어서도, 활성 에너지선에 의해 경화 가능한 감광성 수지 조성물이, 솔더 레지스트, 컬러 필터, 블랙 매트릭스, 블랙 칼럼 스페이서, 포토 스페이서, 보호막용 레지스트 등에 사용되고 있다.In recent years, from the viewpoint of resource saving and energy saving, in the fields of various coatings, printing, paints, adhesives, etc., photosensitive resin compositions curable by active energy rays such as ultraviolet rays and electron beams are widely used. Moreover, also in the field of electronic materials, such as a printed wiring board, the photosensitive resin composition which can be hardened|cured by an active energy ray is used for a soldering resist, a color filter, a black matrix, a black column spacer, a photo spacer, the resist for protective films, etc.
컬러 필터는, 일반적으로, 유리 기판 등의 투명 기판과, 투명 기판 상에 형성된 적 (R), 녹 (G) 및 청 (B) 의 화소와, 화소의 경계에 형성되는 블랙 매트릭스와, 화소 및 블랙 매트릭스 상에 형성된 보호막으로 구성된다. 이와 같은 구성의 컬러 필터는, 통상, 투명 기판 상에, 블랙 매트릭스, 화소 및 보호막을 순차 형성함으로써 제조된다. 화소 및 블랙 매트릭스 (이하, 화소 및 블랙 매트릭스를 「착색 패턴」이라고 한다.) 의 형성 방법으로는, 여러 가지 방법이 개시되어 있다. 착색 패턴의 형성 방법으로는, 예를 들어, 감광성 수지 조성물을 레지스트로서 사용하고, 그 감광성 수지 조성물의 도포, 노광, 현상 및 베이킹을 반복하는 포토리소그래피 공법을 포함하는 안료/염료 분산법을 들 수 있다. 이 안료/염료 분산법은, 내광성이나 내열성 등의 내구성이 우수하고, 핀홀 등의 결함이 적은 착색 패턴을 형성할 수 있으므로, 현재 널리 사용되고 있다.A color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundary between the pixels, a pixel and It consists of a protective film formed on a black matrix. The color filter of such a structure is normally manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. Various methods are disclosed as a formation method of a pixel and a black matrix (Hereinafter, a pixel and a black matrix are called "coloring pattern."). As a method of forming a coloring pattern, for example, a pigment/dye dispersion method including a photolithography method in which a photosensitive resin composition is used as a resist and the photosensitive resin composition is applied, exposed, developed and baked is repeated. have. This pigment/dye dispersion method is excellent in durability, such as light resistance and heat resistance, and since it can form a coloring pattern with few defects, such as a pinhole, it is widely used now.
그러나, 안료/염료 분산법은, 상기 이점을 가지고 있는 반면, 블랙 매트릭스, R, G 및 B 의 각 화소의 패턴을 고온에서 반복 형성하는 점에서, 이 방법에 사용되는 감광성 수지 조성물에는 높은 내열 황변성이 요구된다.However, while the pigment/dye dispersion method has the above advantages, the photosensitive resin composition used in this method has high heat resistance sulfur in that the pattern of each pixel of the black matrix, R, G, and B is repeatedly formed at a high temperature. transformation is required.
또, 일반적으로 액정 표시 장치는, 개별적으로 제작한 컬러 필터 기판과, TFT (Thin-Film-Transistor) 기판 사이에, 액정을 끼우고, 이들 부재를 첩합 (貼合) 함으로써 제조된다. 이들 부재를 첩합할 때, 컬러 필터 기판에는, 액정을 배향시키기 위해서 폴리이미드 필름 등의 배향막이 형성된다. 이때, 컬러 필터층은, 폴리이미드 수지에 포함되는 N-메틸피롤리돈 (NMP) 등의 극성이 높은 용제에 노출되기 때문에, 컬러 필터층에 사용되는 감광성 수지 조성물에는 내용제성이 요구된다.Moreover, generally, a liquid crystal display device is manufactured by pinching|interposing a liquid crystal between the color filter board|substrate produced individually, and TFT(Thin-Film-Transistor) board|substrate, and bonding these members together. When bonding these members together, in order to orientate a liquid crystal, orientation films, such as a polyimide film, are formed in a color filter board|substrate. At this time, since the color filter layer is exposed to a solvent with high polarity, such as N-methylpyrrolidone (NMP) contained in polyimide resin, solvent resistance is calculated|required of the photosensitive resin composition used for a color filter layer.
예를 들어, 특허문헌 1 및 2 에서는, 내열성, 내용제성 등이 우수한 컬러 필터용 감광성 수지 조성물이 여러 가지 제안되어 있다. 그러나, 컬러 필터의 제조에 사용되는 감광성 수지 조성물에는, 내열 황변성, 내용제성 및 알칼리 현상성의 추가적인 향상이 요구되고 있다. For example, in
본 발명은, 상기와 같은 과제를 해결하기 위해서 이루어진 것으로, 내열 황변성, 내용제성 및 알칼리 현상성이 우수한 감광성 수지 조성물을 제공하는 것을 목적으로 한다. 또, 본 발명은, 상기 감광성 수지 조성물로 형성되는 내열 황변성 및 내용제성이 우수한 컬러 필터를 제공하는 것을 목적으로 한다. The present invention has been made in order to solve the above problems, and an object of the present invention is to provide a photosensitive resin composition excellent in heat yellowing resistance, solvent resistance, and alkali developability. Moreover, an object of this invention is to provide the color filter excellent in heat yellowing resistance and solvent resistance formed from the said photosensitive resin composition.
본 발명자들은, 상기 과제를 해결하기 위하여 예의 검토한 결과, 특정 구성 단위를 갖고 또한 특정 산가 (mgKOH/g) 를 갖는 2 종 이상의 (메트)아크릴산계 중합체를 특정 질량비로 포함하는 중합체 조성물을 포함하는 감광성 수지 조성물이, 상기 과제를 해결할 수 있는 것을 알아내어, 본 발명을 완성하기에 이르렀다.As a result of intensive studies to solve the above problems, the present inventors have a specific structural unit and a polymer composition comprising two or more (meth)acrylic acid polymers having a specific acid value (mgKOH/g) in a specific mass ratio. The photosensitive resin composition discovered that the said subject was solvable, and came to complete this invention.
즉, 본 발명은, 이하의 [1] ∼ [7] 로 나타낸다. That is, this invention is shown by the following [1] - [7].
[1] 하기 식 1 또는 식 2 로 나타내는 구성 단위를 갖고 또한 산가 (mgKOH/g) 가 상이한 2 종 이상의 (메트)아크릴산계 중합체를 포함하는 중합체 조성물로서, [1] A polymer composition comprising two or more types of (meth)acrylic acid polymers having structural units represented by the following
상기 중합체 조성물은, 상기 2 종 이상의 (메트)아크릴산계 중합체 중, 최대 산가를 갖는 (메트)아크릴산계 중합체 (a) 의 산가를 1 로 한 경우에, 0.01 배 ∼ 0.50 배의 산가를 갖는 (메트)아크릴산계 중합체 (b) 를 포함하고, The polymer composition has an acid value of 0.01 to 0.50 times when the acid value of the (meth)acrylic acid-based polymer (a) having the maximum acid value among the two or more types of (meth)acrylic acid-based polymers is 1 (meth) ) containing an acrylic acid-based polymer (b),
상기 (메트)아크릴산계 중합체 (a) 의 중량 평균 분자량이 1,000 ∼ 10,000 이며, 또한 The (meth)acrylic acid polymer (a) has a weight average molecular weight of 1,000 to 10,000, and
상기 (메트)아크릴산계 중합체 (b) 에 대한 상기 (메트)아크릴산계 중합체 (a) 의 질량비 [(a)/(b)] 가 0.01 ∼ 0.50 인 것을 특징으로 하는 중합체 조성물.The mass ratio [(a)/(b)] of the (meth)acrylic acid-based polymer (a) to the (meth)acrylic acid-based polymer (b) is 0.01 to 0.50.
[화학식 1] [Formula 1]
(식 1 중, R1 은 수소 원자 또는 메틸기를 나타낸다. 식 2 중, R2 는 수소 원자 또는 메틸기를 나타내고, R3 은 산기와 에틸렌성 불포화기를 갖는 탄소수 2 ∼ 30 의 기를 나타낸다.) (In
[2] 상기 (메트)아크릴산계 중합체 (a) 와 상기 (메트)아크릴산계 중합체 (b) 가, 상기 식 1 또는 상기 식 2 로 나타내는 동일한 구성 단위를 적어도 1 개 갖는 것을 특징으로 하는 [1] 에 기재된 중합체 조성물.[2] The (meth)acrylic acid-based polymer (a) and the (meth)acrylic acid-based polymer (b) each have at least one identical structural unit represented by the
[3] 상기 (메트)아크릴산계 중합체 (b) 의 중량 평균 분자량이 1,000 ∼ 10,000 인 것을 특징으로 하는 [1] 또는 [2] 에 기재된 중합체 조성물.[3] The polymer composition according to [1] or [2], wherein the (meth)acrylic acid polymer (b) has a weight average molecular weight of 1,000 to 10,000.
[4] 상기 (메트)아크릴산계 중합체 (b) 의 산가가 상기 (메트)아크릴산계 중합체 (a) 의 산가의 0.01 배 ∼ 0.30 배인 것을 특징으로 하는 [1] ∼ [3] 중 어느 하나에 기재된 중합체 조성물.[4] The acid value of the (meth)acrylic acid polymer (b) is 0.01 to 0.30 times the acid value of the (meth)acrylic acid polymer (a), according to any one of [1] to [3], characterized in that polymer composition.
[5] [1] ∼ [4] 중 어느 하나에 기재된 중합체 조성물 (A), 용제 (B), 반응성 희석제 (C) 및 광 중합 개시제 (D) 를 포함하는 것을 특징으로 하는 감광성 수지 조성물.[5] A photosensitive resin composition comprising the polymer composition (A) according to any one of [1] to [4], a solvent (B), a reactive diluent (C), and a photoinitiator (D).
[6] 착색제 (E) 를 추가로 포함하는 것을 특징으로 하는 [5] 에 기재된 감광성 수지 조성물.[6] The photosensitive resin composition according to [5], further comprising a colorant (E).
[7] [6] 에 기재된 감광성 수지 조성물로 형성된 착색 패턴을 갖는 것을 특징으로 하는 컬러 필터.[7] A color filter having a colored pattern formed from the photosensitive resin composition according to [6].
본 발명에 의하면, 내열 황변성, 내용제성 및 알칼리 현상성이 우수한 감광성 수지 조성물을 제공할 수 있다. 또, 본 발명은, 내열 황변성 및 내용제성이 우수한 착색 패턴을 갖는 컬러 필터를 제공할 수 있다. ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in heat yellowing resistance, solvent resistance, and alkali developability can be provided. Moreover, this invention can provide the color filter which has a coloring pattern excellent in heat-resistant yellowing property and solvent resistance.
도 1 은 본 발명의 일 실시형태의 컬러 필터를 나타내는 개략 단면도이다.BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows the color filter of one Embodiment of this invention.
이하에 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
<중합체 조성물 (A)> <Polymer composition (A)>
본 발명의 중합체 조성물 (A) 는, 산기를 갖는 하기 식 1 또는 식 2 로 나타내는 구성 단위를 갖고 또한 산가 (mgKOH/g) 가 상이한 2 종 이상의 (메트)아크릴산계 중합체를 포함하는 것이다. 또한, 본 발명에 있어서 「(메트)아크릴산」은, 메타크릴산 및 아크릴산에서 선택되는 적어도 1 종을 의미한다.The polymer composition (A) of this invention contains the structural unit represented by following
[화학식 2] [Formula 2]
(식 1 중, R1 은 수소 원자 또는 메틸기를 나타낸다. 식 2 중, R2 는 수소 원자 또는 메틸기를 나타내고, R3 은 산기와 에틸렌성 불포화기를 갖는 탄소수 2 ∼ 30 의 기를 나타낸다.) (In
R3 이 갖는 상기 산기의 예로는, 카르복시기 외에, 2 염기산기 (술폰산기 등), 3 염기산기 (인산기 등) 등의 다염기산기를 들 수 있지만, 그 중에서도 카르복시기가 바람직하다. R3 은 바람직하게는 카르복시기와 에틸렌성 불포화기를 갖는 탄소수 9 ∼ 20 의 기이다. R3 이 갖는 카르복시기를 포함하는 구조의 구체예로는, 하기 식 3 ∼ 20 으로 나타내는 구조 등을 들 수 있다. 이들 중에서도, 특히 원료의 입수 용이함, 합성상의 반응성의 관점에서, 하기 식 4, 11 로 나타내는 구조인 것이 바람직하다. 또, 식 3 ∼ 식 20 의 카르복시기가, 상기 다염기산기로 치환된 것이어도 된다.Examples of the acid group that R 3 has include polybasic acid groups such as dibasic acid groups (sulfonic acid group and the like) and tribasic acid groups (phosphoric acid group and the like) other than a carboxy group. Among them, a carboxy group is preferable. R 3 is preferably a group having 9 to 20 carbon atoms which has a carboxy group and an ethylenically unsaturated group. As a specific example of the structure containing the carboxy group which R<3> has, the structure etc. which are represented by following formula 3-20 are mentioned. Among these, it is preferable that it has a structure represented by following
또, R3 이 갖는 에틸렌성 불포화기를 포함하는 구조의 구체예로서, 하기 식 21, 22 로 나타내는 구조 등을 들 수 있다.Moreover, as a specific example of the structure containing the ethylenically unsaturated group which R<3> has, the structure etc. which are represented by following formula 21, 22 are mentioned.
하기 식 3 ∼ 20 으로 나타내는 구조 및 하기 식 21, 22 로 나타내는 구조는 각각 단독으로 결합하고 있어도 되고, R3 의 탄소수가 30 을 초과하지 않으면 2 종 이상이 결합하고 있어도 된다.The structures represented by the following
[화학식 3] [Formula 3]
R3 의 바람직한 구체예로는 하기 구조이다.Preferred examples of R 3 have the following structure.
[화학식 4] [Formula 4]
상기 구조 중, R4 는 치환기로서 식 4 또는 식 11 과 식 21 또는 22 를 갖는 탄소수 1 ∼ 5 의 알킬기이다. 이들 중에서도, 특히 원료의 입수 용이함, 합성상의 반응성의 관점에서, 탄소수 2 ∼ 3 의 알킬기인 것이 바람직하다. 식 4 또는 식 11 과 식 21 또는 22 는, 알킬기의 동일한 탄소에 결합하고 있어도 되고, 상이한 탄소에 결합하고 있어도 된다.In the above structure, R 4 is an alkyl group having 1 to 5 carbon atoms and having Formula 4 or Formula 11 and Formula 21 or 22 as a substituent. Among these, it is preferable that it is a C2-C3 alkyl group especially from a viewpoint of the availability of a raw material and synthetic reactivity. Formula 4 or Formula 11 and Formula 21 or 22 may be couple|bonded with the same carbon of an alkyl group, and may couple|bond with different carbon.
또, 본 발명의 중합체 조성물 (A) 는, 중합체 조성물 (A) 에 포함되는 2 종 이상의 (메트)아크릴산계 중합체 중, 산가가 최대가 되는 (메트)아크릴산계 중합체 (a) 의 산가를 1 로 한 경우에, 0.01 배 ∼ 0.50 배의 산가를 갖는 (메트)아크릴산계 중합체 (b) 를 포함하는 것에 특징이 있다.In the polymer composition (A) of the present invention, the acid value of the (meth)acrylic acid polymer (a) having the largest acid value among two or more types of (meth)acrylic acid polymers contained in the polymer composition (A) is 1 In one case, it is characterized in that the (meth)acrylic acid-based polymer (b) having an acid value of 0.01 to 0.50 is included.
여기서, 본 발명에 있어서의 산가란, JIS K6901 5.3 에 따라 측정된 (메트)아크릴산계 중합체의 산가로서, (메트)아크릴산계 중합체 1 g 중에 포함되는 산성 성분을 중화하는 데에 필요한 수산화칼륨의 mg 수를 나타내는 것으로 한다.Here, the acid value in the present invention is the acid value of the (meth)acrylic acid polymer measured in accordance with JIS K6901 5.3, and mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the (meth)acrylic acid polymer. to indicate a number.
중합체 조성물 (A) 에 포함되는 2 종 이상의 (메트)아크릴산계 중합체 중, 최대 산가를 갖는 (메트)아크릴산계 중합체 (a) 의 산가는, 50 mgKOH/g ∼ 1000 mgKOH/g 인 것이 바람직하고, 100 mgKOH/g ∼ 600 mgKOH/g 인 것이 보다 바람직하다. (메트)아크릴산계 중합체 (a) 의 산가가 상기 범위 내이면, (메트)아크릴산계 중합체 (b) 와의 상용성이 양호하여, 합성 시 또는 감광성 수지 조성물을 조제할 때에 분리되는 일 없이 혼합할 수 있다.Among the two or more types of (meth)acrylic acid-based polymers contained in the polymer composition (A), the (meth)acrylic acid-based polymer (a) having the maximum acid value preferably has an acid value of 50 mgKOH/g to 1000 mgKOH/g, It is more preferable that they are 100 mgKOH/g - 600 mgKOH/g. When the acid value of the (meth)acrylic acid-based polymer (a) is within the above range, compatibility with the (meth)acrylic acid-based polymer (b) is good, and it can be mixed without separation during synthesis or when preparing the photosensitive resin composition. have.
또, 중합체 조성물 (A) 에 포함되는 2 종 이상의 (메트)아크릴산계 중합체 중, 최대 산가를 갖는 (메트)아크릴산계 중합체 (a) 의 중량 평균 분자량 (Mw) 은 1,000 ∼ 10,000 이며, 2,000 ∼ 10,000 인 것이 바람직하다. (메트)아크릴산계 중합체 (a) 의 중량 평균 분자량 (Mw) 이 상기 범위 내이면, (메트)아크릴산계 중합체 (b) 와의 상용성이 양호하여, 합성 시 또는 감광성 수지 조성물을 조제할 때에 분리되는 일 없이 혼합할 수 있다. Moreover, the weight average molecular weight (Mw) of the (meth)acrylic acid type polymer (a) which has the largest acid value among 2 or more types of (meth)acrylic acid type polymers contained in the polymer composition (A) is 1,000-10,000, 2,000-10,000 It is preferable to be When the weight average molecular weight (Mw) of the (meth)acrylic acid-based polymer (a) is within the above range, compatibility with the (meth)acrylic acid-based polymer (b) is good, and is separated during synthesis or when preparing the photosensitive resin composition It can be mixed without work.
여기서, 본 발명에 있어서의 중량 평균 분자량 (Mw) 이란, 겔 퍼미에이션 크로마토그래피 (GPC) 를 사용하여, 하기 조건으로 측정한 표준 폴리스티렌 환산 중량 평균 분자량을 나타내는 것으로 한다.Here, the weight average molecular weight (Mw) in this invention shall show the standard polystyrene conversion weight average molecular weight measured on the following conditions using gel permeation chromatography (GPC).
칼럼 : 쇼덱스 (등록상표) LF-804+LF-804 (쇼와 전공 주식회사 제조) Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.)
칼럼 온도 : 40 ℃Column temperature: 40℃
시료 : (메트)아크릴산계 중합체의 0.2 % 테트라하이드로푸란 용액 Sample: 0.2% tetrahydrofuran solution of (meth)acrylic acid polymer
전개 용매 : 테트라하이드로푸란 Developing solvent: tetrahydrofuran
검출기 : 시차굴절계 (쇼덱스 RI-71S) (쇼와 전공 주식회사 제조) Detector: Differential refractometer (Shodex RI-71S) (manufactured by Showa Denko Co., Ltd.)
유속 : 1 mL/분Flow rate: 1 mL/min
(메트)아크릴산계 중합체 (b) 는, 최대 산가를 갖는 (메트)아크릴산계 중합체 (a) 의 산가를 1 로 한 경우에, 0.01 배 ∼ 0.50 배의 산가를 갖고, 바람직하게는 0.01 배 ∼ 0.30 배의 산가를 갖는다. 0.01 배 ∼ 0.50 배의 산가를 갖는 (메트)아크릴산계 중합체 (b) 를 중합체 조성물 (A) 에 배합하지 않으면, 우수한 내열 황변성, 내용제성 및 알칼리 현상성을 달성할 수 없다. 알칼리 현상성의 관점에서, (메트)아크릴산계 중합체 (b) 는, 상기 범위의 산가를 나타내는 2 종 이상의 (메트)아크릴산계 중합체의 혼합물인 것이 보다 바람직하다.The (meth)acrylic acid-based polymer (b) has an acid value of 0.01 to 0.50 times, preferably 0.01 to 0.30, when the acid value of the (meth)acrylic acid-based polymer (a) having the maximum acid value is 1 It has the acid value of the ship. If the (meth)acrylic acid-based polymer (b) having an acid value of 0.01 to 0.50 times is not added to the polymer composition (A), excellent heat yellowing resistance, solvent resistance and alkali developability cannot be achieved. From the viewpoint of alkali developability, the (meth)acrylic acid-based polymer (b) is more preferably a mixture of two or more (meth)acrylic acid-based polymers exhibiting an acid value within the above range.
또, (메트)아크릴산계 중합체 (b) 의 중량 평균 분자량 (Mw) 은, 적절히 조정하는 것이 가능하지만, (메트)아크릴산계 중합체 (a) 와의 상용성의 관점에서, 1,000 ∼ 10,000 인 것이 바람직하고, 2,000 ∼ 10,000 인 것이 보다 바람직하다.In addition, the weight average molecular weight (Mw) of the (meth)acrylic acid-based polymer (b) can be appropriately adjusted, but from the viewpoint of compatibility with the (meth)acrylic acid-based polymer (a), it is preferably 1,000 to 10,000, It is more preferable that it is 2,000-10,000.
현상성의 관점에서, (메트)아크릴산계 중합체 (a) 와 (메트)아크릴산계 중합체 (b) 는, 상기 식 1 또는 식 2 로 나타내는 동일한 구성 단위를 적어도 1 개 갖는 것이 바람직하다.From the viewpoint of developability, the (meth)acrylic acid polymer (a) and the (meth)acrylic acid polymer (b) preferably have at least one identical structural unit represented by the formula (1) or the formula (2).
또한, 중합체 조성물 (A) 에 있어서, (메트)아크릴산계 중합체 (b) 에 대한(메트)아크릴산계 중합체 (a) 의 질량비 [(a)/(b)] 는 0.01 ∼ 0.50 이며, 0.01 ∼ 0.30 인 것이 바람직하다. 질량비 [(a)/(b)] 가 상기 범위 내이면, 우수한 내열 황변성, 내용제성 및 알칼리 현상성을 달성할 수 있다.Further, in the polymer composition (A), the mass ratio [(a)/(b)] of the (meth)acrylic acid polymer (a) to the (meth)acrylic acid polymer (b) is 0.01 to 0.50, 0.01 to 0.30 It is preferable to be When the mass ratio [(a)/(b)] is within the above range, excellent heat yellowing resistance, solvent resistance and alkali developability can be achieved.
상기 (메트)아크릴산계 중합체 (a) 및 (메트)아크릴산계 중합체 (b) 의 산가는, 각 중합체의 제조에 사용하는 라디칼 중합성 모노머의 양 및 종류를 변경함으로써, 적절히 조정할 수 있다. (메트)아크릴산계 중합체 (a) 및 (메트)아크릴산계 중합체 (b) 의 제조에 사용할 수 있는 라디칼 중합성 모노머로는, 예를 들어, 부타디엔 등의 디엔류 ; 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, n-프로필(메트)아크릴레이트, 이소프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, sec-부틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, tert-부틸(메트)아크릴 레이트, 펜틸(메트)아크릴레이트, 네오펜틸(메트)아크릴레이트, 벤질(메트)아크릴레이트, 이소아밀(메트)아크릴레이트, 헥실(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, 벤질(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 도데실(메트)아크릴레이트, 시클로펜틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 메틸시클로헥실(메트)아크릴레이트, 에틸시클로헥실(메트)아크릴레이트, 1,4-시클로헥산디메탄올모노(메트)아크릴레이트, 로진(메트)아크릴레이트, 노르보르닐(메트)아크릴레이트, 5-메틸노르보르닐(메트)아크릴레이트, 5-에틸노르보르닐(메트)아크릴레이트, 알릴(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 1,1,1-트리플루오로에틸(메트)아크릴레이트, 퍼플루오로에틸(메트)아크릴레이트, 퍼플루오로-n-프로필(메트)아크릴레이트, 퍼플루오로-이소프로필(메트)아크릴레이트, 트리페닐메틸(메트)아크릴레이트, 쿠밀(메트)아크릴레이트, 3-(N,N-디메틸아미노)프로필(메트)아크릴레이트, 글리세롤모노(메트)아크릴레이트, 부탄트리올모노(메트)아크릴레이트, 펜탄트리올모노(메트)아크릴레이트, 디시클로펜테닐(메트)아크릴레이트, 디시클로펜타닐(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 아다만틸(메트)아크릴레이트, 나프탈렌(메트)아크릴레이트, 안트라센(메트)아크릴레이트 등의 (메트)아크릴산에스테르류 ; 노르보르넨(비시클로[2.2.1]헵트-2-엔), 5-메틸비시클로[2.2.1]헵트-2-엔, 5-에틸비시클로[2.2.1]헵트-2-엔, 테트라시클로[4.4.0.12,5.17,10]도데카-3-엔, 8-메틸테트라시클로[4.4.0.12,5.17,10]도데카-3-엔, 8-에틸테트라시클로[4.4.0.12,5.17,10]도데카-3-엔, 디시클로펜타디엔, 트리시클로[5.2.1.02,6]데카-8-엔, 트리시클로[5.2.1.02,6]데카-3-엔, 트리시클로[4.4.0.12,5]운데카-3-엔, 트리시클로[6.2.1.01,8]운데카-9-엔, 트리시클로[6.2.1.01,8]운데카-4-엔, 테트라시클로[4.4.0.12,5.17,10.01,6]도데카-3-엔, 8-메틸테트라시클로[4.4.0.12,5.17,10.01,6]도데카-3-엔, 8-에틸리덴테트라시클로[4.4.0.12,5.17,12]도데카-3-엔, 8-에틸리덴테트라시클로[4.4.0.12,5.17,10.01,6]도데카-3-엔, 펜타시클로[6.5.1.13,6.02,7.09,13]펜타데카-4-엔, 펜타시클로[7.4.0.12,5.19,12.08,13]펜타데카-3-엔, 5-노르보르넨-2-카르복실산, 5-노르보르넨-2,3-디카르복실산, 5-노르보르넨-2,3-디카르복실산 무수물, (메트)아크릴산아미드, (메트)아크릴산 N,N-디메틸아미드, (메트)아크릴산 N,N-디에틸아미드, (메트)아크릴산 N,N-디프로필아미드, (메트)아크릴산 N,N-디-이소프로필아미드, (메트)아크릴산안트라세닐아미드, N-이소프로필(메트)아크릴아미드, (메트)아크릴모르폴린, 다이아세톤(메트)아크릴아미드 등의 (메트)아크릴산아미드 ; (메트)아크릴산아닐리드, (메트)아크릴로일니트릴, 아크롤레인, 염화비닐, 염화비닐리덴, 불화비닐, 불화비닐리덴, N-비닐피롤리돈, 비닐피리딘, 아세트산비닐, 비닐톨루엔 등의 비닐 화합물 ; 스티렌, 스티렌의 α-, o-, m-, p-알킬, 니트로, 시아노, 아미드 유도체 ; 시트라콘산디에틸, 말레산디에틸, 푸마르산디에틸, 이타콘산디에틸 등의 불포화 디카르복실산디에스테르 ; N-페닐말레이미드, N-시클로헥실말레이미드, N-라우릴말레이미드, N-(4-하이드록시페닐)말레이미드 등의 모노말레이미드류 ; 무수 말레산, 무수 이타콘산, 무수 시트라콘산 등의 불포화 다염기산 무수물, 지환형 에테르기를 갖는 글리시딜(메트)아크릴레이트, 3,4-에폭시시클로헥실메틸(메트)아크릴레이트 및 그 락톤 부가물 [예를 들어, 다이셀 화학 공업 (주) 제조 사이클로머 A200, M100], 3,4-에폭시시클로헥실메틸-3',4'-에폭시시클로헥산카르복실레이트의 모노(메트)아크릴산에스테르, 디시클로펜테닐(메트)아크릴레이트의 에폭시화물, 디시클로펜테닐옥시에틸(메트)아크릴레이트의 에폭시화물, (3-에틸옥세탄-3-일)메틸(메트)아크릴레이트, 4-[3-(3-에틸옥세탄-3-일메톡시)프로폭시]스티렌, 4-[6-(3-에틸옥세탄-3-일메톡시)헥실옥시]스티렌, 4-[5-(3-에틸옥세탄-3-일메톡시)펜틸옥시]스티렌, 2-비닐-2-메틸옥세탄, (메트)아크릴산, 크로톤산, 신남산, 비닐술폰산, 2-(메트)아크릴로일옥시에틸숙신산, 2-아크릴로일옥시에틸프탈산, 2-(메트)아크릴로일옥시에틸헥사하이드로프탈산, 2-(메트)아크릴로일옥시에틸애시드포스페이트, 그 외에도 2-이소시아나토에틸(메트)아크릴레이트, (메트)아크릴산 2-(2-비닐옥시에톡시)에틸 등을 들 수 있다.The acid values of the (meth)acrylic acid polymer (a) and the (meth)acrylic acid polymer (b) can be appropriately adjusted by changing the amount and type of the radically polymerizable monomer used for production of each polymer. As a radically polymerizable monomer which can be used for manufacture of a (meth)acrylic acid type polymer (a) and a (meth)acrylic acid type polymer (b), For example, dienes, such as a butadiene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso Butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylic Rate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate , 5-methyl norbornyl (meth) acrylate, 5-ethyl norbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoro Roethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth) acrylic Rate, cumyl (meth) acrylate, 3-(N,N-dimethylamino) propyl (meth) acrylate, glycerol mono (meth) acrylate, butane triol mono (meth) acrylate, pentane triol mono (meth) ) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, naphthalene (meth) acrylate, anthracene ( (meth)acrylic acid esters, such as meth)acrylate; norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, Tetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17 ,10]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]deca-8-ene, tricyclo[5.2.1.02,6]deca-3-ene, tricyclo[4.4. 0.12,5]undeca-3-ene, tricyclo[6.2.1.01,8]undeca-9-ene, tricyclo[6.2.1.01,8]undeca-4-ene, tetracyclo[4.4.0.12, 5.17,10.01,6]dodeca-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,12 ]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadeca-4- N, pentacyclo[7.4.0.12,5.19,12.08,13]pentadeca-3-ene, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5 -norbornene-2,3-dicarboxylic acid anhydride, (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N, N-dipropylamide, (meth)acrylic acid N,N-di-isopropylamide, (meth)acrylic acid anthracenylamide, N-isopropyl (meth)acrylamide, (meth)acrylmorpholine, diacetone (meth) (meth)acrylic acid amides such as acrylamide; (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene, such as vinyl compounds; styrene, α-, o-, m-, p-alkyl, nitro, cyano, and amide derivatives of styrene; Unsaturated dicarboxylic acid diesters, such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconic acid; Monomaleimides, such as N-phenyl maleimide, N-cyclohexyl maleimide, N-lauryl maleimide, and N-(4-hydroxyphenyl) maleimide; Unsaturated polybasic acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride, glycidyl (meth) acrylate having an alicyclic ether group, 3,4-epoxycyclohexylmethyl (meth) acrylate, and lactone adducts thereof [For example, Daicel Chemical Industry Co., Ltd. cyclomer A200, M100], mono (meth) acrylic acid ester of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, dish Epoxy product of clopentenyl (meth) acrylate, epoxide of dicyclopentenyloxyethyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, 4-[3- (3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethylox) Cetan-3-ylmethoxy)pentyloxy]styrene, 2-vinyl-2-methyloxetane, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2- Acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl acid phosphate, in addition to 2-isocyanatoethyl (meth) acrylate, (meth) ) Acrylic acid 2-(2-vinyloxyethoxy)ethyl, etc. are mentioned.
(메트)아크릴산계 중합체 (a) 및 (메트)아크릴산계 중합체 (b) 는, 상기한 라디칼 중합성 모노머 중에서, 상기 식 1 또는 식 2 로 나타내는 구성 단위를 도입할 수 있는 라디칼 중합성 모노머를 사용하여 중합 반응을 실시함으로써 얻을 수 있다. 구체적으로는, 상기 식 1 로 나타내는 구성 단위를 갖는 (메트)아크릴산계 중합체는, (메트)아크릴산 및 필요에 따라 다른 라디칼 중합성 모노머를 원하는 바에 따라 용제에 용해한 후, 그 용액에 라디칼 중합 개시제를 첨가하고, 50 ℃ ∼ 120 ℃ 에서 1 시간 ∼ 20 시간에 걸쳐 적절히 중합 반응을 실시함으로써 얻을 수 있다. 또, 상기 식 2 로 나타내는 구성 단위를 갖는 (메트)아크릴산계 중합체는, 에폭시기, 옥세타닐기 등, 카르복시기와 반응하는 기를 갖는 라디칼 중합성 모노머 및 필요에 따라 다른 라디칼 중합성 모노머를 원하는 바에 따라 용제에 용해한 후, 그 용액에 라디칼 중합 개시제를 첨가하고, 50 ℃ ∼ 120 ℃ 에서 1 시간 ∼ 20 시간에 걸쳐 적절히 중합 반응을 실시한 후, 얻어진 중합체의 일부에 카르복시기를 갖는 라디칼 중합성 모노머를 부가시키고, 개환해 생성되는 하이드록실기의 일부에 다염기산 무수물을 부가시킴으로써 얻을 수 있다. 얻어진 (메트)아크릴산계 중합체는, 필요에 따라 정제하고, 중합체 성분을 단리하여, 산가를 측정하고, 산가가 상이한 2 종 이상의 (메트)아크릴산계 중합체를 소정 산가의 비 및 질량비가 되도록 배합하여 중합체 조성물 (A) 로 한다.The (meth)acrylic acid-based polymer (a) and the (meth)acrylic acid-based polymer (b) use, among the above-described radically polymerizable monomers, a radically polymerizable monomer capable of introducing a structural unit represented by
또한, 본 발명의 중합체 조성물 (A) 는, 상기 산가의 범위 이외의 (메트)아크릴산계 중합체 (예를 들어, 최대 산가를 갖는 (메트)아크릴산계 중합체 (a) 의 산가를 1 로 한 경우에, 0.01 배 미만의 산가를 갖는 (메트)아크릴산계 중합체 또는 0.50 배 초과 ∼ 1 배 미만의 산가를 갖는 (메트)아크릴산계 중합체) 또는 (메트)아크릴산계 중합체 이외의 중합체를, 본 발명에 의한 효과를 저해하지 않는 정도로 포함해도 된다. 또, 중합체 조성물 (A) 에 포함되는 중합체의 평균 산가는, 현상성의 관점에서, 50 mgKOH/g ∼ 150 mgKOH/g 의 범위인 것이 바람직하고, 80 mgKOH/g ∼ 120 mgKOH/g 의 범위인 것이 보다 바람직하다. 또한, 중합체 조성물 (A) 에 포함되는 중합체의 평균 산가는, 이하의 식에 기초하여 계산되는 계산값으로 한다.In addition, the polymer composition (A) of the present invention is a (meth)acrylic acid-based polymer outside the above acid value range (for example, when the (meth)acrylic acid-based polymer (a) having the maximum acid value has an acid value of 1) , a (meth)acrylic acid-based polymer having an acid value of less than 0.01 times or a (meth)acrylic acid-based polymer having an acid value of more than 0.50 to less than 1 times) or a polymer other than a (meth)acrylic acid-based polymer according to the present invention may be included to the extent that it does not impair Further, the average acid value of the polymer contained in the polymer composition (A) is preferably in the range of 50 mgKOH/g to 150 mgKOH/g, and in the range of 80 mgKOH/g to 120 mgKOH/g in terms of developability. more preferably. In addition, let the average acid value of the polymer contained in a polymer composition (A) be a calculated value calculated based on the following formula|equation.
평균 산가 = (중합체 1 의 산가 × 중합체 1 의 함유량 + 중합체 2 의 산가 × 중합체 2 의 함유량 + 중합체 3 의 산가 × 중합체 3 의 함유량 + ···)/중합체 조성물 (A) 에 포함되는 중합체의 합계 질량 Average acid value = (acid value of polymer 1 x content of
라디칼 중합 개시제로는, 통상, 열에 의해 열 라디칼을 발생하는 열 라디칼 중합 개시제가 사용되고, 유기 과산화물계 라디칼 중합 개시제, 아조계 라디칼 중합 개시제 모두 사용할 수 있다. 유기 과산화물계 라디칼 중합 개시제로는, 예를 들어, 케톤퍼옥사이드, 퍼옥시케탈, 하이드로퍼옥사이드, 디알킬퍼옥사이드, 디아실퍼옥사이드, 퍼옥시에스테르, 퍼옥시카보네이트, 퍼옥시디카보네이트 등이 바람직하고, 그 중에서도 하이드로퍼옥사이드, 디알킬퍼옥사이드, 디아실퍼옥사이드, 퍼옥시에스테르 (예를 들어, tert-부틸퍼옥시-2-에틸헥사노에이트) 가 특히 바람직하다. 아조계 라디칼 중합 개시제로는, 예를 들어, 2,2'-아조비스이소부티로니트릴, 2,2'-아조비스(2-메틸부티로니트릴), 디메틸-2,2'-아조비스(2-메틸프로피오네이트) 등이 바람직하다. 이들 라디칼 중합 개시제는, 단독으로 사용해도 되고, 또는 2 종 이상을 사용해도 된다.As the radical polymerization initiator, a thermal radical polymerization initiator that generates thermal radicals by heat is usually used, and both an organic peroxide radical polymerization initiator and an azo radical polymerization initiator can be used. As the organic peroxide radical polymerization initiator, for example, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxycarbonate, peroxydicarbonate, etc. are preferable, Among them, hydroperoxide, dialkylperoxide, diacylperoxide, and peroxyester (eg, tert-butylperoxy-2-ethylhexanoate) are particularly preferable. Examples of the azo radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobis( 2-methylpropionate) and the like. These radical polymerization initiators may be used independently and may use 2 or more types.
본 발명에 사용되는 라디칼 중합 개시제의 10 시간 반감기 온도는, 50 ℃ ∼ 120 ℃ 가 바람직하고, 50 ℃ ∼ 90 ℃ 가 보다 바람직하다. 10 시간 반감기 온도가 50 ℃ ∼ 120 ℃ 인 라디칼 중합 개시제를 사용함으로써, 라디칼 중합 반응이 충분히 진행되고, 얻어지는 (메트)아크릴산계 중합체의 내열 황변성이 향상되어, 안정적인 품질의 (메트)아크릴산계 중합체가 얻어진다.50 degreeC - 120 degreeC are preferable and, as for the 10-hour half-life temperature of the radical polymerization initiator used for this invention, 50 degreeC - 90 degreeC are more preferable. By using a radical polymerization initiator having a 10-hour half-life temperature of 50° C. to 120° C., the radical polymerization reaction proceeds sufficiently, and the heat yellowing resistance of the obtained (meth)acrylic acid-based polymer is improved, and the (meth)acrylic acid-based polymer of stable quality is obtained
라디칼 중합 개시제의 사용량은 특별히 제한되지 않지만, 라디칼 중합성 모노머 100 질량부에 대해, 0.5 질량부 ∼ 100 질량부가 바람직하고, 1 질량부 ∼ 50 질량부가 보다 바람직하다. 사용량을 0.5 질량부 ∼ 100 질량부로 함으로써, 보존 시에 라디칼 중합 개시제의 분해에서 기인하는, (메트)아크릴산계 중합체의 열화를 억제할 수 있다.Although the usage-amount in particular of a radical polymerization initiator is not restrict|limited, 0.5 mass part - 100 mass parts are preferable with respect to 100 mass parts of radically polymerizable monomers, and 1 mass part - 50 mass parts are more preferable. By the usage-amount being 0.5 mass part - 100 mass parts, deterioration of the (meth)acrylic-acid type polymer resulting from decomposition|disassembly of a radical polymerization initiator at the time of storage can be suppressed.
라디칼 중합성 모노머의 부가 및 다염기산 무수물의 부가에서는, 부가 반응 촉매를 필요에 따라 사용해도 된다. 부가 반응 촉매로는, 예를 들어, 트리에틸아민, 벤질디메틸아민, 트리에틸렌디아민과 같은 제 3 급 아민, 트리에틸벤질암모늄클로라이드와 같은 제 4 급 암모늄염, 트리페닐포스핀, 트리파라톨릴포스핀, 트리스(2,6-디메톡시페닐)포스핀과 같은 인 화합물, 크롬의 킬레이트 화합물 등을 들 수 있다. 이들 부가 반응 촉매는, 단독으로 사용해도 되고, 또는 2 종 이상을 사용해도 된다. 부가 반응 촉매의 사용량은, 특별히 제한되지 않지만, 라디칼 중합성 모노머 100 질량부에 대해, 0.1 질량부 ∼ 1.0 질량부인 것이 바람직하고, 0.2 질량부 ∼ 0.6 질량부인 것이 보다 바람직하다. 0.1 질량부 이상이면, 충분한 반응률이 얻어지므로 바람직하다. 1.0 질량부 이하이면, 촉매에 의한 착색의 영향을 억제할 수 있어 바람직하다.In addition of a radically polymerizable monomer and addition of a polybasic acid anhydride, you may use an addition reaction catalyst as needed. Examples of the addition reaction catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and triethylenediamine, quaternary ammonium salts such as triethylbenzylammonium chloride, triphenylphosphine, and triparatolylphosphine. , a phosphorus compound such as tris(2,6-dimethoxyphenyl)phosphine, a chelate compound of chromium, and the like. These addition reaction catalysts may be used independently and may use 2 or more types. Although the usage-amount in particular of an addition reaction catalyst is not restrict|limited, It is preferable that they are 0.1 mass part - 1.0 mass part with respect to 100 mass parts of radically polymerizable monomers, It is more preferable that they are 0.2 mass part - 0.6 mass part. If it is 0.1 mass part or more, since sufficient reaction rate is obtained, it is preferable. If it is 1.0 mass part or less, the influence of the coloring by a catalyst can be suppressed, and it is preferable.
라디칼 중합성 모노머의 부가 및 다염기산 무수물의 부가에서는, 겔화 방지를 위해서 중합 금지제를 사용해도 된다. 중합 금지제로는, 예를 들어, 하이드로퀴논, 메토퀴논, 메틸하이드로퀴논, 하이드로퀴논모노메틸에테르, 부틸하이드록시톨루엔 등을 들 수 있다. 이들 중합 금지제는, 단독으로 사용해도 되고, 또는 2 종 이상을 사용해도 된다. 중합 금지제의 사용량은, 특별히 제한되지 않지만, 라디칼 중합성 모노머 100 질량부에 대해, 0.1 질량부 ∼ 1.0 질량부인 것이 바람직하고, 0.2 질량부 ∼ 0.6 질량부인 것이 보다 바람직하다. 중합 금지제의 사용량이, 0.1 질량부 이상이면, 겔화를 억제할 수 있어 바람직하다. 1.0 질량부 이하이면, 감광성 수지 조성물에 사용한 경우에 경화를 저해하는 일도 없어 바람직하다.In addition of a radically polymerizable monomer and addition of a polybasic acid anhydride, you may use a polymerization inhibitor for gelatinization prevention. As a polymerization inhibitor, hydroquinone, metoquinone, methyl hydroquinone, hydroquinone monomethyl ether, butylhydroxytoluene, etc. are mentioned, for example. These polymerization inhibitors may be used independently and may use 2 or more types. Although the usage-amount in particular of a polymerization inhibitor is not restrict|limited, It is preferable that they are 0.1 mass parts - 1.0 mass parts with respect to 100 mass parts of radically polymerizable monomers, It is more preferable that they are 0.2 mass parts - 0.6 mass parts. Gelation can be suppressed as the usage-amount of a polymerization inhibitor is 0.1 mass part or more, and it is preferable. If it is 1.0 mass part or less, when it uses for the photosensitive resin composition, hardening is not impaired, and it is preferable.
중합에 사용하는 용제로는, 특별히 한정되지 않지만, 얻어지는 (메트)아크릴산계 중합체의 용해성의 관점에서, 글리콜에테르 용제가 바람직하다. 구체적으로는, 에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노메틸에테르, 폴리에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노이소프로필에테르, 디에틸렌글리콜모노부틸에테르, 에틸렌글리콜모노이소부틸에테르, 에틸렌글리콜모노헥실에테르, 에틸렌글리콜모노 2-에틸헥실에테르, 에틸렌글리콜모노페닐에테르, 에틸렌글리콜모노벤질에테르, 에틸렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노페닐에테르, 프로필렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르, 디에틸렌글리콜디부틸에테르 및 디프로필렌글리콜디메틸에테르 등을 들 수 있다. 이들 용제는 단독으로 사용해도 되고, 또는 2 종 이상을 사용해도 된다. 이들 중에서도, 입수 용이성 및 반응성의 관점에서, 프로필렌글리콜모노메틸에테르 및 프로필렌글리콜모노메틸에테르아세테이트가 바람직하다.Although it does not specifically limit as a solvent used for superposition|polymerization, From a solubility viewpoint of the (meth)acrylic acid type polymer obtained, a glycol ether solvent is preferable. Specifically, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, Ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl Ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, etc. are mentioned. These solvents may be used independently and may use 2 or more types. Among these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable from an availability and a reactive viewpoint.
용제의 사용량은, 특별히 한정되지 않지만, 라디칼 중합성 모노머 100 질량부에 대해, 바람직하게는 30 질량부 ∼ 1,000 질량부, 보다 바람직하게는 50 질량부 ∼ 800 질량부이다. 특히, 용제의 사용량을 1,000 질량부 이하로 함으로써, 연쇄 이동 작용에 의해 (메트)아크릴산계 중합체의 분자량의 저하를 억제하고, 또한 (메트)아크릴산계 중합체의 점도를 적절한 범위로 제어할 수 있다. 또, 용제의 사용량을 30 질량부 이상으로 함으로써, 이상한 중합 반응을 방지하여, 중합 반응을 안정적으로 실시할 수 있음과 함께, (메트)아크릴산계 중합체의 착색이나 겔화를 방지할 수도 있다.Although the usage-amount of a solvent is not specifically limited, Preferably it is 30 mass parts - 1,000 mass parts with respect to 100 mass parts of radically polymerizable monomers, More preferably, they are 50 mass parts - 800 mass parts. In particular, when the amount of the solvent used is 1,000 parts by mass or less, a decrease in the molecular weight of the (meth)acrylic acid polymer by chain transfer action can be suppressed, and the viscosity of the (meth)acrylic acid polymer can be controlled within an appropriate range. Moreover, by making the usage-amount of a solvent into 30 mass parts or more, while being able to prevent an abnormal polymerization reaction and a polymerization reaction can be performed stably, coloring and gelatinization of a (meth)acrylic-acid type polymer can also be prevented.
라디칼 중합성 모노머를 미리 용제에 용해하여 첨가하는 경우에는, 라디칼 중합성 모노머 100 질량부에 대해, 용제를 바람직하게는 1 질량부 ∼ 500 질량부, 보다 바람직하게는 10 질량부 ∼ 300 질량부로 혼합하여, 반응 용기에 첨가한다. 또, 라디칼 중합 개시제를 미리 용제에 용해하여 첨가하는 경우에는, 라디칼 중합 개시제 100 질량부에 대해, 용제를 바람직하게는 100 질량부 ∼ 10000 질량부, 보다 바람직하게는 150 질량부 ∼ 5000 질량부로 혼합하여, 반응 용기에 첨가한다. 또한, 라디칼 중합성 모노머와 라디칼 중합 개시제를 혼합하여 반응 용기에 첨가하는 경우에는, 당해 혼합물 100 질량부에 대해, 용제를 바람직하게는 1 질량부 ∼ 500 질량부, 보다 바람직하게는 10 질량부 ∼ 300 질량부로 혼합하여, 반응 용기에 첨가한다.When adding a radically polymerizable monomer in advance melt|dissolving in a solvent, with respect to 100 mass parts of radically polymerizable monomers, Preferably the solvent is 1 mass part - 500 mass parts, More preferably, it mixes in 10 mass parts - 300 mass parts and added to the reaction vessel. In addition, when adding a radical polymerization initiator by dissolving it in a solvent beforehand, with respect to 100 mass parts of radical polymerization initiators, Preferably a solvent is 100 mass parts - 10000 mass parts, More preferably, it mixes in 150 mass parts - 5000 mass parts. and added to the reaction vessel. In addition, when mixing a radically polymerizable monomer and a radical polymerization initiator and adding it to a reaction container, with respect to 100 mass parts of the said mixture, Preferably 1 mass part - 500 mass parts of a solvent, More preferably, 10 mass parts - It mixes in 300 mass parts and adds to the reaction vessel.
라디칼 중합성 모노머 및 라디칼 중합 개시제를 반응 용기에 첨가하는 방법은 특별히 한정되지 않는다. 첨가량, 첨가 속도나 첨가 시간을 제어하는 것이 용이한 점 등에서, 이들을 적하하여 반응 용기에 첨가하는 것이 바람직하다. 또, 이들을 혼합하여 혼합물로서 첨가해도 되고, 따로따로 첨가해도 된다. The method of adding a radically polymerizable monomer and a radical polymerization initiator to a reaction container is not specifically limited. It is preferable to add these to a reaction container by dripping these from the point which it is easy to control the addition amount, addition rate, and addition time, etc. Moreover, these may be mixed and added as a mixture, and may be added separately.
본 발명에서 사용하는 반응 용기는, 공업적으로 라디칼 중합성 모노머를 중합시키기 위해서 사용하는 반응 용기이면 특별히 한정되지 않는다. 예를 들어, 혼합 기능, 온도 조절 기능을 구비하고, 원료의 공급과 반응액의 취출을 실시할 수 있는 공급구와 취출구를 갖는 반응 용기를 들 수 있다.The reaction container used by this invention will not be specifically limited if it is a reaction container used in order to polymerize a radically polymerizable monomer industrially. For example, a reaction vessel having a mixing function and a temperature control function and having a supply port and an outlet port capable of supplying a raw material and taking out a reaction solution is mentioned.
라디칼 중합성 모노머의 적하 시간은 특별히 제한되지 않지만, 바람직하게는 30 분 ∼ 300 분, 보다 바람직하게는 60 분 ∼ 250 분에 걸쳐 첨가한다. 라디칼 중합 개시제의 적하 시간도 동일하게 특별히 제한되지 않지만, 바람직하게는 30 분 ∼ 300 분, 보다 바람직하게는 60 분 ∼ 250 분에 걸쳐 첨가한다. 또한, 작업 효율의 관점에서, 라디칼 중합성 모노머와 라디칼 중합 개시제의 적하 시간이 동일하게 되도록 조정하는 것이 바람직하다.Although the dripping time in particular of a radically polymerizable monomer is not restrict|limited, Preferably it is 30 minutes - 300 minutes, More preferably, it adds over 60 minutes - 250 minutes. Although the dripping time in particular of a radical polymerization initiator is not restrict|limited similarly, either, Preferably it is 30 minutes - 300 minutes, More preferably, it adds over 60 minutes - 250 minutes. Moreover, it is preferable to adjust so that the dripping time of a radically polymerizable monomer and a radical polymerization initiator may become the same from a viewpoint of work efficiency.
또한, 라디칼 중합성 모노머 및 라디칼 중합 개시제의 혼합물을 반응 용기에 적하하는 경우도 첨가 시간은 특별히 제한되지 않지만, 반응 용기에 바람직하게는 30 분 ∼ 300 분, 보다 바람직하게는 60 분 ∼ 250 분에 걸쳐 첨가한다.In addition, when the mixture of the radically polymerizable monomer and the radical polymerization initiator is added dropwise to the reaction vessel, the addition time is not particularly limited, but preferably 30 minutes to 300 minutes, more preferably 60 minutes to 250 minutes to the reaction vessel. added over
라디칼 중합성 모노머를 용제에 용해하여 적하에 의해 반응 용기에 첨가하는 경우, 적하 속도는 특별히 제한되지 않지만, 라디칼 중합성 모노머 및 용제의 총량을 100 ml 로 한 경우, 바람직하게는 0.1 ml/분 ∼ 5 ml/분, 보다 바람직하게는 0.2 ml/분 ∼ 4 ml/분이다. 또, 라디칼 중합 개시제를 용제에 용해하여 적하에 의해 반응 용기에 첨가하는 경우, 그 적하 속도는, 라디칼 중합 개시제 및 용제의 총량을 100 ml 로 한 경우, 바람직하게는 0.1 ml/분 ∼ 5 ml/분, 보다 바람직하게는 0.2 ml/분 ∼ 4 ml/분이다. 또한, 라디칼 중합성 모노머 및 라디칼 중합 개시제를 혼합물로 용제에 용해하여 반응 용기에 첨가할 때의 적하 속도는, 라디칼 중합성 모노머, 라디칼 중합 개시제 및 용제의 총량을 100 ml 로 한 경우, 통상, 0.1 ml/분 ∼ 5 ml/분, 바람직하게는 0.2 ml/분 ∼ 4 ml/분이다.When the radical polymerizable monomer is dissolved in a solvent and added to the reaction vessel by dropwise, the dropping rate is not particularly limited, but when the total amount of the radical polymerizable monomer and the solvent is 100 ml, preferably 0.1 ml/min to 5 ml/min, more preferably 0.2 ml/min to 4 ml/min. Moreover, when the radical polymerization initiator is dissolved in a solvent and added to the reaction vessel by dripping, the dropping rate is preferably 0.1 ml/min to 5 ml/ when the total amount of the radical polymerization initiator and the solvent is 100 ml. min, more preferably 0.2 ml/min to 4 ml/min. In addition, when the radical polymerizable monomer and the radical polymerization initiator are dissolved in a solvent as a mixture and added to the reaction vessel, the dropping rate is usually 0.1 when the total amount of the radical polymerizable monomer, the radical polymerization initiator and the solvent is 100 ml. ml/min to 5 ml/min, preferably 0.2 ml/min to 4 ml/min.
<감광성 수지 조성물> <Photosensitive resin composition>
본 발명에 있어서는, 상기 서술한 중합체 조성물 (A), 용제 (B), 반응성 희석제 (C) 및 광 중합 개시제 (D) 를 혼합하여 감광성 수지 조성물로 할 수 있다.In this invention, the polymer composition (A) mentioned above, a solvent (B), a reactive diluent (C), and a photoinitiator (D) can be mixed and it can be set as the photosensitive resin composition.
감광성 수지 조성물에 있어서의 중합체 조성물 (A) 의 함유량은, 당해 감광성 수지 조성물 중의 용제를 제외한 성분의 총합을 100 질량부로 했을 때에, 바람직하게는 5 질량부 ∼ 85 질량부, 보다 바람직하게는 9 질량부 ∼ 74 질량부, 더욱 바람직하게는 14 질량부 ∼ 64 질량부이다. When content of the polymer composition (A) in the photosensitive resin composition makes the total of components except the solvent in the said photosensitive resin composition 100 mass parts, Preferably it is 5 mass parts - 85 mass parts, More preferably, 9 mass parts It is a part - 74 mass parts, More preferably, they are 14 mass parts - 64 mass parts.
용제 (B) 는, (메트)아크릴산계 중합체와 반응하지 않는 불활성인 용제 (B) 이면 특별히 한정되지 않는다.A solvent (B) will not be specifically limited if it is an inactive solvent (B) which does not react with a (meth)acrylic-acid type polymer.
용제 (B) 로는, 상기 서술한 바와 같은 (메트)아크릴산계 중합체를 제조할 때에 사용한 용제와 동일한 것을 사용할 수 있고, (메트)아크릴산계 중합체의 제조 후에 포함되어 있는 용제를 그대로 사용할 수도 있고, 추가로 첨가할 수도 있다. 또, 그 밖의 성분을 첨가할 때에, 거기에 공존하고 있는 것이어도 된다. 구체적으로는, 용제 (B) 의 예로서, 프로필렌글리콜모노메틸에테르아세테이트, 디프로필렌글리콜모노메틸에테르아세테이트, 아세트산에틸, 아세트산부틸, 아세트산이소프로필, 프로필렌글리콜모노메틸에테르, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥산온, 에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜에틸에테르아세테이트 등을 들 수 있다. 이들 용제 (B) 는, 단독으로 사용해도 되고, 또는 2 종 이상을 사용해도 된다. 또, 이들 중에서도, (메트)아크릴산계 중합체를 제조할 때에 있어서 사용되는 프로필렌글리콜모노메틸에테르아세테이트 등의 글리콜에테르 용제가 바람직하다.As the solvent (B), the same solvent as used for producing the (meth)acrylic acid polymer as described above can be used, and the solvent included after the production of the (meth)acrylic acid polymer can be used as it is, and further may be added as Moreover, when adding another component, it may be coexisting there. Specifically, as an example of the solvent (B), propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl Ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, etc. are mentioned. These solvents (B) may be used independently and may use 2 or more types. Moreover, among these, glycol ether solvents, such as the propylene glycol monomethyl ether acetate used when manufacturing a (meth)acrylic acid type polymer, are preferable.
감광성 수지 조성물에 있어서의 용제 (B) 의 함유량은, 당해 감광성 수지 조성물 중의 용제 (B) 를 제외한 성분의 총합을 100 질량부로 하면, 일반적으로 30 질량부 ∼ 1,000 질량부, 바람직하게는 50 질량부 ∼ 800 질량부이며, 보다 바람직하게는 100 질량부 ∼ 700 질량부이다. 이 범위의 함유량이면, 적절한 점도를 갖는 감광성 수지 조성물이 된다.When content of the solvent (B) in the photosensitive resin composition makes the total of the components except the solvent (B) in the said photosensitive resin composition 100 mass parts, it is 30 mass parts - 1,000 mass parts normally, Preferably it is 50 mass parts - 800 mass parts, More preferably, they are 100 mass parts - 700 mass parts. If it is content in this range, it will become the photosensitive resin composition which has an appropriate viscosity.
반응성 희석제 (C) 는, 분자 내에 중합성 관능기로서 적어도 하나의 중합 가능한 에틸렌성 불포화기를 갖는 화합물이다. 이와 같은 반응성 희석제 (C) 는, 이것을 중합체 조성물 (A) 와 병용함으로써, 점도를 조정하거나, 경화물의 강도나 기재에 대한 밀착성을 향상시킬 수 있다.A reactive diluent (C) is a compound which has at least 1 polymerizable ethylenically unsaturated group as a polymerizable functional group in a molecule|numerator. By using this reactive diluent (C) together with a polymer composition (A), a viscosity can be adjusted or it can improve the intensity|strength of hardened|cured material, and adhesiveness to a base material.
반응성 희석제 (C) 로는 특별히 한정되지 않지만, 예를 들어, 스티렌, α-메틸스티렌, α-클로로메틸스티렌, 비닐톨루엔, 디비닐벤젠, 디알릴프탈레이트, 디알릴벤젠포스포네이트 등의 방향족 비닐계 모노머류 ; 아세트산비닐, 아디프산비닐 등의 폴리카르복실산 모노머류 ; 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, 부틸(메트)아크릴레이트, β-하이드록시에틸(메트)아크릴레이트, 하이드록시프로필(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 프로필렌글리콜디(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 트리메틸올프로판디(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트, 트리스(하이드록시에틸)이소시아누레이트의 트리(메트)아크릴레이트 등의 (메트)아크릴계 모노머 ; 트리알릴시아누레이트 등을 들 수 있다. 이들 반응성 희석제 (C) 는, 단독으로 사용해도 되고, 또는 2 종 이상을 사용해도 된다. Although it does not specifically limit as a reactive diluent (C), For example, Aromatic vinyl types, such as styrene, (alpha)-methylstyrene, (alpha)-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzenephosphonate. monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylol propane di (meth) acrylate, trimethylol propane tri ( (meth)acrylic monomers such as tri(meth)acrylate of meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate ; triallyl cyanurate etc. are mentioned. These reactive diluents (C) may be used independently and may use 2 or more types.
감광성 수지 조성물에 있어서의 반응성 희석제 (C) 의 함유량은, 당해 감광성 수지 조성물 중의 용제 (B) 를 제외한 성분의 총합을 100 질량부로 하면, 바람직하게는 10 질량부 ∼ 90 질량부, 보다 바람직하게는 20 질량부 ∼ 80 질량부이며, 더욱 바람직하게는 25 질량부 ∼ 70 질량부이다. 이 범위의 함유량이면, 적절한 점도를 갖는 감광성 수지 조성물이 되고, 감광성 수지 조성물은 적절한 광 경화성을 갖는다.When content of the reactive diluent (C) in the photosensitive resin composition makes the total of components except the solvent (B) in the said photosensitive resin composition 100 mass parts, Preferably it is 10 mass parts - 90 mass parts, More preferably They are 20 mass parts - 80 mass parts, More preferably, they are 25 mass parts - 70 mass parts. If it is content in this range, it becomes the photosensitive resin composition which has an appropriate viscosity, and the photosensitive resin composition has suitable photocurability.
광 중합 개시제 (D) 로는, 특별히 한정되지 않지만, 예를 들어, 벤조인, 벤조인메틸에테르, 벤조인에틸에테르 등의 벤조인과 그 알킬에테르류 ; 아세토페논, 2,2-디메톡시-2-페닐아세토페논, 1,1-디클로로아세토페논, 4-(1-t-부틸디옥시-1-메틸에틸)아세토페논 등의 아세토페논류 ; 2-메틸안트라퀴논, 2-아밀안트라퀴논, 2-t-부틸안트라퀴논, 1-클로로안트라퀴논 등의 안트라퀴논류 ; 2,4-디메틸티오크산톤, 2,4-디이소프로필티오크산톤, 2-클로로티오크산톤 등의 티오크산톤류 ; 아세토페논디메틸케탈, 벤질디메틸케탈 등의 케탈류 ; 벤조페논, 4-(1-t-부틸디옥시-1-메틸에틸)벤조페논, 3,3',4,4'-테트라키스(t-부틸디옥시카르보닐)벤조페논 등의 벤조페논류 ; 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노-프로판-1-온 ; 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)부탄온-1 ; 아실포스핀옥사이드류 ; 및 크산톤류 등을 들 수 있다. 이들 광 중합 개시제 (D) 는, 단독으로 사용해도 되고, 또는 2 종 이상을 사용해도 된다.Although it does not specifically limit as a photoinitiator (D), For example, Benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and its alkyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone such as 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone ; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; Acyl phosphine oxides; and xanthone. These photoinitiators (D) may be used independently and may use 2 or more types.
감광성 수지 조성물에 있어서의 광 중합 개시제 (D) 의 함유량은, 당해 감광성 수지 조성물 중의 용제 (B) 를 제외한 성분의 총합을 100 질량부로 했을 때에, 바람직하게는 0.1 질량부 ∼ 30 질량부, 보다 바람직하게는 0.5 질량부 ∼ 20 질량부, 더욱 바람직하게는 1 질량부 ∼ 15 질량부이다. 광 중합 개시제 (D) 의 함유량이 상기 범위 내이면, 감광성 수지 조성물의 광 경화성이 보다 적절해진다.When content of the photoinitiator (D) in the photosensitive resin composition makes the total of the components except the solvent (B) in the said photosensitive resin composition 100 mass parts, Preferably it is 0.1 mass part - 30 mass parts, More preferably Preferably it is 0.5 mass part - 20 mass parts, More preferably, they are 1 mass part - 15 mass parts. When content of a photoinitiator (D) is in the said range, the photocurability of the photosensitive resin composition becomes more suitable.
본 발명의 감광성 수지 조성물에, 착색제 (E) 를 추가로 배합함으로써, 컬러 필터용의 감광성 수지 조성물로 할 수 있다. 착색제 (E) 는, 용제에 용해 또는 분산되는 것이면 특별히 한정되지 않고, 예를 들어, 염료나 안료 등을 들 수 있다.By further mix|blending a coloring agent (E) with the photosensitive resin composition of this invention, it can be set as the photosensitive resin composition for color filters. A coloring agent (E) will not be specifically limited if it melt|dissolves or disperse|distributes to a solvent, For example, dye, a pigment, etc. are mentioned.
특히, 종래의 감광성 수지 조성물에서는, 염료를 사용하면 정밀도가 높은 착색 패턴을 얻을 수 있었지만, 안료를 사용한 경우에 비해 착색 패턴의 내열 황변성이 낮아진다는 문제가 있었다. 이에 대하여, 본 발명의 감광성 수지 조성물에서는, 염료를 사용하여도 내열 황변성이 우수한 착색 패턴을 얻을 수 있다. In particular, in the conventional photosensitive resin composition, when dye was used, although the coloring pattern with high precision was obtained, there existed a problem that the heat-resistant yellowing property of a coloring pattern became low compared with the case where a pigment was used. On the other hand, in the photosensitive resin composition of this invention, even if it uses dye, the coloring pattern excellent in heat-resistant yellowing property can be obtained.
염료로는, 용제나 알칼리 현상액에 대한 용해성, 감광성 수지 조성물 중의 다른 성분과의 상호 작용, 내열성 등의 관점에서, 카르복실산 등의 산성기를 갖는 산성 염료, 산성 염료의 질소 화합물과의 염, 산성 염료의 술폰아미드체 등을 사용하는 것이 바람직하다. 이와 같은 염료의 예로는, acid alizarin violet N ; acid black 1, 2, 24, 48 ; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147 ; solvent blue 38, 44 ; acid chrome violet K ; acid Fuchsin ; acid green 1, 3, 5, 25, 27, 50 ; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95 ; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274 ; acid violet 6B, 7, 9, 17, 19 ; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116 ; food yellow 3 ; solvent yellow 82 및 이들의 유도체 등을 들 수 있다. 이들 중에서도, 아조계, 크산텐계, 안트라퀴논계 혹은 프탈로시아닌계의 산성 염료가 바람직하다. 이들 염료는, 목적으로 하는 화소의 색에 따라, 단독으로 사용해도 되고, 또는 2 종 이상을 사용해도 된다.Examples of the dye include an acid dye having an acid group such as carboxylic acid from the viewpoint of solubility in a solvent or alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., a salt of an acid dye with a nitrogen compound, acid It is preferable to use the sulfonamide form of a dye, etc. Examples of such a dye include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue 38, 44; acid chrome violet K ; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50 ; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95 ; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19 ; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 ; solvent yellow 82 and derivatives thereof. Among these, the acid dye of an azo type, a xanthene type, an anthraquinone type, or a phthalocyanine type is preferable. These dyes may be used independently, or 2 or more types may be used according to the color of the pixel made into object.
안료의 예로는, C. I. 피그먼트 옐로우 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 등의 황색 안료 ; C. I. 피그먼트 오렌지 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 등의 등색 안료 ; C. I. 피그먼트 레드 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 등의 적색 안료 ; C. I. 피그먼트 블루 15, 15 : 3, 15 : 4, 15 : 6, 60 등의 청색 안료 ; C. I. 피그먼트 바이올렛 1, 19, 23, 29, 32, 36, 38 등의 바이올렛색 안료 ; C. I. 피그먼트 그린 7, 36, 58 등의 녹색 안료 ; C. I. 피그먼트 브라운 23, 25 등의 갈색 안료 ; C. I. 피그먼트 블랙 1, 7, 카본 블랙, 티탄 블랙, 산화철 등의 흑색 안료 등을 들 수 있다. 이들 안료는, 목적으로 하는 화소의 색에 따라, 단독으로 사용해도 되고, 또는 2 종 이상을 사용해도 된다. Examples of the pigment include
또한, 목적으로 하는 화소의 색에 따라, 상기 염료 및 안료를 조합하여 사용할 수도 있다.Moreover, according to the color of the pixel made into object, you may use combining the said dye and a pigment.
감광성 수지 조성물에 있어서의 착색제 (E) 의 함유량은, 당해 감광성 수지 조성물 중의 용제를 제외한 성분의 총합을 100 질량부로 했을 때에, 바람직하게는 5 질량부 ∼ 80 질량부, 보다 바람직하게는 5 질량부 ∼ 70 질량부, 더욱 바람직하게는 10 질량부 ∼ 60 질량부이다.When content of the coloring agent (E) in the photosensitive resin composition makes the total of components except the solvent in the said photosensitive resin composition 100 mass parts, Preferably it is 5 mass parts - 80 mass parts, More preferably, 5 mass parts - 70 mass parts, More preferably, it is 10 mass parts - 60 mass parts.
착색제 (E) 로서 안료를 사용하는 경우, 안료의 분산성을 향상시키는 관점에서, 공지된 분산제를 감광성 수지 조성물에 배합해도 된다. 분산제로는, 시간 경과 분산 안정성이 우수한 고분자 분산제를 사용하는 것이 바람직하다. 고분자 분산제의 예로는, 우레탄계 분산제, 폴리에틸렌이민계 분산제, 폴리옥시에틸렌알킬에테르계 분산제, 폴리옥시에틸렌글리콜디에스테르계 분산제, 소르비탄 지방족 에스테르계 분산제, 지방족 변성 에스테르계 분산제 등을 들 수 있다. 이와 같은 고분자 분산제로서, EFKA (에프카 케미컬즈 비브이 (EFKA) 사 제조), Disperbyk (빅케미사 제조), 디스파론 (쿠스모토 화성 주식회사 제조), SOLSPERSE (제네카사 제조) 등의 상품명으로 시판되고 있는 것을 사용해도 된다. 감광성 수지 조성물에 있어서의 분산제의 함유량은, 사용하는 안료 등의 종류에 따라 적절히 설정하면 된다.When using a pigment as a coloring agent (E), you may mix|blend a well-known dispersing agent with the photosensitive resin composition from a viewpoint of improving the dispersibility of a pigment. As a dispersing agent, it is preferable to use the polymer dispersing agent excellent in time-lapse|temporal dispersion stability. Examples of the polymer dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, a sorbitan aliphatic ester-based dispersant, and an aliphatic modified ester-based dispersant. As such a polymer dispersing agent, EFKA (manufactured by EFKA), Disperbyk (manufactured by Big Chemi, Inc.), Disparon (manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (manufactured by Zeneca) are commercially available. You can use what you have. What is necessary is just to set content of the dispersing agent in the photosensitive resin composition suitably according to the kind, such as a pigment to be used.
감광성 수지 조성물에는, 상기 성분에 추가하여, 소정 특성을 부여하기 위해서, 공지된 커플링제, 레벨링제, 열 중합 금지제 등의 공지된 첨가제를 첨가해도 된다. 이들 첨가제의 첨가량은, 본 발명의 효과를 저해하지 않는 범위이면 특별히 한정되지 않는다.In addition to the said component, in addition to the said component, in order to provide a predetermined characteristic, you may add well-known additives, such as a well-known coupling agent, a leveling agent, and a thermal polymerization inhibitor, to the photosensitive resin composition. The addition amount of these additives will not be specifically limited if it is a range which does not impair the effect of this invention.
감광성 수지 조성물은, 공지된 혼합 장치를 사용하여, 상기 성분을 혼합함으로써 제조할 수 있다. 또, 원하는 바에 따라, 먼저 중합체 조성물 (A) 및 용제 (B) 를 포함하는 조성물을 조제한 후, 반응성 희석제 (C), 광 중합 개시제 (D) 및 착색제 (E) 를 혼합하여 제조할 수도 있다.The photosensitive resin composition can be manufactured by mixing the said component using a well-known mixing apparatus. Moreover, if desired, after preparing the composition containing a polymer composition (A) and a solvent (B) first, it can also mix and manufacture a reactive diluent (C), a photoinitiator (D), and a coloring agent (E).
다음으로, 본 발명의 감광성 수지 조성물을 사용하여 제작된 컬러 필터에 대해 설명한다.Next, the color filter produced using the photosensitive resin composition of this invention is demonstrated.
본 발명의 컬러 필터는, 상기 감광성 수지 조성물로 형성된 착색 패턴을 갖는다.The color filter of this invention has the coloring pattern formed from the said photosensitive resin composition.
이하, 본 발명의 컬러 필터에 대해, 도면을 사용하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, the color filter of this invention is demonstrated using drawings.
도 1 은, 본 발명의 일 실시형태의 컬러 필터를 나타내는 개략 단면도이다.BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows the color filter of one Embodiment of this invention.
도 1 에 나타내는 바와 같이, 본 발명의 컬러 필터는, 기판 (1) 과, 기판 (1) 의 일방의 면 상에 형성되는, RGB 의 화소 (2) 및 화소 (2) 의 경계에 형성되는 블랙 매트릭스 (3) 과, 화소 (2) 및 블랙 매트릭스 (3) 상에 형성되는 보호막 (4) 을 구비한다.As shown in FIG. 1, the color filter of this invention is black formed in the boundary between the board|
본 발명의 컬러 필터는, 화소 (2) 를 구성하는 R, G 및 B, 그리고 블랙 매트릭스 (3) (착색 패턴) 에서 선택되는 1 종 이상의 착색 패턴이 상기 감광성 수지 조성물을 사용하여 형성되는 것을 제외하면, 그 밖의 구성은 공지된 것을 채용할 수 있다.In the color filter of the present invention, at least one color pattern selected from R, G and B constituting the
또한, 도 1 에 나타낸 컬러 필터는 일례이며, 본 발명의 컬러 필터는, 이 구성으로만 한정되지 않는다.In addition, the color filter shown in FIG. 1 is an example, and the color filter of this invention is not limited only to this structure.
다음으로, 본 발명의 컬러 필터의 제조 방법에 대해 설명한다.Next, the manufacturing method of the color filter of this invention is demonstrated.
먼저, 기판 (1) 의 일방의 면에 착색 패턴을 형성한다. 구체적으로는, 기판 (1) 의 일방의 면에, 블랙 매트릭스 (3) 및 화소 (2) 를 순차 형성한다.First, a coloring pattern is formed in one surface of the board|
기재 (1) 로는, 특별히 한정되지 않지만, 유리 기판, 실리콘 기판, 폴리카보네이트 기판, 폴리에스테르 기판, 폴리아미드 기판, 폴리아미드이미드 기판, 폴리이미드 기판, 알루미늄 기판, 프린트 배선 기판, 어레이 기판 등을 사용할 수 있다.The
착색 패턴은, 포토리소그래피법에 의해 형성할 수 있다. 구체적으로는, 기판 (1) 의 일방의 면에, 상기 서술한 감광성 수지 조성물을 도포하여 도포막을 형성한 후, 소정 패턴의 포토마스크를 통하여 도포막을 노광하여 노광 부분을 광 경화시킨다. 그리고, 미노광 부분을 알칼리 수용액으로 현상한 후, 베이킹함으로써, 소정의 착색 패턴을 형성할 수 있다.A coloring pattern can be formed by the photolithographic method. After apply|coating the above-mentioned photosensitive resin composition to one surface of the board|
감광성 수지 조성물의 도포 방법으로는, 특별히 한정되지 않지만, 스크린 인쇄법, 롤 코트법, 커튼 코트법, 스프레이 코트법, 스핀 코트법 등을 사용할 수 있다.Although it does not specifically limit as a coating method of the photosensitive resin composition, The screen printing method, the roll coat method, the curtain coat method, the spray coat method, the spin coat method, etc. can be used.
또, 감광성 수지 조성물의 도포 후, 필요에 따라 순환식 오븐, 적외선 히터, 핫 플레이트 등의 가열 수단을 사용하여 가열함으로써 용제 (B) 를 휘발시켜도 된다. 가열 조건은, 특별히 한정되지 않고, 사용하는 감광성 수지 조성물의 종류에 따라 적절히 설정하면 된다. 일반적으로는, 50 ℃ ∼ 120 ℃ 의 온도에서 30 초 ∼ 30 분 가열하면 된다. Moreover, after application|coating of the photosensitive resin composition, you may volatilize a solvent (B) by heating using heating means, such as a circulation oven, an infrared heater, and a hotplate, as needed. Heating conditions are not specifically limited, What is necessary is just to set suitably according to the kind of photosensitive resin composition to be used. Generally, what is necessary is just to heat at the temperature of 50 degreeC - 120 degreeC for 30 second - 30 minutes.
감광성 수지 조성물로 이루어지는 도포막의 노광에 사용되는 광원으로는, 특별히 한정되지 않지만, 예를 들어, 저압 수은 램프, 중압 수은 램프, 고압 수은 램프, 크세논 램프, 메탈 할라이드 램프 등을 사용할 수 있다. 또, 노광량도, 특별히 한정되지 않고, 사용하는 감광성 수지 조성물의 종류에 따라 적절히 조정하면 된다.Although it does not specifically limit as a light source used for exposure of the coating film which consists of a photosensitive resin composition, For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be used. Moreover, an exposure amount is not specifically limited, either, What is necessary is just to adjust suitably according to the kind of photosensitive resin composition to be used.
현상에 사용되는 알칼리 수용액으로는, 특별히 한정되지 않는다. 알칼리 수용액의 구체예로는, 예를 들어, 탄산나트륨, 탄산칼륨, 탄산칼슘, 수산화나트륨, 수산화칼륨 등의 수용액 ; 에틸아민, 디에틸아민, 디메틸에탄올아민 등의 아민계 화합물의 수용액 ; 3-메틸-4-아미노-N,N-디에틸아닐린, 3-메틸-4-아미노-N-에틸-N-β-하이드록시에틸아닐린, 3-메틸-4-아미노-N-에틸-N-β-메탄술폰아미드에틸아닐린, 3-메틸-4-아미노-N-에틸-N-β-메톡시에틸아닐린 및 이들의 황산염, 염산염 또는 p-톨루엔술폰산염 등의 p-페닐렌디아민계 화합물의 수용액 등을 사용할 수 있다. 이들 중에서도, p-페닐렌디아민계 화합물의 수용액을 사용하는 것이 바람직하다. 또한, 이들 수용액에는, 필요에 따라 소포제나 계면 활성제를 첨가해도 된다. 또, 상기 알칼리 수용액에 의한 현상 후, 수세해 건조시키는 것이 바람직하다.It does not specifically limit as aqueous alkali solution used for image development. As a specific example of aqueous alkali solution, For example, aqueous solutions, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide; Aqueous solutions of amine compounds, such as ethylamine, diethylamine, and dimethylethanolamine; 3-Methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N -β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and p-phenylenediamine-based compounds such as sulfate, hydrochloride, or p-toluenesulfonate salts thereof of an aqueous solution and the like can be used. Among these, it is preferable to use the aqueous solution of a p-phenylenediamine type compound. In addition, you may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash with water and to dry after image development by the said aqueous alkali solution.
베이킹의 조건은, 특별히 한정되지 않고, 사용하는 감광성 수지 조성물의 종류에 따라 가열 처리를 실시하면 된다. 일반적으로는, 130 ℃ ∼ 250 ℃ 의 온도에서 10 분 ∼ 60 분간 가열하면 된다.The conditions of baking are not specifically limited, What is necessary is just to heat-process according to the kind of photosensitive resin composition to be used. Generally, what is necessary is just to heat at the temperature of 130 degreeC - 250 degreeC for 10 minutes - 60 minutes.
감광성 수지 조성물을 사용하여, 상기 서술한 바와 같은 도포, 노광, 현상 및 베이킹을, 블랙 매트릭스 (3) 용의 감광성 수지 조성물, 및 화소 (2) 용의 감광성 수지 조성물을 사용하여 순차 반복함으로써, 원하는 착색 패턴을 형성할 수 있다.By using the photosensitive resin composition and repeating the above-mentioned application|coating, exposure, image development, and baking one by one using the photosensitive resin composition for
또한, 상기에서는, 광 경화에 의한 착색 패턴의 형성 방법을 설명했지만, 광 중합 개시제 (E) 대신에, 경화 촉진제 및 공지된 에폭시 수지를 배합한 감광성 수지 조성물을 사용하면, 잉크젯법에 의해 도포한 후, 가열함으로써, 원하는 착색 패턴을 형성할 수도 있다. In addition, in the above, although the formation method of the coloring pattern by photocuring was demonstrated, when the photosensitive resin composition which mix|blended the hardening accelerator and the well-known epoxy resin is used instead of the photoinitiator (E), the inkjet method applied Then, a desired coloring pattern can also be formed by heating.
다음으로, 착색 패턴 (화소 (2) 및 블랙 매트릭스 (3)) 상에 보호막 (4) 을 형성한다. 보호막 (4) 으로는, 특별히 한정되지 않고, 공지된 재료 및 형성 방법을 사용하여 형성된다.Next, the
이와 같이 하여 제조되는 컬러 필터는, 알칼리 현상성이 우수함과 함께, 내열 황변성 및 내용제성이 우수한 착색 패턴을 부여하는 감광성 수지 조성물을 사용하여 제조되고 있기 때문에, 내열 황변성 및 내용제성이 우수한 착색 패턴 (화소 (2) 및 블랙 매트릭스 (3)) 을 갖는다. 그 때문에, 본 실시형태의 감광성 수지 조성물은, 각종 레지스트, 특히, 유기 EL 디스플레이, 액정 표시 장치, 고체 촬상 소자에 장착되는 컬러 필터를 제조하기 위해서 사용되는 레지스트로서 사용하는 것에 적합하다.Since the color filter manufactured in this way is excellent in alkali developability and is manufactured using the photosensitive resin composition which provides the coloring pattern excellent in heat yellowing resistance and solvent resistance, it is excellent in heat yellowing resistance and solvent resistance. It has a pattern (a pixel (2) and a black matrix (3)). Therefore, the photosensitive resin composition of this embodiment is suitable for using as a resist used in order to manufacture various resists, especially the color filter attached to organic electroluminescent display, a liquid crystal display device, and a solid-state image sensor.
실시예Example
이하, 실시예 및 비교예에 의해 본 발명을 더욱 구체적으로 설명하지만, 본 발명은 이하의 실시예로 한정되는 것은 아니다. 실시예에 사용한 화합물은 이하와 같다.Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to the following Example. The compounds used in the Examples are as follows.
GMA : 글리시딜메타크릴레이트 (니치유사 제조) GMA: glycidyl methacrylate (manufactured by Nichiyu Corporation)
OXMA : (3-에틸옥세탄-3-일)메틸메타크릴레이트 (우베 흥산사 제조) OXMA: (3-ethyloxetan-3-yl)methyl methacrylate (manufactured by Ube Heungsan)
MAA : 메타크릴산 (쿠라레사 제조) MAA: methacrylic acid (manufactured by Kurare)
AA : 아크릴산 (토아 합성사 제조) AA: Acrylic acid (manufactured by Toa Synthetic)
DCPMA : 디시클로펜타닐메타아크릴레이트 (히타치 화성 공업사 제조) DCPMA: dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Industry Co., Ltd.)
SM : 스티렌 (이데미츠 흥산사 제조) SM: Styrene (manufactured by Idemitsu Heungsan)
THPA : 테트라하이드로프탈산 무수물 (신닛폰 이화사 제조) THPA: tetrahydrophthalic anhydride (manufactured by Nippon Ewha Corporation)
V-601 : 디메틸-2,2'-아조비스(2-메틸프로피오네이트) (와코사 제조, 10 시간 반감기 온도 : 66 ℃) V-601: Dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Wako Corporation, 10-hour half-life temperature: 66°C)
퍼부틸 O : tert-부틸퍼옥시-2-에틸헥사노에이트 (니치유사 제조, 10 시간 반감기 온도 : 72 ℃) Perbutyl O: tert-butylperoxy-2-ethylhexanoate (manufactured by Nichiyo Co., Ltd., 10-hour half-life temperature: 72°C)
프로필렌글리콜모노메틸에테르 (쿠라레사 제조) Propylene glycol monomethyl ether (manufactured by Kuraray)
디에틸렌글리콜메틸에틸에테르 (쿠라레사 제조) Diethylene glycol methyl ethyl ether (manufactured by Kuraray)
프로필렌글리콜모노메틸에테르아세테이트 (쿠라레사 제조) Propylene glycol monomethyl ether acetate (manufactured by Kurare)
DPHA : 디펜타에리트리톨헥사아크릴레이트 (신나카무라 공업사 제조) DPHA: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Kogyo)
이르가큐어 907 : 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노-프로판-1-온 (BASF 재팬사 제조) Irgacure 907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (manufactured by BASF Japan)
VALIFAST BLUE 2620 (solvent blue 44) : 청색 염료 (오리엔트 화학 공업사 제조)VALIFAST BLUE 2620 (solvent blue 44): blue dye (manufactured by Orient Chemical Industry Co., Ltd.)
이하의 합성예 1 ∼ 15 에 나타내는 산가가 상이한 (메트)아크릴산계 중합체를 합성하였다. 또한, (메트)아크릴산계 중합체의 산가 및 중량 평균 분자량은, 상기 서술한 측정 방법에 따라 실시하였다.(meth)acrylic acid polymers having different acid values shown in Synthesis Examples 1 to 15 below were synthesized. In addition, the acid value and weight average molecular weight of the (meth)acrylic acid type polymer were implemented according to the above-mentioned measuring method.
[합성예 1] [Synthesis Example 1]
교반 장치, 적하 깔때기, 콘덴서, 온도계 및 가스 도입관을 구비한 플라스크에, 프로필렌글리콜모노메틸에테르 303.7 g 을 첨가하고, 질소 가스 치환하면서 교반하고, 88 ℃ 로 승온시켰다.To a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 303.7 g of propylene glycol monomethyl ether was added, stirred while replacing with nitrogen gas, and the temperature was raised to 88°C.
이어서, 메타크릴산 116.7 g (1.0 몰) 으로 이루어지는 모노머액에, 디메틸-2,2'-아조비스(2-메틸프로피오네이트) 23.3 g 및 디에틸렌글리콜메틸에틸에테르 30.9 g 을 혼합한 것을 적하 깔때기로부터 2 시간에 걸쳐서 상기 플라스크 중에 적하하였다. 120 ℃ 까지 승온시키고 30 분간 교반해 중합 반응을 실시해, 메타크릴산계 중합체를 생성시켰다. 이것을 시료 1 로 하였다. 얻어진 메타크릴산계 중합체의 중량 평균 분자량 (Mw) 은 3,900 이며, 산가는 543.6 이었다.Next, a mixture of 23.3 g of dimethyl-2,2'-azobis(2-methylpropionate) and 30.9 g of diethylene glycol methyl ethyl ether is added dropwise to a monomer solution comprising 116.7 g (1.0 mol) of methacrylic acid. It was dripped in the said flask over 2 hours from the funnel. It heated up to 120 degreeC, it stirred for 30 minutes, the polymerization reaction was performed, and the methacrylic acid-type polymer was produced|generated. This was referred to as
[합성예 2 ∼ 11] [Synthesis Examples 2 to 11]
표 1 및 2 에 기재된 원료를 사용하는 것 이외에는, 실시예 1 과 동일하게 히여, 중합 반응을 실시해 메타크릴산계 중합체 시료 2 ∼ 11 을 얻었다. 단 표 2 에 기재된 원료를 사용하는 경우, 적하 후 88 ℃ 에서 5 시간 교반하여 중합 반응을 실시하였다. 얻어진 메타크릴산계 중합체의 중량 평균 분자량 (Mw) 및 산가를 표 1 및 2 에 나타낸다.Except using the raw material of Tables 1 and 2, it carried out similarly to Example 1, the polymerization reaction was performed, and the methacrylic acid-type polymer samples 2-11 were obtained. However, when using the raw material of Table 2, it polymerized by stirring at 88 degreeC after dripping for 5 hours. Tables 1 and 2 show the weight average molecular weight (Mw) and acid value of the obtained methacrylic acid polymer.
[합성예 12] [Synthesis Example 12]
교반 장치, 적하 깔때기, 콘덴서, 온도계 및 가스 도입관을 구비한 플라스크에, 프로필렌글리콜모노메틸에테르아세테이트 58.6 g 을 첨가하고, 질소 가스 치환하면서 교반하고, 118 ℃ 로 승온시켰다.To a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 58.6 g of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen gas, and the temperature was raised to 118°C.
이어서, 글리시딜메타크릴레이트 81.8 g (1.0 몰) 으로 이루어지는 모노머액에, tert-부틸퍼옥시-2-에틸헥사노에이트 9.2 g (니치유사 제조, 퍼부틸 O, 0.068 몰) 및 프로필렌글리콜모노메틸에테르아세테이트 25.4 g 을 혼합한 것을 적하 깔때기로부터 2 시간에 걸쳐서 상기 플라스크 중에 적하하였다. 적하 종료 후, 120 ℃ 까지 승온시키고 30 분간 교반하여 중합 반응을 실시해, 중합체를 생성시켰다. 그 후, 플라스크 내를 공기로 치환하고, 아크릴산 41.5 g (1.0 몰), 트리페닐포스핀 0.4 g (부가 반응 촉매) 및 메틸하이드로퀴논 0.2 g (중합 금지제) 을 상기 중합체 용액 중에 투입하고, 110 ℃ 에서 10 시간에 걸쳐 반응을 계속하고, 글리시딜메타크릴레이트 유래의 에폭시기와 아크릴산의 반응에 의해 글리시딜메타크릴레이트 유래의 에폭시기를 개열하면 동시에 중합체의 측사슬에 에틸렌성 불포화 결합을 도입하였다. 이어서, 플라스크에 테트라하이드로프탈산 무수물 87.6 g (1.0 몰) 을 첨가하여 110 ℃ 에서 3 시간에 걸쳐 반응을 계속하고, 글리시딜메타크릴레이트 유래의 에폭시기의 개열에 의해 생성된 하이드록실기와 테트라하이드로프탈산 무수물의 무수물기를 반응시켜 측사슬에 카르복실기를 도입하여, 아크릴산계 중합체를 생성시켰다. 다음으로, 반응 용액에, 프로필렌글리콜모노메틸에테르아세테이트 145.2 g 을 첨가하고, 이것을 시료 12 로 하였다. 얻어진 아크릴산계 중합체의 중량 평균 분자량 (Mw) 은 9,600 이며, 산가는 146.9 였다.Next, to a monomer solution composed of 81.8 g (1.0 mol) of glycidyl methacrylate, 9.2 g of tert-butylperoxy-2-ethylhexanoate (manufactured by Nichiyo Co., Ltd., perbutyl O, 0.068 mol) and propylene glycol mono What mixed 25.4 g of methyl ether acetate was dripped in the said flask over 2 hours from the dropping funnel. After completion|finish of dripping, the temperature was raised to 120 degreeC, it stirred for 30 minutes, the polymerization reaction was performed, and the polymer was produced|generated. Thereafter, the inside of the flask was purged with air, and 41.5 g (1.0 mol) of acrylic acid, 0.4 g of triphenylphosphine (addition reaction catalyst) and 0.2 g of methylhydroquinone (polymerization inhibitor) were added into the polymer solution, 110 The reaction is continued at °C for 10 hours, and when the epoxy group derived from glycidyl methacrylate is cleaved by reaction of the epoxy group derived from glycidyl methacrylate with acrylic acid, an ethylenically unsaturated bond is introduced into the side chain of the polymer at the same time. did. Then, 87.6 g (1.0 mol) of tetrahydrophthalic anhydride was added to the flask, the reaction was continued at 110° C. for 3 hours, and the hydroxyl group and tetrahydro A carboxyl group was introduced into the side chain by reacting the anhydride group of the phthalic anhydride to produce an acrylic acid-based polymer. Next, 145.2 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and this was set as sample 12. The weight average molecular weight (Mw) of the obtained acrylic acid polymer was 9,600, and the acid value was 146.9.
[합성예 13 ∼ 15] [Synthesis Examples 13 to 15]
표 3 에 기재된 원료를 사용하는 것 이외에는, 합성예 12 와 동일하게 하여, 중합 반응을 실시해 아크릴산계 중합체 시료 13 ∼ 15 를 얻었다. 디시클로펜타닐메타아크릴레이트 및 스티렌은, 글리시딜메타크릴레이트와 혼합하여 모노머 혼합물로서 사용하였다. 얻어진 아크릴산계 중합체의 중량 평균 분자량 (Mw) 및 산가를 표 3 에 나타낸다.Except using the raw material of Table 3, it carried out similarly to Synthesis Example 12, polymerization reaction was performed, and acrylic acid-type polymer samples 13-15 were obtained. Dicyclopentanyl methacrylate and styrene were mixed with glycidyl methacrylate and used as a monomer mixture. Table 3 shows the weight average molecular weight (Mw) and acid value of the obtained acrylic acid polymer.
[실시예 1 ∼ 21 및 비교예 1 ∼ 18] [Examples 1-21 and Comparative Examples 1-18]
<감광성 수지 조성물의 조제> <Preparation of the photosensitive resin composition>
합성예 1 ∼ 15 에서 합성한 (메트)아크릴산계 중합체 시료 1 ∼ 15 를 이용하고, 표 4 에 나타내는 배합 성분 및 배합량에 따라 실시예 1 ∼ 21 및 비교예 1 ∼ 18 의 컬러 필터용 감광성 수지 조성물을 조제하였다. 또, 실시예 1 ∼ 21 및 비교예 1 ∼ 18 의 컬러 필터용 감광성 수지 조성물을 조제할 때에 사용한 중합체 조성물 (A) 의 조성을, 표 5 ∼ 11 에 나타냈다.Using the (meth)acrylic
또한, 표 4 에 있어서의 중합체 조성물 (A) 의 배합량에는, (메트)아크릴산계 중합체를 합성할 때에 사용한 용제는 포함되지 않는다. 즉, 용제 (B) 의 배합량은, 합성예 1 ∼ 11 에서는, 메타크릴산계 중합체를 합성할 때에 사용한 프로필렌글리콜모노메틸에테르와, 디에틸렌글리콜메틸에틸에테르의 합산이며, 합성예 12 ∼ 15 에서는, 아크릴산계 중합체를 합성할 때에 사용한 프로필렌글리콜모노메틸에테르아세테이트와, 추가로 배합한 프로필렌글리콜모노메틸에테르아세테이트의 합산이다.In addition, the solvent used when synthesize|combining a (meth)acrylic-acid type polymer is not contained in the compounding quantity of the polymer composition (A) in Table 4. That is, the compounding quantity of the solvent (B) is the sum of propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether used when synthesizing the methacrylic acid-based polymer in Synthesis Examples 1 to 11, and in Synthesis Examples 12 to 15, It is the sum of the propylene glycol monomethyl ether acetate used when synthesize|combining the acrylic acid type polymer, and the propylene glycol monomethyl ether acetate further mix|blended.
<감광성 수지 조성물의 평가> <Evaluation of the photosensitive resin composition>
(1) 내열 황변성 (1) Heat-resistance yellowing resistance
조제된 감광성 수지 조성물을 가로 세로 5 cm 유리 기판 (무알칼리 유리 기판) 상에, 노광 후의 두께가 2.5 ㎛ 가 되도록 스핀 코트한 후, 90 ℃ 에서 3 분간 가열하여 용제를 휘발시켜, 유리 기판 상에 도포막을 형성하였다.The prepared photosensitive resin composition is spin-coated on a 5 cm horizontal glass substrate (alkali-free glass substrate) so that the thickness after exposure may be set to 2.5 μm, and then heated at 90° C. for 3 minutes to volatilize the solvent, and on the glass substrate A coating film was formed.
다음으로, 얻어진 도포막에 파장 365 nm 의 광을 노광하고, 노광 부분을 광 경화시킨 후, 230 ℃ 에서 30 분간 베이킹하여, 경화 도막을 제작하였다.Next, after exposing the light of wavelength 365nm to the obtained coating film, and photocuring an exposure part, it baked at 230 degreeC for 30 minute(s), and produced the cured coating film.
베이킹 전후의 도막의 색 변화를 분광 광도계 UV-1650PC (주식회사 시마즈 제작소 제조) 로 측정하였다. 상기 230 ℃ 에서 30 분간 베이킹 조작 전후의 투과율의 변화 (ΔEab) 를 조사함으로써 내열 황변성의 평가를 실시하였다. 이 평가의 기준은 이하와 같다. 결과를 표 12 및 13 에 나타낸다.The color change of the coating film before and behind baking was measured with the spectrophotometer UV-1650PC (made by Shimadzu Corporation). Heat-resistant yellowing property was evaluated by examining the change (ΔEab) of the transmittance before and after the baking operation at 230°C for 30 minutes. The criteria for this evaluation are as follows. The results are shown in Tables 12 and 13.
◎ : ΔEab 가 5 이하이다 ◎: ΔEab is 5 or less
○ : ΔEab 가 5 보다 크고 10 이하이다 ○: ΔEab is greater than 5 and less than or equal to 10
△ : ΔEab 가 10 보다 크고 15 이하이다Δ: ΔEab is greater than 10 and less than or equal to 15
× : ΔEab 가 15 보다 크다×: ΔEab is greater than 15
(2) 내용제성 (2) Solvent resistance
조제된 감광성 수지 조성물을 가로 세로 5 cm 유리 기판 (무알칼리 유리 기판) 상에, 노광 후의 두께가 2.5 ㎛ 가 되도록 스핀 코트한 후, 90 ℃ 에서 3 분간 가열하여 용제를 휘발시켜, 유리 기판 상에 도포막을 형성하였다.The prepared photosensitive resin composition is spin-coated on a 5 cm horizontal glass substrate (alkali-free glass substrate) so that the thickness after exposure may be set to 2.5 μm, and then heated at 90° C. for 3 minutes to volatilize the solvent, and on the glass substrate A coating film was formed.
다음으로, 얻어진 도포막에 파장 365 nm 의 광을 노광하고, 노광 부분을 광 경화시킨 후, 230 ℃ 에서 30 분간 베이킹하여, 경화 도막을 제작하였다.Next, after exposing the light of wavelength 365nm to the obtained coating film, and photocuring an exposure part, it baked at 230 degreeC for 30 minute(s), and produced the cured coating film.
n-메틸-2-피롤리돈에 상기 경화 도막이 형성된 유리 기판을 23 ℃ 에서 1 시간 침지시켰다. n-메틸-2-피롤리돈에의 침지 전후의 투과율의 변화 (ΔEab) 를 분광 광도계 UV-1650PC (주식회사 시마즈 제작소 제조) 로 측정하고, 그 결과에 기초하여 내용제성의 평가를 실시하였다. 이 평가의 기준은 이하와 같다. 결과를 표 12 및 13 에 나타낸다.The glass substrate on which the said cured coating film was formed in n-methyl-2-pyrrolidone was immersed at 23 degreeC for 1 hour. The change in transmittance (ΔEab) before and after immersion in n-methyl-2-pyrrolidone was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation), and solvent resistance was evaluated based on the result. The criteria for this evaluation are as follows. The results are shown in Tables 12 and 13.
◎ : ΔEab 가 1 이하이다 ◎: ΔEab is 1 or less
○ : ΔEab 가 1 보다 크고 3 이하이다 ○: ΔEab is greater than 1 and less than or equal to 3
△ : ΔEab 가 3 보다 크고 5 이하이다Δ: ΔEab is greater than 3 and less than or equal to 5
× : ΔEab 가 5 보다 크다×: ΔEab is greater than 5
(3) 알칼리 현상성 (3) alkali developability
조제된 감광성 수지 조성물을 가로 세로 5 cm 유리 기판 (무알칼리 유리 기판) 상에, 노광 후의 두께가 2.5 ㎛ 가 되도록 스핀 코트한 후, 90 ℃ 에서 3 분간 가열하여 용제를 휘발시켜, 유리 기판 상에 도포막을 형성하였다.The prepared photosensitive resin composition is spin-coated on a 5 cm horizontal glass substrate (alkali-free glass substrate) so that the thickness after exposure may be set to 2.5 μm, and then heated at 90° C. for 3 minutes to volatilize the solvent, and on the glass substrate A coating film was formed.
다음으로, 도포막으로부터 100 ㎛ 의 거리에 소정 패턴의 포토마스크를 배치하고, 이 포토마스크를 통하여 파장 365 nm 의 광을 노광하여, 노광 부분을 광 경화시켰다.Next, a photomask of a predetermined pattern was placed at a distance of 100 µm from the coating film, and light having a wavelength of 365 nm was exposed through the photomask to light-cure the exposed portion.
다음으로, 0.1 질량부의 탄산나트륨을 포함하는 수용액을 23 ℃ 의 온도 및 0.3 MPa 의 압력으로 90 초간 스프레이함으로써, 미노광 부분을 용해하여 현상한 후, 230 ℃ 에서 30 분간 베이킹함으로써 소정 패턴을 형성하였다.Next, by spraying an aqueous solution containing 0.1 parts by mass of sodium carbonate at a temperature of 23 ° C. and a pressure of 0.3 MPa for 90 seconds, the unexposed portion was dissolved and developed, and then a predetermined pattern was formed by baking at 230 ° C. for 30 minutes.
알칼리 현상 후의 잔류물은, (주) 히타치 하이테크놀로지즈 제조 전자현미경 S-3400 을 사용하여, 알칼리 현상 후의 패턴을 관찰함으로써 확인하였다. 이 평가의 기준은 이하와 같다. 결과를 표 12 및 13 에 나타낸다.The residue after alkali development was confirmed by observing the pattern after alkali development using Hitachi High-Technologies Co., Ltd. product electron microscope S-3400. The criteria for this evaluation are as follows. The results are shown in Tables 12 and 13.
◎ : 잔류물 없음 ◎: no residue
○ : 잔류물 거의 없음 ○: Almost no residue
△ : 잔류물 조금 있음 △: some residue
× : 잔류물 있고, 패턴 남지 않음×: Residue, no pattern left
표 12 및 13 에 나타내는 결과로부터, 실시예 1 ∼ 21 의 감광성 수지 조성물은, 비교예 1 ∼ 18 의 감광성 수지 조성물과 비교해, 우수한 내열 황변성, 내용제성 및 알칼리 현상성을 갖는 것을 확인할 수 있었다. 특히, 산가가 낮은 (메트)아크릴산계 중합체 (b) 의 종류가 많을수록, 우수한 알칼리 현상성을 나타내는 것을 확인할 수 있었다. 실시예 3, 6, 9, 12, 15, 18 및 21 에서는, 산가가 상이한 4 종의 (메트)아크릴산계 중합체를 사용했지만, 산가가 상이한 5 종 이상의 (메트)아크릴산계 중합체를 사용해도 동일한 결과가 얻어진다고 생각된다.From the results shown in Tables 12 and 13, the photosensitive resin composition of Examples 1-21 compared with the photosensitive resin composition of Comparative Examples 1-18, and has confirmed that it has the outstanding heat yellowing resistance, solvent resistance, and alkali developability. In particular, it was confirmed that the more the types of the (meth)acrylic acid-based polymer (b) having a low acid value, the better the alkali developability. In Examples 3, 6, 9, 12, 15, 18 and 21, 4 types of (meth)acrylic acid type polymers having different acid values were used, but the same results were obtained even when 5 or more types of (meth)acrylic acid type polymers having different acid values were used. is thought to be obtained.
이에 대하여, 비교예 1 ∼ 8, 15 ∼ 18 에 나타내는 바와 같이 1 종의 (메트)아크릴산계 중합체만을 포함하는 감광성 수지 조성물, 비교예 12 에 나타내는 바와 같이 (메트)아크릴산계 중합체 (b) 에 대한 (메트)아크릴산계 중합체 (a) 의 질량비가 0.50 을 초과하는 감광성 수지 조성물 그리고 비교예 13 및 14 에 나타내는 바와 같이 (메트)아크릴산계 중합체 (b) 의 산가가 (메트)아크릴산계 중합체 (a) 의 산가의 0.50 배를 초과하는 감광성 수지 조성물은, 내열 황변성, 내용제성 및 알칼리 현상성의 적어도 하나가 불충분하였다. 또, 비교예 9 ∼ 11 에 나타내는 바와 같이, 산가가 상이한 2 종 이상의 (메트)아크릴산계 중합체를 배합하였다고 해도, (메트)아크릴산계 중합체 (a) 의 중량 평균 분자량이 지나치게 큰 경우에는, 배합 시에 분리되는 것을 확인할 수 있었다.On the other hand, as shown in Comparative Examples 1 to 8 and 15 to 18, the photosensitive resin composition containing only one type of (meth)acrylic acid polymer, and as shown in Comparative Example 12, the (meth)acrylic acid polymer (b) As shown in the photosensitive resin composition in which the mass ratio of the (meth)acrylic acid type polymer (a) exceeds 0.50, and Comparative Examples 13 and 14, the acid value of the (meth)acrylic acid type polymer (b) is (meth)acrylic acid type polymer (a) The photosensitive resin composition exceeding 0.50 times the acid value of was insufficient in at least one of heat yellowing resistance, solvent resistance, and alkali developability. Further, as shown in Comparative Examples 9 to 11, even when two or more types of (meth)acrylic acid-based polymers having different acid values are blended, when the weight average molecular weight of the (meth)acrylic acid-based polymer (a) is too large, at the time of blending It was confirmed that the separation was
산업상 이용가능성Industrial Applicability
본 발명에서 얻어지는 감광성 수지 조성물을 사용한 경화 도막은, 내열 황변성, 내용제성 및 알칼리 현상성이 우수한 점에서 각종 레지스트 분야에서의 이용 가치가 매우 높고, 유기 EL 표시 장치, 액정 표시 장치, 고체 촬상 소자에 장착되는 컬러 필터로서 바람직하다. The cured coating film using the photosensitive resin composition obtained in the present invention is excellent in heat yellowing resistance, solvent resistance, and alkali developability, and therefore has very high utility value in various resist fields, and is an organic EL display device, a liquid crystal display device, and a solid-state image sensor. It is preferable as a color filter to be mounted on.
1 : 기판
2 : 화소
3 : 블랙 매트릭스
4 : 보호막1: substrate
2: pixel
3: Black Matrix
4: Shield
Claims (7)
상기 중합체 조성물은, 상기 2 종 이상의 (메트)아크릴산계 중합체 중, 최대 산가를 갖는 (메트)아크릴산계 중합체 (a) 의 산가를 1 로 한 경우에, 0.01 배 ∼ 0.30 배의 산가를 갖는 (메트)아크릴산계 중합체 (b) 를 포함하고,
상기 (메트)아크릴산계 중합체 (a) 의 중량 평균 분자량이 1,000 ∼ 10,000 이며, 또한
상기 (메트)아크릴산계 중합체 (b) 에 대한 상기 (메트)아크릴산계 중합체 (a) 의 질량비 [(a)/(b)] 가 0.01 ∼ 0.30 인 것을 특징으로 하는 중합체 조성물.
(식 1 중, R1 은 수소 원자 또는 메틸기를 나타낸다. 식 2 중, R2 는 수소 원자 또는 메틸기를 나타내고, R3 은 산기와 에틸렌성 불포화기를 갖는 탄소수 2 ∼ 30 의 기를 나타낸다.)A polymer composition comprising two or more types of (meth)acrylic acid polymers having structural units represented by the following Formula 1 or Formula 2 and having different acid values (mgKOH/g),
The polymer composition has an acid value of 0.01 to 0.30 times when the acid value of the (meth)acrylic acid polymer (a) having the maximum acid value among the two or more types of (meth)acrylic acid polymers is 1 (meth) ) containing an acrylic acid-based polymer (b),
The (meth)acrylic acid polymer (a) has a weight average molecular weight of 1,000 to 10,000, and
The mass ratio [(a)/(b)] of the (meth)acrylic acid-based polymer (a) to the (meth)acrylic acid-based polymer (b) is 0.01 to 0.30.
(In Formula 1, R 1 represents a hydrogen atom or a methyl group. In Formula 2, R 2 represents a hydrogen atom or a methyl group, and R 3 represents a group having 2 to 30 carbon atoms having an acid group and an ethylenically unsaturated group.)
상기 (메트)아크릴산계 중합체 (a) 와 상기 (메트)아크릴산계 중합체 (b) 가, 상기 식 1 또는 상기 식 2 로 나타내는 동일한 구성 단위를 적어도 하나 갖는 것을 특징으로 하는 중합체 조성물. The method of claim 1,
The (meth)acrylic acid-based polymer (a) and the (meth)acrylic acid-based polymer (b) each have at least one identical structural unit represented by the formula (1) or the formula (2).
상기 (메트)아크릴산계 중합체 (b) 의 중량 평균 분자량이 1,000 ∼ 10,000 인 것을 특징으로 하는 중합체 조성물.The method of claim 1,
A polymer composition, characterized in that the (meth)acrylic acid-based polymer (b) has a weight average molecular weight of 1,000 to 10,000.
착색제 (E) 를 추가로 포함하는 것을 특징으로 하는 감광성 수지 조성물.6. The method of claim 5,
A coloring agent (E) is further included, The photosensitive resin composition characterized by the above-mentioned.
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