JP5736038B2 - Copolymer, resin composition and photosensitive resin composition containing the copolymer, and color filter - Google Patents
Copolymer, resin composition and photosensitive resin composition containing the copolymer, and color filter Download PDFInfo
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- JP5736038B2 JP5736038B2 JP2013509840A JP2013509840A JP5736038B2 JP 5736038 B2 JP5736038 B2 JP 5736038B2 JP 2013509840 A JP2013509840 A JP 2013509840A JP 2013509840 A JP2013509840 A JP 2013509840A JP 5736038 B2 JP5736038 B2 JP 5736038B2
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- Prior art keywords
- copolymer
- resin composition
- meth
- acrylate
- photosensitive resin
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims description 96
- 239000011342 resin composition Substances 0.000 title claims description 88
- 239000000178 monomer Substances 0.000 claims description 106
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 74
- 239000002904 solvent Substances 0.000 claims description 59
- 239000000049 pigment Substances 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 27
- 239000003085 diluting agent Substances 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 239000003086 colorant Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 4
- 150000007519 polyprotic acids Polymers 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 37
- -1 ethylhexyl group Chemical group 0.000 description 32
- 238000004383 yellowing Methods 0.000 description 32
- 239000000758 substrate Substances 0.000 description 30
- 239000003513 alkali Substances 0.000 description 23
- 238000002156 mixing Methods 0.000 description 23
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 22
- 238000007334 copolymerization reaction Methods 0.000 description 22
- 239000000975 dye Substances 0.000 description 22
- 230000035945 sensitivity Effects 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 21
- 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 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 19
- ZMZHRHTZJDBLEX-UHFFFAOYSA-N (2-phenylphenyl) prop-2-enoate Chemical class C=CC(=O)OC1=CC=CC=C1C1=CC=CC=C1 ZMZHRHTZJDBLEX-UHFFFAOYSA-N 0.000 description 18
- 238000011161 development Methods 0.000 description 18
- 230000018109 developmental process Effects 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 15
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 15
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000007259 addition reaction Methods 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 13
- 238000004040 coloring Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005979 thermal decomposition reaction Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000013329 compounding Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 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 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 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
- 125000003118 aryl group Chemical group 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
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 4
- 230000007261 regionalization Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 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 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 239000001056 green pigment Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000004973 liquid crystal related substance 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 0 **(*Cc(cccc1)c1-c1ccccc1)C(C(*)=C)=O Chemical compound **(*Cc(cccc1)c1-c1ccccc1)C(C(*)=C)=O 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-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
- 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 2
- 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 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
- 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
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-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
- IWRJDDOFBDGNGX-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione;pyrrole-2,5-dione Chemical class O=C1NC(=O)C=C1.C1=CC(O)=CC=C1N1C(=O)C=CC1=O IWRJDDOFBDGNGX-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
- 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
- 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
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
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- JMXROTHPANUTOJ-UHFFFAOYSA-H naphthol green b Chemical compound [Na+].[Na+].[Na+].[Fe+3].C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21 JMXROTHPANUTOJ-UHFFFAOYSA-H 0.000 description 1
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
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- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
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- IYDCZCBVYAESDR-UHFFFAOYSA-N pentadec-4-ene Chemical compound CCCCCCCCCCC=CCCC IYDCZCBVYAESDR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- FVGBHSIHHXTYTH-UHFFFAOYSA-N pentane-1,1,1-triol Chemical compound CCCCC(O)(O)O FVGBHSIHHXTYTH-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- COEZWFYORILMOM-UHFFFAOYSA-M sodium 4-[(2,4-dihydroxyphenyl)diazenyl]benzenesulfonate Chemical compound [Na+].OC1=CC(O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 COEZWFYORILMOM-UHFFFAOYSA-M 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- JOHIXGUTSXXADV-UHFFFAOYSA-N undec-2-ene Chemical compound CCCCCCCCC=CC JOHIXGUTSXXADV-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Images
Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Landscapes
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- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、共重合体、その共重合体を含む樹脂組成物及び感光性樹脂組成物、並びにカラーフィルターに関する。特に、本発明は有機ELディスプレイ、液晶表示装置、固体撮像素子に組み込まれるカラーフィルターを製造するために用いられる材料としての共重合体、この共重合体を含む樹脂組成物及び感光性樹脂組成物、並びにこの感光性樹脂組成物を用いて製造されるカラーフィルターに関する。 The present invention relates to a copolymer, a resin composition and a photosensitive resin composition containing the copolymer, and a color filter. In particular, the present invention relates to an organic EL display, a liquid crystal display device, a copolymer as a material used for producing a color filter incorporated in a solid-state imaging device, a resin composition containing the copolymer, and a photosensitive resin composition. And a color filter produced using the photosensitive resin composition.
近年、省資源や省エネルギーの観点から、各種コーティング、印刷、塗料、接着剤などの分野において、紫外線や電子線などの活性エネルギー線により硬化可能な感光性樹脂組成物が広く使用されている。また、プリント配線基板などの電子材料の分野においても、活性エネルギー線により硬化可能な感光性樹脂組成物がソルダーレジストやカラーフィルター用レジストなどに使用されている。 In recent years, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of various coatings, printing, paints, adhesives and the like from the viewpoint of resource saving and energy saving. Also in the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be cured by active energy rays are used for solder resists, color filter resists, and the like.
カラーフィルターは、一般に、ガラス基板などの透明基板と、透明基板上に形成された赤(R)、緑(G)及び青(B)の画素と、画素の境界に形成されるブラックマトリックスと、画素及びブラックマトリックス上に形成される保護膜とから構成される。このような構成を有するカラーフィルターは、通常、透明基板上にブラックマトリックス、画素及び保護膜を順次形成することによって製造される。画素及びブラックマトリックス(以下、画素及びブラックマトリックスのことを「着色パターン」という。)の形成方法としては、様々な製造方法が提案されているが、感光性樹脂組成物をレジストとして用い、塗布、露光、現像及びベーキングを繰り返すフォトリソグラフィ工法で作成される顔料/染料分散法は、耐光性や耐熱性などの耐久性に優れ、ピンホールなどの欠陥が少ない着色パターンを与えるため、現在の主流となっている。 The 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 pixel boundary, It is comprised from the protective film formed on a pixel and a black matrix. A color filter having such a configuration is usually manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. Various manufacturing methods have been proposed as a method for forming a pixel and a black matrix (hereinafter, the pixel and the black matrix are referred to as a “colored pattern”). The pigment / dye dispersion method created by a photolithographic method that repeats exposure, development and baking is superior in durability such as light resistance and heat resistance, and gives a colored pattern with few defects such as pinholes. It has become.
一般に、フォトリソグラフィ工法に用いられる感光性樹脂組成物は、アルカリ可溶性樹脂、反応性希釈剤、光重合開始剤、着色剤及び溶剤を含有する。顔料/染料分散法では、上記の利点を有している反面、ブラックマトリクス、R、G、Bのパターンを繰り返し形成することから、塗膜のバインダーとなるアルカリ可溶性樹脂に高い耐熱分解性と耐熱黄変性が要求される。耐熱分解性を向上させる方法として、従来から、マレイミドを含む単量体を共重合成分とする樹脂組成物(例えば、特許文献1)等が提案されている。しかし、マレイミドを含む単量体を共重合成分とする樹脂組成物では、分子中に含まれる窒素原子を原因とした黄色から黄褐色の着色を有しており、塗膜の透明性を悪化させる。さらに、加熱処理を行う後硬化時に着色が進行するという問題があった。また、メタクリル酸とベンジルメタクリレート、ヒドロキシエチルメタクリレート、ブチルメタクリレート等を含むアクリル系共重合体を用いたものが知られているが、耐熱分解性が十分でなくパターン固着時の加熱工程で熱分解物がアウトガスとなって発生し、基板や装置を汚染することが問題となっている。 Generally, the photosensitive resin composition used for the photolithographic method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The pigment / dye dispersion method has the above-mentioned advantages, but the pattern of black matrix, R, G, and B is repeatedly formed. Therefore, the alkali-soluble resin serving as the binder of the coating film has high heat decomposition resistance and heat resistance. Yellowing is required. As a method for improving the thermal decomposition resistance, a resin composition (for example, Patent Document 1) using a monomer containing maleimide as a copolymerization component has been proposed. However, a resin composition having a monomer containing maleimide as a copolymerization component has a yellow to tan coloration caused by nitrogen atoms contained in the molecule, and deteriorates the transparency of the coating film. . Furthermore, there has been a problem that coloring progresses during post-curing after heat treatment. In addition, those using acrylic copolymers containing methacrylic acid and benzyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, etc. are known, but the thermal decomposition is not sufficient and the thermal decomposition products in the heating process at the time of pattern fixation Is generated as an outgas, which contaminates the substrate and the device.
また、耐熱黄変性向上のために脂環式のシクロヘキシルメタクリレート等を使用したアクリル共重合体を用いると、耐熱分解性が十分でない。更にパターニング性や感度を向上させる手段として、パラクミルフェノールのエチレンオキサイド(EO)変性またはプロピレンオキサイド(PO)変性(メタ)アクリレートを用いる事が提案されている(例えば、特許文献2、3)。また、液晶配向用突起形成用ネガ型レジストとしてヒドロキシエチル化フェニルフェノール(メタ)アクリレートを用いることが提案されている(例えば特許文献4)。しかし、カラーフィルター用のバインダーとして耐熱分解性や耐熱黄変性を満足するものは出来ていない。
Further, when an acrylic copolymer using alicyclic cyclohexyl methacrylate or the like is used for improving heat yellowing resistance, the heat decomposability is not sufficient. Further, it has been proposed to use ethylene oxide (EO) modification or propylene oxide (PO) modification (meth) acrylate of paracumylphenol as means for improving patterning property and sensitivity (for example,
上述のように、従来の感光性樹脂組成物は、感度や現像性が十分でない場合や、耐熱分解性及び耐熱黄変性に優れた着色パターンが得られない場合がある。
従って、本発明は、上記のような課題を解決するためになされたものであり、感度や現像性が良好であると共に、耐熱分解性及び耐熱黄変性に優れた着色パターンを与える感光性樹脂としての共重合体、それを含む樹脂組成物及び感光性樹脂組成物を提供することを目的とする。また、耐熱分解性及び耐熱黄変性に優れた着色パターンを有するカラーフィルターを提供することを目的とする。As described above, the conventional photosensitive resin composition may not have sufficient sensitivity and developability, or a colored pattern excellent in heat decomposition resistance and heat yellowing may not be obtained.
Accordingly, the present invention has been made to solve the above-mentioned problems, and as a photosensitive resin that gives a colored pattern that has good sensitivity and developability and is excellent in heat decomposition and heat yellowing. It is an object to provide a copolymer of the above, a resin composition containing the copolymer, and a photosensitive resin composition. It is another object of the present invention to provide a color filter having a coloring pattern excellent in heat decomposability and heat yellowing.
本発明者らは、上記のような課題を解決すべく鋭意検討した結果、特定の共重合体を感光性樹脂組成物に用いることで、上記課題を解決し得ることを見出し、本発明に至った。
すなわち、本発明は、[1]炭素数10〜20の橋かけ環式炭化水素基を有する重合性モノマー(a−1)及び/または下記化学式(1)で示される重合性モノマー(a−1’)と、下記化学式(2)で示される重合性モノマー(a−2)、並びにエチレン性不飽和基を有するラジカル重合性モノマー(a−3)を重合してなり、かつ重量平均分子量(ポリスチレン換算の重量平均分子量)が1000〜50000であって、さらにカルボキシル基を含有し、酸価が20〜300KOHmg/gである共重合体(A)である。
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific copolymer in the photosensitive resin composition, and the present invention has been achieved. It was.
That is, the present invention provides [1] a polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a polymerizable monomer represented by the following chemical formula (1) (a-1 '), A polymerizable monomer (a-2) represented by the following chemical formula (2), and a radical polymerizable monomer (a-3) having an ethylenically unsaturated group, and having a weight average molecular weight (polystyrene). It is a copolymer (A) having a weight average molecular weight (converted) of 1,000 to 50,000, further containing a carboxyl group, and having an acid value of 20 to 300 KOHmg / g .
(式(1)中のX及びYは、それぞれ独立して、水素原子、直鎖又は分岐していてもよい炭素数1〜4の炭化水素基を示し、R1及びR2はそれぞれ独立して水素原子、カルボキシル基、または置換基を有していてもよい炭素数1〜20の炭化水素基であって、R1及びR2を結ぶ環状構造をとっていてもよい。)(X and Y in Formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 are each independently A hydrogen atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may have a cyclic structure connecting R 1 and R 2. )
また、本発明は[2]不飽和基を含有する[1]の共重合体(A)、
[3]前記炭素数10〜20の橋かけ環式炭化水素基を有する重合性モノマー(a−1)がジシクロペンテニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレートから選ばれる少なくとも1種を含む[1]または[2]の共重合体(A)、
[4]前記重合性モノマー(a−1)及び/又は(a−1’)がモル比で2〜50%、前記重合性モノマー(a−2)が10〜80%、前記重合性モノマー(a−3)が18〜88%の割合で重合されている、[1]〜[3]のいずれかの共重合体(A)、
[5]前記エチレン性不飽和基を有するラジカル重合性モノマーが、不飽和一塩基酸、不飽和多塩基酸無水物、またはグリシジル(メタ)アクリレートから選択される1種または2種以上である、[1]〜[4]のいずれかの共重合体(A)、
[6][1]〜[5]のいずれかの共重合体(A)および溶剤(B)を含有する樹脂組成物、
[7]更に反応性希釈剤(C)を含有する[6]の樹脂組成物
[8][1]〜[5]のいずれかの共重合体(A)、溶剤(B)、反応性希釈剤(C)及び光重合開始剤(D)を含有する感光性樹脂組成物、
[9]更に染料および/または顔料からなる着色剤(E)を含有する、[8]の感光性樹脂組成物、
[10]カラーフィルター用感光性樹脂組成物である、[9]の感光性樹脂組成物、
[11][10]の感光性樹脂組成物を含有するレジスト塗膜を硬化させてなるカラーフィルターである。
The present invention also provides [2 ] a copolymer (A) of [1 ] containing an unsaturated group,
[3] before Symbol polymerizable monomer (a-1) is dicyclopentenyl (meth) acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, dicyclopentanyl (meth) acrylate, isobornyl (meth) [1] or [2] copolymer (A) containing at least one selected from acrylate and adamantyl (meth) acrylate,
[4] before Symbol polymerizable monomer (a-1) and / or (a-1 ') 2 to 50 percent by molar ratio, the polymerizable monomer (a-2) 10 to 80% of the polymerizable monomer (A-3) is polymerized in a proportion of 18 to 88%, the copolymer (A) according to any one of [1] to [3] ,
[5] radical polymerizable monomer having a pre-Symbol ethylenically unsaturated group, the unsaturated monobasic acid is the unsaturated polybasic acid anhydride, or glycidyl (meth) one or more members selected from acrylate Copolymer (A) of any one of [1] to [4]
[6] [1] to one of the copolymer (A) and Solvent (B) a resin composition containing the [5],
[7] A further reactive diluent containing (C) a resin composition of [6]
[8 ] A photosensitive resin composition containing the copolymer (A) of any one of [ 1] to [ 5 ], a solvent (B), a reactive diluent (C), and a photopolymerization initiator (D),
[9] further to a coloring agent comprising a dye and / or pigment (E), the photosensitive resin composition of [8],
[10] Color is a filter for a photosensitive resin composition, the photosensitive resin composition of [9],
[11 ] A color filter obtained by curing a resist coating film containing the photosensitive resin composition according to [10] .
本発明によれば、感度や現像性が良好であると共に、耐熱分解性及び耐熱黄変性に優れた硬化塗膜を形成することのできる共重合体、またはその共重合体を含む感光性樹脂組成物を提供することができる。また、本発明の感光性樹脂組成物から形成される硬化塗膜は、耐熱性と感度に優れており、現像性を有することから各種レジスト分野での利用価値が極めて高く、その中でも耐熱分解性及び耐熱黄変性に優れた着色パターンを有するカラーフィルターを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the sensitivity and developability are favorable, and the copolymer which can form the cured coating film excellent in heat-resistant decomposability | degradability and heat-resistant yellowing, or the photosensitive resin composition containing the copolymer Things can be provided. In addition, the cured coating film formed from the photosensitive resin composition of the present invention is excellent in heat resistance and sensitivity, and has developability, so it has extremely high utility value in various resist fields. And a color filter having a coloring pattern excellent in heat-resistant yellowing.
まず、本発明の共重合体(A)について説明する。
本発明の共重合体(A)は、炭素数10〜20の橋かけ環式炭化水素基を有する重合性モノマー(a−1)及び/または化学式(1)で示される重合性モノマー(a−1’)と、化学式(2)で示される重合性モノマー(a−2)を重合してなり、かつ重量平均分子量(ポリスチレン換算の重量平均分子量)が1000〜50000である。First, the copolymer (A) of the present invention will be described.
The copolymer (A) of the present invention comprises a polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and / or a polymerizable monomer represented by the chemical formula (1) (a- 1 ') and the polymerizable monomer (a-2) represented by the chemical formula (2) are polymerized, and the weight average molecular weight (polystyrene equivalent weight average molecular weight) is 1000 to 50000.
(式(1)中のX及びYは、それぞれ独立して、水素原子、直鎖又は分岐していてもよい炭素数1〜4の炭化水素基を示し、R1及びR2はそれぞれ独立して水素原子、カルボキシル基又は置換基を有していてもよい炭素数1〜20の炭化水素基であって、R1及びR2を結ぶ環状構造をとっていてもよい。)(X and Y in Formula (1) each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 are each independently A hydrogen atom, a carboxyl group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may have a cyclic structure connecting R 1 and R 2. )
共重合体(A)を構成する重合性モノマー(a−1)は、炭素数10〜20の橋かけ環式炭化水素基を有する。ここで、橋かけ環式炭化水素とは、アダマンタン、ノルボルナンに代表される、下記式(3)又は(4)で表される構造を有するものを意味し、橋かけ環式炭化水素基とは、当該構造における一部の水素を除いた残りの部分に相当する基をいう。 The polymerizable monomer (a-1) constituting the copolymer (A) has a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. Here, the bridged cyclic hydrocarbon means one having a structure represented by the following formula (3) or (4) represented by adamantane and norbornane, and the bridged cyclic hydrocarbon group: And a group corresponding to the remaining part of the structure excluding part of hydrogen.
(式(3)中、A1、B1は、それぞれ、直鎖または分岐アルキレン基(環式を含む。)を示し、R4は水素原子またはメチル基を示す。A1、B1は同一であっても、異なっていてもよく、A1、B1の分枝どうしがつながって環状となっていてもよい。)(In Formula (3), A 1 and B 1 each represent a linear or branched alkylene group (including a cyclic group), R 4 represents a hydrogen atom or a methyl group, and A 1 and B 1 are the same. Or they may be different, and the branches of A 1 and B 1 may be connected to form a ring.)
(式(4)中、A2、B2、Lは、それぞれ、直鎖または分岐アルキレン基(環式を含む。)を示し、R5は水素原子またはメチル基を示す。A2、B2、Lは同一であっても、異なっていてもよく、A2、B2、Lの分枝どうしがつながって環状となっていてもよい。)(In the formula (4), A 2 , B 2 and L each represent a linear or branched alkylene group (including a cyclic group), and R 5 represents a hydrogen atom or a methyl group. A 2 and B 2 , L may be the same or different, and the branches of A 2 , B 2 , and L may be connected to form a ring.)
モノマー(a−1)としては、炭素数10〜20の橋かけ環式炭化水素基を有する(メタ)アクリレートが好ましく、アダマンチル(メタ)アクリレート又は下記式(5)で表される構造を有する(メタ)アクリレートがより好ましい。 The monomer (a-1) is preferably a (meth) acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and has a structure represented by adamantyl (meth) acrylate or the following formula (5) ( More preferred is (meth) acrylate.
(式(5)中、R6〜R8はそれぞれ水素原子またはメチル基を表す。R9、R10は水素原子もしくはメチル基、又は互いに連結して飽和もしくは不飽和の環を形成していても良く、当該環は好ましくは5員環もしくは6員環である。*は(メタ)アクリレート基に連結される結合手を表す。)(In the formula (5), R 6 to R 8 each represent a hydrogen atom or a methyl group. R 9 and R 10 are each a hydrogen atom or a methyl group, or are linked to each other to form a saturated or unsaturated ring. The ring is preferably a 5-membered ring or a 6-membered ring. * Represents a bond connected to the (meth) acrylate group.)
上記モノマー(a−1)の例としては、ジシクロペンテニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレートなどが挙げられる。これらの中でも、耐熱分解性、密着性、現像性などの観点からジシクロペンタニルメタクリレートが更に好ましい。これらは、単独で又は2種以上を組み合わせて用いることができる。 Examples of the monomer (a-1) include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate and the like. Among these, dicyclopentanyl methacrylate is more preferable from the viewpoint of thermal decomposition resistance, adhesion, developability, and the like. These can be used alone or in combination of two or more.
また、本発明の共重合体(A)の別の構成モノマーとして、下記の一般式(1): Further, as another constituent monomer of the copolymer (A) of the present invention, the following general formula (1):
(式中、X及びYはそれぞれ独立して、水素原子、又は炭素数1〜4の直鎖若しくは分岐鎖の炭化水素基を表し、R1及びR2はそれぞれ独立して、水素原子、カルボキシル基又は置換基を有していても良い炭素数1〜20の炭化水素基を表し、R1及びR2が連結された環状構造を形成してもよい)を使用することができる。(In the formula, X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms; R 1 and R 2 each independently represent a hydrogen atom, a carboxyl group; Represents a hydrocarbon group having 1 to 20 carbon atoms which may have a group or a substituent, and may form a cyclic structure in which R 1 and R 2 are linked).
モノマー(a−1’)は、一般式(1)で示される化学構造を有していれば特に限定されない。一般式(1)において、炭素数1〜4の直鎖若しくは分岐鎖の炭化水素基を表すX及びYの例としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、t−ブチル基などが挙げられる。また、置換基を有していても良い炭素数1〜20の炭化水素基における置換基としてはアルコキシ基、アリール基などが挙げられる。R1及びR2の例としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、t−ブチル基、t−アミル基、ステアリル基、ラウリル基、2−エチルヘキシル基などの直鎖又は分岐鎖のアルキル基;フェニルなどのアリール基;シクロヘキシル基、t−ブチルシクロヘキシル基、ジシクロペンタジエニル基、トリシクロデカニル基、イソボルニル基、アダマンチル基、2−メチル−2−アダマンチル基などの脂環式基;1−メトキシエチル基、1−エトキシエチル基などのアルコキシ基で置換されたアルキル基;ベンジルなどのアリール基で置換されたアルキル基などが挙げられる。The monomer (a-1 ′) is not particularly limited as long as it has a chemical structure represented by the general formula (1). In the general formula (1), examples of X and Y representing a linear or branched hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Isobutyl group, t-butyl group and the like. Moreover, an alkoxy group, an aryl group, etc. are mentioned as a substituent in a C1-C20 hydrocarbon group which may have a substituent. Examples of R 1 and R 2 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2- Linear or branched alkyl group such as ethylhexyl group; aryl group such as phenyl; cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl Examples include alicyclic groups such as a 2-adamantyl group; alkyl groups substituted with an alkoxy group such as 1-methoxyethyl group and 1-ethoxyethyl group; alkyl groups substituted with an aryl group such as benzyl.
一般式(1)で示される化学構造を有するモノマー(a−1’)の例としては、ノルボルネン(ビシクロ[2.2.1]ヘプト−2−エン)、5−メチルビシクロ[2.2.1]ヘプト−2−エン、5−エチルビシクロ[2.2.1]ヘプト−2−エン、テトラシクロ[4.4.0.12,5.17,10]ドデカ−3−エン、8−メチルテトラシクロ[4.4.0.12,5.17,10]ドデカ−3−エン、8−エチルテトラシクロ[4.4.0.12,5.17,10]ドデカ−3−エン、ジシクロペンタジエン、トリシクロ[5.2.1.02,6]デカ−8−エン、トリシクロ[5.2.1.02,6]デカ−3−エン、トリシクロ[4.4.0.12,5]ウンデカ−3−エン、トリシクロ[6.2.1.01,8]ウンデカ−9−エン、トリシクロ[6.2.1.01,8]ウンデカ−4−エン、テトラシクロ[4.4.0.12,5.17,10.01,6]ドデカ−3−エン、8−メチルテトラシクロ[4.4.0.12,5.17,10.01,6]ドデカ−3−エン、8−エチリデンテトラシクロ[4.4.0.12,5.17,12]ドデカ−3−エン、8−エチリデンテトラシクロ[4.4.0.12,5.17,10.01,6]ドデカ−3−エン、ペンタシクロ[6.5.1.13,6.02,7.09,13]ペンタデカ−4−エン、ペンタシクロ[7.4.0.12,5.19,12.08,13]ペンタデカ−3−エン、5−ノルボルネン−2−カルボン酸、5−ノルボルネン−2,3−ジカルボン酸、5−ノルボルネン−2,3−ジカルボン酸無水物などが挙げられる。これらの中でも、耐熱分解性、密着性、現像特性などの観点から、ノルボルネン、ジシクロペンタジエン、5−ノルボルネン−2,3−ジカルボン酸無水物が好ましい。これらは、単独で又は2種以上を組み合わせて用いることができる。Examples of the monomer (a-1 ′) having the chemical structure represented by the general formula (1) include norbornene (bicyclo [2.2.1] hept-2-ene) and 5-methylbicyclo [2.2. 1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 2,6 ] dec-8-ene, tricyclo [5.2.1.0 2,6 ] dec-3 -Ene, tricyclo [4.4.0.1 2,5 ] undec-3-ene, tricyclo [6.2.1.0 1,8 ] undec-9-ene, tricyclo [6.2.1.0 1,8 ] undec-4-ene, tetracyclo [4.4.0.1 2,5 . 1 7,10 . 0 1,6 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 . 0 1,6 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 2,5 . 1 7,12 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 2,5 . 1 7,10 . 0 1,6 ] dodec-3-ene, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] pentadeca-4-ene, pentacyclo [7.4.0.1 2,5. 1 9,12 . 0 8,13] pentadeca-3-ene, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and 5-norbornene-2,3-dicarboxylic anhydride. Among these, norbornene, dicyclopentadiene, and 5-norbornene-2,3-dicarboxylic acid anhydride are preferable from the viewpoints of thermal decomposition resistance, adhesion, development characteristics, and the like. These can be used alone or in combination of two or more.
本発明の必須構成モノマーとして、下記化学式(2)で示される重合性モノマー(a−2)を使用する。 As an essential constituent monomer of the present invention, a polymerizable monomer (a-2) represented by the following chemical formula (2) is used.
(式(2)のR3は水素原子またはメチル基でnは1〜4の整数を表す。)(R 3 in formula (2) is a hydrogen atom or a methyl group, and n represents an integer of 1 to 4.)
重合性モノマー(a−2)としては、特に限定されず一般式中のn=1〜4の混合物でも構わないが、所望の耐熱分解性を得る為には一般式中n=1のエトキシ化o−フェニルフェノール(メタ)アクリレートが好ましい。市販品として、東亜合成(株)製アロニックスTO−1463、新中村化学工業(株)製NKエステルA−LEN−10、日本化薬(株)製KAYARAD OPP−1等が存在する。 The polymerizable monomer (a-2) is not particularly limited, and may be a mixture of n = 1 to 4 in the general formula. However, in order to obtain a desired thermal decomposition resistance, n = 1 in the general formula. o-Phenylphenol (meth) acrylate is preferred. Examples of commercially available products include Aronix TO-1463 manufactured by Toa Gosei Co., Ltd., NK Ester A-LEN-10 manufactured by Shin-Nakamura Chemical Co., Ltd., KAYARAD OPP-1 manufactured by Nippon Kayaku Co., Ltd.
また、その他のモノマーとして(a−1)、(a−1’)及び(a−2)以外の共重合可能なモノマー(a−3)を重合することも可能である。重合性モノマー(a−3)は、一般にエチレン性不飽和基を有するラジカル重合性化合物であり、その例としては、ブタジエンなどのジエン類;メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、イソ−プロピル(メタ)アクリレート、n−ブチル(メタ)アクリルレート、sec−ブチル(メタ)アクリレート、イソ−ブチル(メタ)アクリレート、tert−ブチル(メタ)アクリルレート、ペンチル(メタ)アクリレート、ネオペンチル(メタ)アクリレート、ベンジル(メタ)アクリレート、イソアミル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ドデシル(メタ)アクリレート、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、メチルシクロヘキシル(メタ)アクリレート、エチルシクロヘキシル(メタ)アクリレート、1,4−シクロヘキサンジメタノールモノ(メタ)アクリレート、ロジン(メタ)アクリレート、ノルボルニル(メタ)アクリレート、5−メチルノルボルニル(メタ)アクリレート、5−エチルノルボルニル(メタ)アクリレート、アリル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、1,1,1−トリフルオロエチル(メタ)アクリレート、パーフルオロエチル(メタ)アクリレート、パーフルオロ−n−プロピル(メタ)アクリレート、パーフルオロ−イソ−プロピル(メタ)アクリレート、トリフェニルメチル(メタ)アクリレート、クミル(メタ)アクリレート、3−(N,N−ジメチルアミノ)プロピル(メタ)アクリレート、グリセリロールモノ(メタ)アクリレート、ブタントリオールモノ(メタ)アクリレート、ペンタントリオールモノ(メタ)アクリレート、ナフタレン(メタ)アクリレート、アントラセン(メタ)アクリレートなどの(メタ)アクリル酸エステル類;(メタ)アクリル酸アミド、(メタ)アクリル酸N,N−ジメチルアミド、(メタ)アクリル酸N,N−ジエチルアミド、(メタ)アクリル酸N,N−ジプロピルアミド、(メタ)アクリル酸N,N−ジ−イソ−プロピルアミド、(メタ)アクリル酸アントラセニルアミドなどの(メタ)アクリル酸アミド;(メタ)アクリル酸アニリド、(メタ)アクリロイルニトリル、アクロレイン、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、N−ビニルピロリドン、ビニルピリジン、酢酸ビニル、ビニルトルエンなどのビニル化合物;スチレン、スチレンのα−、o−、m−、p−アルキル、ニトロ、シアノ、アミド誘導体;シトラコン酸ジエチル、マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチルなどの不飽和ジカルボン酸ジエステル;N−フェニルマレイミド、N−シクロヘキシルマレイミド、N−ラウリルマレイミド、N−(4−ヒドロキシフェニル)マレイミドなどのモノマレイミド類;(メタ)アクリル酸、クロトン酸、桂皮酸などの不飽和一塩基酸;グリシジル(メタ)アクリレート、脂環式エポキシを有する3,4−エポキシシクロヘキシルメチル(メタ)アクリレートおよびそのラクトン付加物[例えば、ダイセル化学工業(株)製サイクロマーA200、M100]、3,4−エポキシシクロヘキシルメチル−3´,4´−エポキシシクロヘキサンカルボキシレートのモノ(メタ)アクリル酸エステル、ジシクロペンテニル(メタ)アクリレートのエポキシ化物、ジシクロペンテニルオキシエチル(メタ)アクリレートのエポキシ化物などのエポキシ基を有するラジカル重合性モノマー;無水マレイン酸、無水イタコン酸、無水シトラコン酸などの不飽和多塩基酸無水物が挙げられる。これらは、単独で又は2種以上を組み合わせて用いることができる。 Moreover, it is also possible to polymerize the copolymerizable monomer (a-3) other than (a-1), (a-1 ′) and (a-2) as other monomers. The polymerizable monomer (a-3) is generally a radically polymerizable compound having an ethylenically unsaturated group. Examples thereof include dienes such as butadiene; methyl (meth) acrylate, ethyl (meth) acrylate, n- Propyl (meth) acrylate, iso-propyl (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, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopent (Meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate , 5-methylnorbornyl (meth) acrylate, 5-ethylnorbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate , Perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl ( Acrylate), 3- (N, N-dimethylamino) propyl (meth) acrylate, glyceryl mono (meth) acrylate, butanetriol mono (meth) acrylate, pentanetriol mono (meth) acrylate, naphthalene (meth) acrylate, (Meth) acrylic acid esters such as anthracene (meth) acrylate; (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid (Meth) acrylic amides such as N, N-dipropylamide, (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide; (meth) acrylic acid anilide, ( (Meth) acryloylnitrile, acrolein, vinyl chloride, salt Vinyl compounds such as vinylidene fluoride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene; styrene, α-, o-, m-, p-alkyl of styrene, nitro, cyano, Amide derivatives; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide Monomaleimides such as; (meth) acrylic acid, crotonic acid, cinnamic acid and other unsaturated monobasic acids; glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having alicyclic epoxy, and the like Lactone adduct [eg , Daicel Chemical Industries, Ltd., Cyclomer A200, M100], 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate mono (meth) acrylate, dicyclopentenyl (meth) acrylate Radical polymerizable monomers having an epoxy group such as an epoxidized product and an epoxidized product of dicyclopentenyloxyethyl (meth) acrylate; unsaturated polybasic acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. These can be used alone or in combination of two or more.
本共重合体(A)は現像性を向上させる為カルボキシル基を有することが好ましい。共重合体(A)にカルボキシルを付加する手法としては、重合性モノマー(a−3)としてカルボキシル基を有するモノマーを共重合することが挙げられる。更に感光性を高める為、そのカルボキシル基の一部にエポキシ基を有するモノマーを付加し二重結合も導入することが好ましい。または、重合性モノマー(a−3)として先にエポキシ基を有するモノマーを共重合し、カルボキシル基を有するモノマーを付加して生じた水酸基に酸無水物を付加することでもカルボキシル基と二重結合が付加できる。もしくは、重合性モノマー(a−3)として不飽和多塩基酸無水物を共重合させ、その酸無水物に水酸基を有するモノマーを付加することでもカルボキシル基と二重結合が付加できる。 The copolymer (A) preferably has a carboxyl group in order to improve developability. As a method for adding carboxyl to the copolymer (A), a monomer having a carboxyl group may be copolymerized as the polymerizable monomer (a-3). In order to further improve the photosensitivity, it is preferable to add a monomer having an epoxy group to a part of the carboxyl group and introduce a double bond. Alternatively, a carboxyl group and a double bond can be obtained by copolymerizing a monomer having an epoxy group as the polymerizable monomer (a-3) and adding an acid anhydride to a hydroxyl group generated by adding a monomer having a carboxyl group. Can be added. Alternatively, a carboxyl group and a double bond can be added by copolymerizing an unsaturated polybasic acid anhydride as the polymerizable monomer (a-3) and adding a monomer having a hydroxyl group to the acid anhydride.
モノマー(a−1)とモノマー(a−1’)は一方を用いても良く、両方を用いても良いが、これをまとめて「モノマー(a−1)及び/又はモノマー(a−1’)」と表し、量については、その全体を意味するものとすると、モノマー(a−1)及び/又はモノマー(a−1’)の配合割合は特に制限はないが、モノマー(a−1)及び/又はモノマー(a−1’)、モノマー(a−2)、並びに、重合性モノマー(a−3)の合計を100モル%とした場合に、好ましくは2〜50モル%、より好ましくは2〜30モル%である。モノマー(a−1)及び/又はモノマー(a−1’)の配合割合が2モル%未満であると、所望の耐熱黄変性が得られなくなる可能性がある。一方、この配合割合が50モル%を超えると、モノマー(a−2)の配合割合が少なくなり、所望の耐熱分解性が得られなくなる可能性がある。 One of the monomer (a-1) and the monomer (a-1 ′) may be used, or both of them may be used, but these may be collectively referred to as “monomer (a-1) and / or monomer (a-1 ′). ) ", And the amount means the whole of the monomer (a-1) and / or the monomer (a-1 ') is not particularly limited, the monomer (a-1) And / or when the total of the monomer (a-1 ′), the monomer (a-2), and the polymerizable monomer (a-3) is 100 mol%, preferably 2 to 50 mol%, more preferably 2 to 30 mol%. When the blending ratio of the monomer (a-1) and / or the monomer (a-1 ′) is less than 2 mol%, the desired heat-resistant yellowing may not be obtained. On the other hand, when the blending ratio exceeds 50 mol%, the blending ratio of the monomer (a-2) decreases, and the desired heat decomposability may not be obtained.
また、モノマー(a−2)の配合割合は特に制限はないが、モノマー(a−1)及び/又はモノマー(a−1’)、モノマー(a−2)、並びに重合性モノマー(a−3)の合計を100モル%とした場合に、好ましくは10〜80モル%、より好ましくは20〜70モル%である。モノマー(a−2)の配合割合が10モル%未満であると、所望の耐熱分解性が得られなくなる可能性がある。一方、この配合割合が80モル%を超えると、モノマー(a−1)及び/又はモノマー(a−1’)配合割合が少なくなり、所望の耐熱黄変性が得られなくなる可能性がある。 The mixing ratio of the monomer (a-2) is not particularly limited, but the monomer (a-1) and / or monomer (a-1 ′), monomer (a-2), and polymerizable monomer (a-3) ) Is preferably 10 to 80 mol%, more preferably 20 to 70 mol%. When the blending ratio of the monomer (a-2) is less than 10 mol%, desired heat decomposability may not be obtained. On the other hand, when the blending ratio exceeds 80 mol%, the blending ratio of the monomer (a-1) and / or the monomer (a-1 ′) decreases, and the desired heat-resistant yellowing may not be obtained.
モノマー(a−3)を加える場合、その配合割合は特に制限はないが、モノマー(a−1)及び/又はモノマー(a−1’)、モノマー(a−2)、並びに重合性モノマー(a−3)の合計を100モル%とした場合に、好ましくは18〜88モル%、より好ましくは25〜70モル%である。モノマー(a−3)の配合割合が18モル%以上のほうが、現像性、感度をより高めるためには効果的である。一方、この配合割合が88モル%を超えると、モノマー(a−1)及び/又はモノマー(a−1’)、モノマー(a−2)の配合割合が少なくなり、所望の耐熱分解性、耐熱黄変性が得られなくなる可能性がある。 When the monomer (a-3) is added, the blending ratio is not particularly limited, but the monomer (a-1) and / or monomer (a-1 ′), monomer (a-2), and polymerizable monomer (a When the sum of -3) is 100 mol%, it is preferably 18 to 88 mol%, more preferably 25 to 70 mol%. A compounding ratio of the monomer (a-3) of 18 mol% or more is more effective for further improving developability and sensitivity. On the other hand, when the blending ratio exceeds 88 mol%, the blending ratio of the monomer (a-1) and / or the monomer (a-1 ′) and the monomer (a-2) decreases, and the desired thermal decomposition resistance and heat resistance. Yellowing may not be obtained.
モノマー(a−1)及び/又はモノマー(a−1’)、モノマー(a−2)、並びに重合性モノマー(a−3)(任意)を原料として用いる共重合反応は、当該技術分野において公知のラジカル重合方法に従って行うことができる。例えば、モノマー(a−1)及び/又はモノマー(a−1’)、モノマー(a−2)、並びに任意のモノマーを溶剤に溶解した後、その溶液に重合開始剤を添加し、50〜130℃で1〜20時間反応させればよい。 Copolymerization reaction using monomer (a-1) and / or monomer (a-1 ′), monomer (a-2), and polymerizable monomer (a-3) (optional) as raw materials is known in the art. The radical polymerization method can be used. For example, the monomer (a-1) and / or the monomer (a-1 ′), the monomer (a-2), and an arbitrary monomer are dissolved in a solvent, and then a polymerization initiator is added to the solution. What is necessary is just to make it react at 1 degreeC for 20 hours.
この共重合反応に用いることが可能な溶剤としては、特に限定されないが、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテートなどのグリコールエーテル系溶剤;トルエン、キシレンなどの炭化水素系溶剤、酢酸エチルなどの反応性官能基を有していない溶剤が挙げられる。これらは、単独で又は2種以上を組み合わせて用いることができる。また、これらの中でも、グリコールエーテル系溶剤が好ましい。 Solvents that can be used for this copolymerization reaction are not particularly limited. For example, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; hydrocarbon solvents such as toluene and xylene; ethyl acetate Examples thereof include a solvent having no reactive functional group. These can be used alone or in combination of two or more. Of these, glycol ether solvents are preferred.
溶剤の配合量は、特に限定されないが、モノマー(a−1)及び/又はモノマー(a−1’)、モノマー(a−2)、並びに重合性モノマー(a−3)の合計を100質量部とした場合に、一般に30〜1000質量部、好ましくは50〜800質量部である。特に、溶剤の配合量を1000質量部以下とすることで、連鎖移動作用によって共重合体の分子量の低下を抑制し、且つ共重合体の粘度を適切な範囲に制御することができる。また、溶剤の配合量を30質量部以上とすることで、異常な重合反応を防止し、重合反応を安定して行うことができると共に、共重合体の着色やゲル化を防止することもできる。 Although the compounding quantity of a solvent is not specifically limited, The total of a monomer (a-1) and / or monomer (a-1 '), a monomer (a-2), and a polymerizable monomer (a-3) is 100 mass parts. In general, it is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. In particular, by setting the blending amount of the solvent to 1000 parts by mass or less, it is possible to suppress a decrease in the molecular weight of the copolymer by a chain transfer action and to control the viscosity of the copolymer within an appropriate range. Further, by setting the blending amount of the solvent to 30 parts by mass or more, an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably performed, and the coloring and gelation of the copolymer can also be prevented. .
また、この共重合反応に用いることが可能な重合開始剤としては、特に限定されないが、例えば、アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、過酸化ベンゾイル、t−ブチルパーオキシ−2−エチルヘキサノエートなどが挙げられる。これらは、単独で又は2種以上を組み合わせて用いることができる。
重合開始剤の配合量は、モノマー(a−1)及び/又はモノマー(a−1’)、モノマー(a−2)、並びに重合性モノマー(a−3)の合計を100質量部とした場合に、一般に0.5〜20質量部、好ましくは1.0〜10質量部である。
なお、有機溶剤を使用せずに、モノマー(a−1)及び/又はモノマー(a−1’)、モノマー(a−2)、並びに重合性モノマー(a−3)(任意)と重合開始剤とを使用して塊状重合を行ってもよい。In addition, the polymerization initiator that can be used for the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2- Examples include ethyl hexanoate. These can be used alone or in combination of two or more.
The amount of the polymerization initiator is 100 parts by mass of the total of the monomer (a-1) and / or the monomer (a-1 ′), the monomer (a-2), and the polymerizable monomer (a-3). Generally, it is 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass.
In addition, a monomer (a-1) and / or a monomer (a-1 '), a monomer (a-2), a polymerizable monomer (a-3) (optional), and a polymerization initiator are used without using an organic solvent. And bulk polymerization may be performed.
上記の共重合反応で得られた共重合体(A)にカルボキシル基、エポキシ基もしくは酸無水物基が存在する場合は、さらに二重結合を導入することが可能である。これにより、感光性樹脂組成物の感度や現像性が向上する。
共重合体(A)中のカルボキシル基、エポキシ基もしくは酸無水物基に二重結合を付加する反応は、共重合体にそれぞれエポキシ基含有モノマー、カルボキシル基含有モノマー、水酸基含有モノマーと重合禁止剤及び触媒を添加し、50〜150℃、好ましくは80〜130℃で反応を行えばよい。なお、この付加反応では、共重合反応に用いた溶剤が含まれていても特に問題はないため、共重合反応が終了した後に溶剤を除去することなく付加反応を行うことができる。
また、ここでは上記の重合性モノマー(a−3)で挙げられた化合物を使用することができる。
ここで、重合禁止剤は、共重合体の重合によるゲル化を防ぐために添加される。重合禁止剤としては、特に限定されないが、例えば、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテルなどが挙げられる。また、触媒としては、特に限定されないが、例えば、トリエチルアミンのような第3級アミン、トリエチルベンジルアンモニウムクロライドのような第4級アンモニウム塩、トリフェニルホスフィンのようなリン化合物、クロムのキレート化合物などが挙げられる。When a carboxyl group, an epoxy group, or an acid anhydride group is present in the copolymer (A) obtained by the above copolymerization reaction, a double bond can be further introduced. Thereby, the sensitivity and developability of the photosensitive resin composition are improved.
The reaction of adding a double bond to the carboxyl group, epoxy group or acid anhydride group in the copolymer (A) is carried out by adding an epoxy group-containing monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer and a polymerization inhibitor to the copolymer And a catalyst may be added, and the reaction may be carried out at 50 to 150 ° C, preferably 80 to 130 ° C. In this addition reaction, there is no particular problem even if the solvent used in the copolymerization reaction is included. Therefore, the addition reaction can be carried out without removing the solvent after the completion of the copolymerization reaction.
Moreover, the compound quoted by said polymerizable monomer (a-3) can be used here.
Here, the polymerization inhibitor is added to prevent gelation due to polymerization of the copolymer. Although it does not specifically limit as a polymerization inhibitor, For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, etc. are mentioned. The catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelate compounds of chromium. Can be mentioned.
上記のようにして得られる共重合体(A)の酸価(JIS K6901 5.3)は、制限はないが、感光性樹脂に使用する場合、通常20〜300KOHmg/g、好ましくは30〜200KOHmg/gである。この酸価が20KOHmg/g未満であると、感光性樹脂としての現像性が低下してしまうことがある。一方、この酸価が300KOHmg/gを超えると、アルカリ現像液に対して露光部分(光硬化部分)が溶解し易くなることがある。
また、共重合体(A)の分子量(ポリスチレン換算の重量平均分子量)は、通常1000〜50000、好ましくは3000〜40000である。この分子量が1000未満であると、現像後に着色パターンの欠けが発生し易くなることがある。一方、この分子量が50000を超えると、現像時間が長くなり過ぎてしまい、実用性に欠けることがある。
また、共重合体(A)が不飽和基を有する場合、その不飽和基当量は制限はないが通常100〜4000g/mol、好ましくは200〜3000g/molである。この不飽和基当量が100g/mol以上の方が耐熱分解性、耐熱黄変性をより高めるには効果的である。一方、この不飽和基当量が4000g/mol未満の方が感度をより高めるには効果的である。The acid value (JIS K6901 5.3) of the copolymer (A) obtained as described above is not limited, but when used in a photosensitive resin, it is usually 20 to 300 KOHmg / g, preferably 30 to 200 KOHmg. / G. If the acid value is less than 20 KOHmg / g, the developability as a photosensitive resin may be lowered. On the other hand, when the acid value exceeds 300 KOHmg / g, the exposed portion (photocured portion) may be easily dissolved in the alkali developer.
Moreover, the molecular weight (polystyrene conversion weight average molecular weight) of a copolymer (A) is 1000-50000 normally, Preferably it is 3000-40000. If the molecular weight is less than 1000, a lack of a colored pattern may easily occur after development. On the other hand, if the molecular weight exceeds 50,000, the development time becomes too long, and the practicality may be lacking.
Moreover, when a copolymer (A) has an unsaturated group, the unsaturated group equivalent is although there is no restriction | limiting, Usually, it is 100-4000 g / mol, Preferably it is 200-3000 g / mol. When the unsaturated group equivalent is 100 g / mol or more, it is more effective to further improve the heat decomposition resistance and heat yellowing. On the other hand, when the unsaturated group equivalent is less than 4000 g / mol, it is effective to further increase the sensitivity.
さらに、本発明は共重合体(A)、溶剤(B)および任意に反応性希釈剤(C)を含む樹脂組成物に関する。また本発明の感光性樹脂組成物は、共重合体(A)、溶剤(B)、反応性希釈剤(C)、光重合開始剤(D)および任意に着色剤(E)を含む。 The present invention further relates to a resin composition comprising a copolymer (A), a solvent (B) and optionally a reactive diluent (C). Moreover, the photosensitive resin composition of this invention contains a copolymer (A), a solvent (B), a reactive diluent (C), a photoinitiator (D), and the coloring agent (E) arbitrarily.
溶剤(B)は、共重合体(A)と反応しない不活性な溶剤であれば特に限定されない。
溶剤(B)としては、共重合体(A)を製造する際(共重合反応)に用いた溶剤と同じものを用いることができ、共重合反応後に含まれている溶剤をそのまま用いることもでき、更に加えることもできる。また、その他の成分を加える際に、そこに共存しているものでも良い。具体的には、溶剤(B)の例として、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、酢酸エチル、酢酸ブチル、酢酸イソプロピル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールエチルエーテルアセテートなどが挙げられる。これらは、単独で又は2種以上を組み合わせて用いることができる。また、これらの中でも、共重合体(A)を製造する際(共重合反応)において使用されるプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテートなどのグリコールエーテル系溶剤が好ましい。The solvent (B) is not particularly limited as long as it is an inert solvent that does not react with the copolymer (A).
As the solvent (B), the same solvent as used in the production of the copolymer (A) (copolymerization reaction) can be used, and the solvent contained after the copolymerization reaction can be used as it is. You can add more. Further, when other components are added, they may coexist there. Specific examples of the solvent (B) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether , Tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate and the like. These can be used alone or in combination of two or more. Among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate used in producing the copolymer (A) (copolymerization reaction) are preferable.
本実施の形態の樹脂組成物又は感光性樹脂組成物における溶剤(B)の配合量は、当該組成物中の溶剤(B)を除く成分の総和を100質量部とすると、一般に30〜1000質量部、好ましくは50〜800質量部であり、より好ましくは100〜700質量部である。この範囲の配合量であれば、適切な粘度を有する樹脂組成物又は感光性樹脂組成物となる。 The compounding amount of the solvent (B) in the resin composition or photosensitive resin composition of the present embodiment is generally 30 to 1000 masses when the total of the components excluding the solvent (B) in the composition is 100 mass parts. Parts, preferably 50 to 800 parts by mass, more preferably 100 to 700 parts by mass. If it is the compounding quantity of this range, it will become the resin composition or photosensitive resin composition which has a suitable viscosity.
反応性希釈剤(C)としては特に限定されないが、例えば、スチレン、α−メチルスチレン、α−クロロメチルスチレン、ビニルトルエン、ジビニルベンゼン、ジアリルフタレート、ジアリルベンゼンホスホネートなどの芳香族ビニル系モノマー類;酢酸ビニル、アジピン酸ビニルなどのポリカルボン酸モノマー類;メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、β−ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリス(ヒドロキシエチル)イソシアヌレートのトリ(メタ)アクリレートなどの(メタ)アクリル系モノマー;トリアリルシアヌレートなどが挙げられる。これらは、単独で又は2種以上を組み合わせて用いることができる。 Although it does not specifically limit as a reactive diluent (C), For example, aromatic vinyl-type monomers, such as styrene, alpha-methyl styrene, alpha-chloromethyl styrene, vinyl toluene, divinyl benzene, diallyl phthalate, diallyl benzene phosphonate; 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 group (Meth) such as pandi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate Acrylic monomers; triallyl cyanurate and the like. These can be used alone or in combination of two or more.
本実施の形態の樹脂組成物又は感光性樹脂組成物における反応性希釈剤(C)の配合量は、当該組成物中の溶剤(B)を除く成分の総和を100質量部とすると、一般に10〜90質量部、好ましくは20〜80質量部であり、より好ましくは25〜70質量部である。この範囲の配合量であれば、適切な粘度を有する樹脂組成物又は感光性樹脂組成物となり、感光性樹脂組成物は適切な光硬化性を有する。The amount of the reactive diluent in the resin composition or photosensitive resin composition of the present embodiment (C), when the sum of the components excluding the solvent (B) in the composition is 100 parts by weight, generally 10 It is -90 mass parts, Preferably it is 20-80 mass parts, More preferably, it is 25-70 mass parts. If it is the compounding quantity of this range, it will become the resin composition or photosensitive resin composition which has an appropriate viscosity, and the photosensitive resin composition has appropriate photocurability.
光重合開始剤(D)としては、特に限定されないが、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテルなどのベンゾインとそのアルキルエーテル類;アセトフェノン、2,2−ジメトキシ−2−フェニルアセトフェノン、1,1−ジクロロアセトフェノン、4−(1−t−ブチルジオキシ−1−メチルエチル)アセトフェノンなどのアセトフェノン類;2−メチルアントラキノン、2−アミルアントラキノン、2−t−ブチルアントラキノン、1−クロロアントラキノンなどのアントラキノン類;2,4−ジメチルチオキサントン、2,4−ジイソプロピルチオキサントン、2−クロロチオキサントンなどのチオキサントン類;アセトフェノンジメチルケタール、ベンジルジメチルケタールなどのケタール類;ベンゾフェノン、4−(1−t−ブチルジオキシ−1−メチルエチル)ベンゾフェノン、3,3’,4,4’−テトラキス(t−ブチルジオキシカルボニル)ベンゾフェノンなどのベンゾフェノン類;2−メチル−1−[4−(メチルチオ)フェニル]−2−モルホリノ−プロパン−1−オン;2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)ブタノン−1;アシルホスフィンオキサイド類;及びキサントン類などが挙げられる。これらは、単独で又は2種以上を組み合わせて用いることができる。 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 ethers; acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 1, Acetophenones such as 1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as zophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 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; acylphosphine oxides; and xanthones It is done. These can be used alone or in combination of two or more.
本実施の形態の感光性樹脂組成物における光重合開始剤(D)の配合量は、感光性樹脂組成物中の溶剤(B)を除く成分の総和を100質量部とすると、一般に0.1〜30質量部、好ましくは0.5〜20質量部、より好ましくは1〜15質量部である。この範囲の配合量であれば、適切な光硬化性を有する感光性樹脂組成物となる。 The blending amount of the photopolymerization initiator (D) in the photosensitive resin composition of the present embodiment is generally 0.1 when the sum of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. -30 mass parts, Preferably it is 0.5-20 mass parts, More preferably, it is 1-15 mass parts. If it is the compounding quantity of this range, it will become the photosensitive resin composition which has appropriate photocurability.
着色剤(E)は、溶剤(B)に溶解又は分散するものであれば特に限定されず、例えば、染料や顔料などが挙げられる。
特に、従来の感光性樹脂組成物では、染料を用いると輝度が高い着色パターンを得ることができたが、顔料を用いた場合に比べて着色パターンの耐熱性が低くなるという問題があった。これに対して、本実施の形態の感光性樹脂組成物では、染料を用いても耐熱性に優れた着色パターンを得ることができる。The colorant (E) is not particularly limited as long as it dissolves or disperses in the solvent (B), and examples thereof include dyes and pigments.
In particular, in the conventional photosensitive resin composition, when a dye is used, a colored pattern having high luminance can be obtained, but there is a problem that the heat resistance of the colored pattern is lower than that when a pigment is used. On the other hand, in the photosensitive resin composition of this Embodiment, even if it uses dye, the coloring pattern excellent in heat resistance can be obtained.
染料としては、溶剤(B)やアルカリ現像液に対する溶解性、感光性樹脂組成物中の他の成分との相互作用、耐熱性などの観点から、カルボン酸などの酸性基を有する酸性染料、酸性染料の窒素化合物との塩、酸性染料のスルホンアミド体などを用いることが好ましい。このような染料の例としては、acid alizarin violet N;acid black1、2、24、48;acid blue1、7、9、25、29、40、45、62、70、74、80、83、90、92、112、113、120、129、147;acid chrome violet K;acid Fuchsin;acid green1、3、5、25、27、50;acid orange6、7、8、10、12、50、51、52、56、63、74、95;acid red1、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 yellow1、3、9、11、17、23、25、29、34、36、42、54、72、73、76、79、98、99、111、112、114、116; food yellow3及びこれらの誘導体などが挙げられる。これらの中でも、アゾ系、キサンテン系、アンスラキノン系もしくはフタロシアニン系の酸性染料が好ましい。これらは、目的とする画素の色に応じて、単独で又は2種以上を組み合わせて用いることができる。 Examples of the dye include acidic dyes having acidic groups such as carboxylic acid, acidic acids, from the viewpoints of solubility in the solvent (B) and the alkaline developer, interaction with other components in the photosensitive resin composition, and heat resistance. It is preferable to use a salt of a dye with a nitrogen compound, a sulfonamide of an acidic dye, or the like. Examples of such dyes 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; acid chroma 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 red1, 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, 38, 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 yellow1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow3 and these Derivatives and the like. Among these, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These can be used alone or in combination of two or more depending on the color of the target pixel.
顔料の例としては、C.I.ピグメントイエロー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などの黄色顔料;C.I.ピグメントオレンジ13、31、36、38、40、42、43、51、55、59、61、64、65、71、73などの橙色顔料;C.I.ピグメントレッド9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265などの赤色顔料;C.I.ピグメントブルー15、15:3、15:4、15:6、60などの青色顔料;C.I.ピグメントバイオレット1、19、23、29、32、36、38などのバイオレット色顔料;C.I.ピグメントグリーン7、36、58などの緑色顔料;C.I.ピグメントブラウン23、25などの茶色顔料;C.I.ピグメントブラック1、7、カーボンブラック、チタンブラック、酸化鉄などの黒色顔料などが挙げられる。これらは、目的とする画素の色に応じて、単独で又は2種以上を組み合わせて用いることができる。
なお、目的とする画素の色に応じて、上記の染料及び顔料を組み合わせて用いることもできる。Examples of pigments include C.I. I.
Note that the above dyes and pigments may be used in combination depending on the target pixel color.
本実施の形態の感光性樹脂組成物において着色剤(E)を配合する場合の配合量は、感光性樹脂組成物中の溶剤(B)を除く成分の総和を100質量部とすると、一般に5〜80質量部、好ましくは5〜70質量部、より好ましくは10〜60質量部である。 In the photosensitive resin composition of the present embodiment, when the colorant (E) is blended, the amount of the component excluding the solvent (B) in the photosensitive resin composition is generally 5 parts by mass. -80 mass parts, preferably 5-70 mass parts, more preferably 10-60 mass parts.
着色剤(E)として顔料を用いる場合、顔料の分散性を向上させる観点から、公知の分散剤を感光性樹脂組成物に配合してもよい。分散剤としては、経時の分散安定性に優れる高分子分散剤を用いることが好ましい。高分子分散剤の例としては、ウレタン系分散剤、ポリエチレンイミン系分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレングリコールジエステル系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性エステル系分散剤などが挙げられる。このような高分子分散剤として、EFKA(エフカーケミカルズビーブイ(EFKA)社製)、Disperbyk(ビックケミー社製)、ディスパロン(楠本化成株式会社製)、SOLSPERSE(ゼネカ社製)などの商品名で市販されているものを用いてもよい。
本実施の形態の感光性樹脂組成物における分散剤の配合量は、使用する顔料などの種類に応じて適宜設定すればよい。When a pigment is used as the colorant (E), a known dispersant may be added to the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant excellent in dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. System dispersants and the like. As such a polymer dispersant, commercially available under trade names such as EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by GENEKA). You may use what is done.
What is necessary is just to set the compounding quantity of the dispersing agent in the photosensitive resin composition of this Embodiment suitably according to kinds, such as a pigment to be used.
本実施の形態の感光性樹脂組成物が着色剤(E)を含む場合、共重合体(A)、溶剤(B)、反応性希釈剤(C)、光重合開始剤(D)、着色剤(E)の配合量は一般に、感光性樹脂組成物中の溶剤(B)を除く成分の総和を100質量部とすると、共重合体(A)が5〜80質量部、溶剤(B)が30〜1000質量部、反応性希釈剤(C)が10〜90質量部、光重合開始剤(D)が0.1〜30質量部、着色剤(E)が5〜80質量部であり、好ましくは、共重合体(A)が8〜70質量部、溶剤(B)が50〜800質量部、反応性希釈剤(C)が20〜80質量部、光重合開始剤(D)が0.5〜20質量部、着色剤(E)が5〜70質量部であり、更に好ましくは、共重合体(A)が10〜60質量部、溶剤(B)が100〜700質量部、反応性希釈剤(C)が25〜70質量部、光重合開始剤(D)が1〜15質量部、着色剤(E)が10〜60質量部である。 When the photosensitive resin composition of this Embodiment contains a coloring agent (E), a copolymer (A), a solvent (B), a reactive diluent (C), a photoinitiator (D), a coloring agent In general, the blending amount of (E) is 5 to 80 parts by mass of the copolymer (A) and the solvent (B) when the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. 30-1000 parts by mass, reactive diluent (C) is 10-90 parts by mass, photopolymerization initiator (D) is 0.1-30 parts by mass, and colorant (E) is 5-80 parts by mass, Preferably, the copolymer (A) is 8 to 70 parts by mass, the solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) is 20 to 80 parts by mass, and the photopolymerization initiator (D) is 0. 5 to 20 parts by mass, the colorant (E) is 5 to 70 parts by mass, and more preferably, the copolymer (A) is 10 to 60 parts by mass and the solvent (B) is 100 to 7 parts. 0 parts by weight reactive diluent (C) 25 to 70 parts by weight, the photopolymerization initiator (D) is 1 to 15 parts by weight, the coloring agent (E) is 10 to 60 parts by weight.
本実施の形態の感光性樹脂組成物が着色剤(E)を含まない場合でも、共重合体(A)、溶剤(B)、反応性希釈剤(C)、光重合開始剤(D)の配合量は、上記の数値が適用可能である。
本実施の形態の樹脂組成物における、共重合体(A)、溶剤(B)の配合量は、樹脂組成物中の溶剤(B)を除く成分の総和を100質量部とすると、共重合体(A)が、50〜100質量部であり、溶剤(B)が30〜1000質量部、好ましくは50〜800質量部、より好ましくは100〜700質量部である。
本実施の形態の樹脂組成物が反応性希釈剤(C)を含む場合、共重合体(A)、溶剤(B)、反応性希釈剤(C)の配合量は、樹脂組成物中の溶剤(B)を除く成分の総和を100質量部とすると、共重合体(A)は、10〜90質量部、溶剤(B)が30〜1000質量部、反応性希釈剤(C)が10〜90質量部であり、好ましくは、共重合体(A)は、20〜80質量部、溶剤(B)が50〜800質量部、反応性希釈剤(C)が20〜80質量部であり、より好ましくは、共重合体(A)は、30〜75質量部、溶剤(B)が100〜700質量部、反応性希釈剤(C)が25〜70質量部である。Even when the photosensitive resin composition of the present embodiment does not contain the colorant (E), the copolymer (A), the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D). The above numerical values can be applied to the blending amount.
In the resin composition of the present embodiment, the amount of copolymer (A) and solvent (B) is such that the total amount of components excluding solvent (B) in the resin composition is 100 parts by mass. (A) is 50 to 100 parts by mass, and the solvent (B) is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, and more preferably 100 to 700 parts by mass.
When the resin composition of this Embodiment contains a reactive diluent (C), the compounding quantity of a copolymer (A), a solvent (B), and a reactive diluent (C) is the solvent in a resin composition. When the total sum of the components excluding (B) is 100 parts by mass, the copolymer (A) is 10 to 90 parts by mass, the solvent (B) is 30 to 1000 parts by mass, and the reactive diluent (C) is 10 to 10 parts by mass. 90 parts by mass, preferably, the copolymer (A) is 20-80 parts by mass, the solvent (B) is 50-800 parts by mass, and the reactive diluent (C) is 20-80 parts by mass, More preferably, the copolymer (A) is 30 to 75 parts by mass, the solvent (B) is 100 to 700 parts by mass, and the reactive diluent (C) is 25 to 70 parts by mass.
本実施の形態の感光性樹脂組成物は、上記の成分に加えて、所定の特性を付与するために、公知のカップリング剤、レベリング剤、熱重合禁止剤などの公知の添加剤を配合してもよい。これらの添加剤の配合量は、本発明の効果を阻害しない範囲であれば特に限定されない。 In addition to the above components, the photosensitive resin composition of the present embodiment contains known additives such as known coupling agents, leveling agents, thermal polymerization inhibitors, etc., in order to impart predetermined characteristics. May be. The amount of these additives is not particularly limited as long as it does not impair the effects of the present invention.
本実施の形態の感光性樹脂組成物は、公知の混合装置を用い、上記の成分を混合することによって製造することができる。
なお、本実施の形態の感光性樹脂組成物は、先に共重合体(A)および溶剤(B)を含む樹脂組成物を調製した後、反応性希釈剤(C)、光重合開始剤(D)、および任意の着色剤(E)を混合して製造することも可能である。なお、当該樹脂組成物は、本実施の形態の感光性樹脂組成物を調製するために用いることが出来るほか、他の用途で使用することも可能である。The photosensitive resin composition of this Embodiment can be manufactured by mixing said component using a well-known mixing apparatus.
In addition, the photosensitive resin composition of this Embodiment prepares the resin composition containing a copolymer (A) and a solvent (B) previously, Then, a reactive diluent (C), a photoinitiator ( It is also possible to produce a mixture of D) and an optional colorant (E). In addition, the said resin composition can be used for preparing the photosensitive resin composition of this Embodiment, and can also be used for another use.
上記のようにして得られる本実施の形態の感光性樹脂組成物は、アルカリ現像性を有しているので、アルカリ水溶液を用いることによって現像を行うことができる。特に、本実施の形態の感光性樹脂組成物は、感度や現像性に優れると共に、耐熱分解性及び耐熱黄変性に優れた着色パターンを与えることができる。そのため、本実施の形態の感光性樹脂組成物は、各種レジスト、特に、有機ELディスプレイ、液晶表示装置、固体撮像素子に組み込まれるカラーフィルターを製造するために用いられるレジストとして用いるのに適している。また、本実施の形態の感光性樹脂組成物は、耐熱分解性及び耐熱黄変性などの様々な特性に優れた硬化膜を与えるので、各種コーティング、接着剤、印刷インキ用バインダーなどに用いることもできる。 Since the photosensitive resin composition of the present embodiment obtained as described above has alkali developability, it can be developed by using an alkaline aqueous solution. In particular, the photosensitive resin composition of the present embodiment is excellent in sensitivity and developability, and can give a colored pattern excellent in heat decomposition resistance and heat yellowing resistance. Therefore, the photosensitive resin composition of the present embodiment is suitable for use as various resists, particularly as resists used for manufacturing color filters incorporated in organic EL displays, liquid crystal display devices, and solid-state imaging devices. . In addition, since the photosensitive resin composition of the present embodiment gives a cured film excellent in various properties such as heat decomposability and heat yellowing resistance, it can be used for various coatings, adhesives, binders for printing inks, and the like. it can.
次に、本発明の感光性樹脂組成物を用いて調製したカラーフィルターについて説明する。本発明のカラーフィルターは、上記の感光性樹脂組成物から得られる着色パターンを有する。
以下、本発明の一実施形態のカラーフィルターについて、図面を用いて説明する。
図1は、本実施のカラーフィルターの断面図である。図1において、カラーフィルターは、基板1と、基板1上に形成される、RGBの画素2及び画素2の境界に形成されるブラックマトリックス3と、画素2及びブラックマトリックス3上に形成される保護膜4とから構成される。この構成において、画素2及びブラックマトリックス3(着色パターン)が上記の感光性樹脂組成物を用いて形成されることを除けば、その他の構成は公知のものを採用することができる。なお、図1に示したカラーフィルターは一例であり、この構成のみに限定されない。Next, a color filter prepared using the photosensitive resin composition of the present invention will be described. The color filter of the present invention has a colored pattern obtained from the photosensitive resin composition.
Hereinafter, a color filter according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view of the color filter of the present embodiment. In FIG. 1, the color filter includes a
次に、本発明の一実施形態のカラーフィルターの製造方法について説明する。
まず、基材1上に着色パターンを形成する。具体的には、基材1上に、ブラックマトリックス3及び画素2を順次形成する。ここで、基材1としては、特に限定されないが、ガラス基板、シリコン基板、ポリカーボネート基板、ポリエステル基板、ポリアミド基板、ポリアミドイミド基板、ポリイミド基板、アルミニウム基板、プリント配線基板、アレイ基板などを用いることができる。Next, the manufacturing method of the color filter of one Embodiment of this invention is demonstrated.
First, a colored pattern is formed on the
着色パターンは、フォトリソグラフィ法により形成することができる。具体的には、上記の感光性樹脂組成物を基板1上に塗布して塗布膜を形成した後、所定のパターンのフォトマスクを介して塗布膜を露光して露光部分を光硬化させる。そして、未露光部分をアルカリ水溶液で現像した後、ベーキングすることにより、所定のパターンを形成することができる。
感光性樹脂組成物の塗布方法としては、特に限定されないが、スクリーン印刷法、ロールコート法、カーテンコート法、スプレーコート法、スピンコート法などを用いることができる。また、感光性樹脂組成物の塗布後、必要に応じて、循環式オーブン、赤外線ヒーター、ホットプレートなどの加熱手段を用いて加熱することにより溶剤(B)を揮発させてもよい。加熱条件は、特に限定されず、使用する感光性樹脂組成物の種類に応じて適宜設定すればよい。一般には、50℃〜120℃の温度で30秒〜30分加熱すればよい。The colored pattern can be formed by a photolithography method. Specifically, after the photosensitive resin composition is applied onto the
Although it does not specifically limit as a coating method of the photosensitive resin composition, A screen printing method, a roll coat method, a curtain coat method, a spray coat method, a spin coat method, etc. can be used. Moreover, after application | coating of the photosensitive resin composition, you may volatilize a solvent (B) by heating using heating means, such as a circulation type oven, an infrared heater, a hotplate, as needed. The heating conditions are not particularly limited, and may be set as appropriate according to the type of photosensitive resin composition to be used. In general, heating may be performed at a temperature of 50 ° C. to 120 ° C. for 30 seconds to 30 minutes.
露光に用いられる光源としては、特に限定されないが、低圧水銀ランプ、中圧水銀ランプ、高圧水銀ランプ、キセノンランプ、メタルハライドランプなどを用いることができる。また、露光量も、特に限定されず、使用する感光性樹脂組成物の種類に応じて適宜調整すればよい。
現像に用いられるアルカリ水溶液としては、特に限定されないが、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、水酸化ナトリウム、水酸化カリウムなどの水溶液;エチルアミン、ジエチルアミン、ジメチルエタノールアミンなどのアミン系化合物の水溶液;3−メチル−4−アミノ−N,N−ジエチルアニリン、3−メチル−4−アミノ−N−エチル−N−β−ヒドロキシエチルアニリン、3−メチル−4−アミノ−N−エチル−N−β−メタンスルホンアミドエチルアニリン、3−メチル−4−アミノ−N−エチル−N−β−メトキシエチルアニリン及びこれらの硫酸塩、塩酸塩又はp−トルエンスルホン酸塩などのp−フェニレンジアミン系化合物の水溶液などを用いることができる。これらの中でも、p−フェニレンジアミン系化合物の水溶液を用いることが好ましい。なお、これらの水溶液には、必要に応じて消泡剤や界面活性剤を添加してもよい。また、上記のアルカリ水溶液による現像の後、水洗して乾燥させることが好ましい。
ベーキングの条件は、特に限定されず、使用する感光性樹脂組成物の種類に応じて加熱処理を行えばよい。一般には、130〜250℃で10〜60分間加熱すればよい。The light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. Further, the exposure amount is not particularly limited, and may be appropriately adjusted according to the type of the photosensitive resin composition to be used.
The aqueous alkali solution used for development is not particularly limited, but an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc .; an aqueous solution of an amine compound such as ethylamine, diethylamine, 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- Aqueous solutions of methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and p-phenylenediamine compounds such as sulfate, hydrochloride or p-toluenesulfonate Etc. can be used. Among these, it is preferable to use an aqueous solution of a p-phenylenediamine compound. In addition, you may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash and dry after development with the above-mentioned alkaline aqueous solution.
The baking conditions are not particularly limited, and heat treatment may be performed according to the type of the photosensitive resin composition to be used. In general, it may be heated at 130 to 250 ° C. for 10 to 60 minutes.
上記のような塗布、露光、現像及びベーキングを、ブラックマトリックス3用の感光性樹脂組成物、及び画素2用の感光性樹脂組成物を用いて順次繰り返すことにより、所望の着色パターンを形成することができる。
なお、上記では、光硬化による着色パターンの形成方法を説明したが、光重合開始剤(D)の代わりに、硬化促進剤及び公知のエポキシ樹脂を配合した感光性樹脂組成物を用いれば、インクジェット法により塗布した後、加熱することにより、所望の着色パターンを形成することもできる。
次に、着色パターン(画素2及びブラックマトリックス3)上に保護膜4を形成する。保護膜4としては、特に限定されず、公知のものを用いて形成すればよい。Forming a desired coloring pattern by sequentially repeating the coating, exposure, development and baking as described above using the photosensitive resin composition for the
In addition, although the formation method of the coloring pattern by photocuring was demonstrated above, if the photosensitive resin composition which mix | blended the hardening accelerator and the well-known epoxy resin was used instead of a photoinitiator (D), it will be inkjet. A desired coloring pattern can also be formed by heating after coating by the method.
Next, the
このようにして製造されるカラーフィルターは、感度や現像性に優れると共に、耐熱分解性及び耐熱黄変性に優れた着色パターンを与える感光性樹脂組成物を用いて製造しているため、耐熱分解性及び耐熱分解性に優れた着色パターンを有する。 The color filter produced in this way is excellent in sensitivity and developability, and is manufactured using a photosensitive resin composition that gives a coloring pattern excellent in heat decomposition resistance and heat yellowing resistance. In addition, it has a coloring pattern excellent in thermal decomposition resistance.
以下、実施例を参照して本発明を詳細に説明するが、本発明はこれらの実施例により限定されない。なお、この実施例において、部及びパーセントとあるのは特に断らない限り、全て質量基準である。また、酸価とは、JIS K6901 5.3に従って測定された共重合体(A)の酸価であって、共重合体(A)1g中に含まれる酸性成分を中和するのに要する水酸化カリウムのmg数を意味する。また、分子量(Mw)とは、ゲルパーミエーションクロマトグラフィー(GPC)を用いて、下記条件にて測定した標準ポリスチレン換算重量平均分子量を意味する。
カラム:ショウデックス(登録商標) LF−804+LF−804(昭和電工株式会社製)
カラム温度:40℃
試料:共重合体の0.2%テトラヒドロフラン溶液
展開溶媒:テトラヒドロフラン
検出器:示差屈折計(ショウデックス RI−71S)(昭和電工株式会社製)
流速: 1mL/minEXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples. In this example, all parts and percentages are based on mass unless otherwise specified. The acid value is the acid value of the copolymer (A) measured according to JIS K6901 5.3, and is the water required to neutralize the acidic component contained in 1 g of the copolymer (A). It means the number of mg of potassium oxide. Moreover, molecular weight (Mw) means the standard polystyrene conversion weight average molecular weight measured on condition of the following using gel permeation chromatography (GPC).
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of copolymer Development solvent: Tetrahydrofuran Detector: Differential refractometer (Showex RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1mL / min
本発明の共重合体(A)の製造例を以下に示す。
<製造実施例1>
攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、189.7gのプロピレングリコールモノメチルエーテルアセテート及び147.4gのエトキシ化o−フェニルフェノールアクリレート(a−2)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、4.4gのジシクロペンタニルメタクリレート(a−1)及び37.0gのメタクリル酸(a−3)からなるモノマー混合物に、0.9gのt−ブチルパーオキシ−2−エチルヘキサノエート(重合開始剤)を添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体(A)を生成させた。
次に、この共重合体に、94.9gのプロピレングリコールモノメチルエーテルを加え、試料No.1(固形分酸価126mgKOH/g、重量平均分子量20000)を得た。Production examples of the copolymer (A) of the present invention are shown below.
<Production Example 1>
After placing 189.7 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) in a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube The mixture was stirred while replacing with nitrogen and heated to 120 ° C. Next, 0.9 g of t-butylperoxy-2-ethylhexano was added to a monomer mixture consisting of 4.4 g of dicyclopentanyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3). What added the acid (polymerization initiator) was dropped into the flask from the dropping funnel. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer (A).
Next, 94.9 g of propylene glycol monomethyl ether was added to this copolymer. 1 (solid content acid value 126 mgKOH / g, weight average molecular weight 20000) was obtained.
<製造実施例2>
同様にフラスコに、189.7gのプロピレングリコールモノメチルエーテルアセテート及び147.4gのエトキシ化o−フェニルフェノールアクリレート(a−2)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、4.4gのジシクロペンタニルメタクリレート(a−1)及び37.0gのメタクリル酸(a−3)からなるモノマー混合物に、0.9gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、14.2gのグリシジルメタクリレート、0.6gのトリフェニルホスフィン(触媒)、及び0.6gのハイドロキノン(重合禁止剤)を加え、120℃で6時間付加反応を行い、共重合体(A)を生成させた。
次に、この共重合体に、116.2gのプロピレングリコールモノメチルエーテルを加え、試料No.2(固形分酸価90mgKOH/g、重量平均分子量22000)を得た。<Production Example 2>
Similarly, 189.7 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, and the mixture was stirred while replacing with nitrogen and heated to 120 ° C. Next, 0.9 g of t-butylperoxy-2-ethylhexano was added to a monomer mixture consisting of 4.4 g of dicyclopentanyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3). What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of hydroquinone (polymerization inhibitor) were added, and the mixture was heated at 120 ° C. for 6 hours. An addition reaction was performed to produce a copolymer (A).
Next, 116.2 g of propylene glycol monomethyl ether was added to this copolymer. 2 (solid content acid value 90 mgKOH / g, weight average molecular weight 22000) was obtained.
<製造実施例3>
同様にフラスコに、160.5gのプロピレングリコールモノメチルエーテルアセテート及び99.2gのエトキシ化o−フェニルフェノールアクリレート(a−2)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、6.6gのジシクロペンタニルメタクリレート(a−1)及び85.2gのグリシジルメタクリレート(a−3)からなるモノマー混合物に、5.3gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、41.9gのアクリル酸、0.7gのトリフェニルホスフィン、及び0.7gのハイドロキノンを加え、120℃で6時間付加反応を行い、共重合体を生成させた。
次に、この共重合体に、60.8gのテトラヒドロ無水フタル酸を加え、115℃で1時間付加反応を行い、共重合体(A)を生成させた。
次に、この共重合体(A)に、287.8gのプロピレングリコールモノメチルエーテルを加え、試料No.3(固形分酸価75mgKOH/g、重量平均分子量21000)を得た。<Production Example 3>
Similarly, after putting 160.5 g of propylene glycol monomethyl ether acetate and 99.2 g of ethoxylated o-phenylphenol acrylate (a-2) into the flask, the mixture was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Next, a monomer mixture composed of 6.6 g of dicyclopentanyl methacrylate (a-1) and 85.2 g of glycidyl methacrylate (a-3) was added to 5.3 g of t-butylperoxy-2-ethylhexano. What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 41.9 g of acrylic acid, 0.7 g of triphenylphosphine, and 0.7 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. Was generated.
Next, 60.8 g of tetrahydrophthalic anhydride was added to the copolymer, and an addition reaction was performed at 115 ° C. for 1 hour to produce a copolymer (A).
Next, 287.8 g of propylene glycol monomethyl ether was added to the copolymer (A). 3 (solid content acid value 75 mgKOH / g, weight average molecular weight 21000) was obtained.
<製造実施例4>
同様にフラスコに、215.1gのプロピレングリコールモノメチルエーテルアセテート及び91.8gのエトキシ化o−フェニルフェノールアクリレート(a−2)、41.7gの無水マレイン酸(a−3)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、4.4gのジシクロペンタニルメタクリレート(a−1)及び25.1gのビニルトルエン(a−3)からなるモノマー混合物に、13.0gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、40.6gの2−ヒドロキシエチルアクリレート、1.0gのトリエチルアミン(触媒)、及び1.0gのハイドロキノンを加え、120℃で6時間付加反応を行い、共重合体(A)を生成させた。
次に、この共重合体(A)に、109.8gのプロピレングリコールモノメチルエーテルを加え、試料No.4(固形分酸価110mgKOH/g、重量平均分子量5800)を得た。<Production Example 4>
Similarly, after putting 215.1 g of propylene glycol monomethyl ether acetate and 91.8 g of ethoxylated o-phenylphenol acrylate (a-2) and 41.7 g of maleic anhydride (a-3) into a flask, nitrogen was added. The mixture was stirred while being replaced and heated to 120 ° C. Next, 13.0 g of t-butylperoxy-2-ethylhexano was added to a monomer mixture consisting of 4.4 g of dicyclopentanyl methacrylate (a-1) and 25.1 g of vinyltoluene (a-3). What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after replacing the inside of the flask with air, 40.6 g of 2-hydroxyethyl acrylate, 1.0 g of triethylamine (catalyst), and 1.0 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours. A copolymer (A) was produced.
Next, 109.8 g of propylene glycol monomethyl ether was added to the copolymer (A). 4 (solid content acid value 110 mgKOH / g, weight average molecular weight 5800) was obtained.
<製造実施例5>
同様にフラスコに、217.2gのプロピレングリコールモノメチルエーテルアセテート及び187.6gのエトキシ化o−フェニルフェノールアクリレート(a−2)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、4.4gのジシクロペンタニルメタクリレート(a−1)及び24.1gのメタクリル酸(a−3)からなるモノマー混合物に、1.1gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、14.2gのグリシジルメタクリレート、0.7gのトリフェニルホスフィン、及び0.7gのハイドロキノンを加え、120℃で6時間付加反応を行い、共重合体(A)を生成させた。
次に、この共重合体に、129.9gのプロピレングリコールモノメチルエーテルを加え、試料No.5(固形分酸価43mgKOH/g、重量平均分子量13900)を得た。<Production Example 5>
Similarly, 217.2 g of propylene glycol monomethyl ether acetate and 187.6 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, and the mixture was stirred while replacing with nitrogen and heated to 120 ° C. Next, 1.1 g of t-butylperoxy-2-ethylhexano was added to a monomer mixture consisting of 4.4 g of dicyclopentanyl methacrylate (a-1) and 24.1 g of methacrylic acid (a-3). What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.7 g of triphenylphosphine, and 0.7 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. (A) was generated.
Next, 129.9 g of propylene glycol monomethyl ether was added to this copolymer. 5 (solid content acid value 43 mgKOH / g, weight average molecular weight 13900) was obtained.
<製造実施例6>
同様にフラスコに、170.1gのプロピレングリコールモノメチルエーテルアセテート及び53.6gのエトキシ化o−フェニルフェノールアクリレート(a−2)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、66.0gのジシクロペンタニルメタクリレート(a−1)及び43.0gのメタクリル酸(a−3)からなるモノマー混合物に、0.8gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、14.2gのグリシジルメタクリレート、0.5gのトリフェニルホスフィン(触媒)、及び0.5gのハイドロキノン(重合禁止剤)を加え、120℃で6時間付加反応を行い、共重合体(A)を生成させた。
次に、この共重合体(A)に、96.3gのプロピレングリコールモノメチルエーテルを加え、試料No.6(固形分酸価125mgKOH/g、重量平均分子量25600)を得た。<Production Example 6>
Similarly, after putting 170.1 g of propylene glycol monomethyl ether acetate and 53.6 g of ethoxylated o-phenylphenol acrylate (a-2) into the flask, the mixture was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Next, 0.8 g of t-butylperoxy-2-ethylhexano was added to a monomer mixture consisting of 66.0 g of dicyclopentanyl methacrylate (a-1) and 43.0 g of methacrylic acid (a-3). What added the acid was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.5 g of triphenylphosphine (catalyst), and 0.5 g of hydroquinone (polymerization inhibitor) were added, and the mixture was heated at 120 ° C. for 6 hours. An addition reaction was performed to produce a copolymer (A).
Next, 96.3 g of propylene glycol monomethyl ether was added to this copolymer (A). 6 (solid content acid value 125 mgKOH / g, weight average molecular weight 25600) was obtained.
<製造実施例7>
同様にフラスコに、187.2gのプロピレングリコールモノメチルエーテルアセテート及び1.9gのノルボルネン(a−1’)、147.4gのエトキシ化o−フェニルフェノールアクリレート(a−2)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、37.0gのメタクリル酸(a−3)に、0.9gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、14.2gのグリシジルメタクリレート、0.6gのトリフェニルホスフィン、及び0.6gのハイドロキノンを加え、120℃で6時間付加反応を行い、共重合体(A)を生成させた。
次に、この共重合体(A)に、114.9gのプロピレングリコールモノメチルエーテルを加え、試料No.7(固形分酸価91mgKOH/g、重量平均分子量21500)を得た。<Production Example 7>
In the same manner, 187.2 g of propylene glycol monomethyl ether acetate and 1.9 g of norbornene (a-1 ′) and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were put into a flask, and then replaced with nitrogen. The mixture was stirred and heated to 120 ° C. Next, a solution obtained by adding 0.9 g of t-butylperoxy-2-ethylhexanoate to 37.0 g of methacrylic acid (a-3) was dropped into the flask from a dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. (A) was generated.
Next, 114.9 g of propylene glycol monomethyl ether was added to this copolymer (A). 7 (solid content acid value 91 mgKOH / g, weight average molecular weight 21500) was obtained.
<製造実施例8>
同様にフラスコに、189.8gのプロピレングリコールモノメチルエーテルアセテート及び147.4gのエトキシ化o−フェニルフェノールアクリレート(a−2)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、4.4gのイソボルニルメタクリレート(a−1)及び37.0gのメタクリル酸(a−3)に、0.9gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、14.2gのグリシジルメタクリレート、0.6gのトリフェニルホスフィン、及び0.6gのハイドロキノンを加え、120℃で6時間付加反応を行い、共重合体(A)を生成させた。
次に、この共重合体(A)に、116.2gのプロピレングリコールモノメチルエーテルを加え、試料No.8(固形分酸価90mgKOH/g、重量平均分子量21800)を得た。<Production Example 8>
Similarly, 189.8 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were added to the flask, and the mixture was stirred while purging with nitrogen and heated to 120 ° C. Next, 4.4 g of isobornyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3) added with 0.9 g of t-butylperoxy-2-ethylhexanoate Was dropped from the dropping funnel into the flask. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. (A) was generated.
Next, 116.2 g of propylene glycol monomethyl ether was added to this copolymer (A). 8 (solid content acid value 90 mgKOH / g, weight average molecular weight 21800) was obtained.
<製造実施例9>
同様にフラスコに、197.8gのプロピレングリコールモノメチルエーテルアセテート及び147.4gのエトキシ化o−フェニルフェノールアクリレート(a−2)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、4.7gの2−メチル−2−アダマンチルメタクリレート(a−1)及び37.0gのメタクリル酸(a−3)に、0.9gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、14.2gのグリシジルメタクリレート、0.6gのトリフェニルホスフィン、及び0.6gのハイドロキノンを加え、120℃で6時間付加反応を行い、共重合体(A)を生成させた。
次に、この共重合体(A)に、108.5gのプロピレングリコールモノメチルエーテルを加え、試料No.9(固形分酸価90mgKOH/g、重量平均分子量22500)を得た。<Production Example 9>
Similarly, after placing 197.8 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) in a flask, the mixture was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Next, 4.7 g of 2-methyl-2-adamantyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3) were added to 0.9 g of t-butylperoxy-2-ethylhexanoate. Was added dropwise from the dropping funnel into the flask. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. (A) was generated.
Next, 108.5 g of propylene glycol monomethyl ether was added to this copolymer (A). 9 (solid content acid value 90 mgKOH / g, weight average molecular weight 22500) was obtained.
以下に、比較品である共重合体の製造例を示す。
<製造比較例1>
同様にフラスコに、218.1gのプロピレングリコールモノメチルエーテルアセテート及び193.0gのエトキシ化o−フェニルフェノールアクリレート(a−2)を入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、24.1gのメタクリル酸(a−3)に、0.9gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、14.2gのグリシジルメタクリレート、0.6gのトリフェニルホスフィン、及び0.6gのハイドロキノンを加え、120℃で6時間付加反応を行い、共重合体を生成させた。
次に、この共重合体に、130.4gのプロピレングリコールモノメチルエーテルを加え、試料No.10(固形分酸価44mgKOH/g、重量平均分子量24800)を得た。Below, the manufacture example of the copolymer which is a comparative product is shown.
<Production Comparative Example 1>
Similarly, 218.1 g of propylene glycol monomethyl ether acetate and 193.0 g of ethoxylated o-phenylphenol acrylate (a-2) were placed in a flask, and the mixture was stirred while purging with nitrogen and heated to 120 ° C. Next, what added 0.9 g of t-butylperoxy-2-ethylhexanoate to 24.1 g of methacrylic acid (a-3) was dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. Was generated.
Next, 130.4 g of propylene glycol monomethyl ether was added to this copolymer. 10 (solid content acid value 44 mgKOH / g, weight average molecular weight 24800) was obtained.
<製造比較例2>
同様にフラスコに、160.0gのプロピレングリコールモノメチルエーテルアセテートを入れた後、窒素置換しながら攪拌し、120℃に昇温した。次に、110.0gのジシクロペンタニルメタクリレート(a−1)、43.0gのメタクリル酸(a−3)に、0.8gのt−ブチルパーオキシ−2−エチルヘキサノエートを添加したものを滴下ロートから前記フラスコ中に滴下した。滴下終了後、120℃で2時間攪拌して共重合反応を行い、共重合体を生成させた。
次に、前記フラスコ内を空気に置換した後、14.2gのグリシジルメタクリレート、0.5gのトリフェニルホスフィン、及び0.5gのハイドロキノンを加え、120℃で6時間付加反応を行い、共重合体を生成させた。
次に、この共重合体に、91.9gのプロピレングリコールモノメチルエーテルを加え、試料No.11(固形分酸価132mgKOH/g、重量平均分子量26300)を得た。<Production Comparative Example 2>
Similarly, after putting 160.0 g of propylene glycol monomethyl ether acetate into the flask, the mixture was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Next, 0.8 g of t-butylperoxy-2-ethylhexanoate was added to 110.0 g of dicyclopentanyl methacrylate (a-1) and 43.0 g of methacrylic acid (a-3). Things were dropped from the dropping funnel into the flask. After completion of the dropping, the mixture was stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction, thereby producing a copolymer.
Next, after the inside of the flask was replaced with air, 14.2 g of glycidyl methacrylate, 0.5 g of triphenylphosphine, and 0.5 g of hydroquinone were added, and an addition reaction was performed at 120 ° C. for 6 hours to obtain a copolymer. Was generated.
Next, 91.9 g of propylene glycol monomethyl ether was added to this copolymer. 11 (solid content acid value 132 mgKOH / g, weight average molecular weight 26300) was obtained.
試料No.1〜11を用いて、透明レジスト、カラーレジスト(顔料タイプ)及びカラーレジスト(染料タイプ)を調製した。
<透明レジストの調製>
試料No.1〜11の固形分100質量部に対して、ペンタエリスリトールテトラアクリレート(反応性希釈剤)30質量部、2,2−ジメトキシ−2−フェニルアセトフェノン(光重合開始剤)4質量部を添加して感光性樹脂組成物を調製し、これを用いて透明レジストを調製した(実施例1〜9及び比較例1、2)。Sample No. A transparent resist, a color resist (pigment type), and a color resist (dye type) were prepared using 1-11.
<Preparation of transparent resist>
Sample No. To 100 parts by mass of
<透明レジストによるパターン形成>
調製された透明レジストを、5cm角ガラス基板(無アルカリガラス基板)上に、最終の硬化塗膜の厚さが2.5μmとなるようにスピンコートした後、90℃で3分間加熱することで溶剤を揮発させた。次に塗膜の全面を露光(露光量50mJ/cm2)し、光硬化させた後、さらに230℃で30分間ベーキングすることで硬化塗膜を得た。<Pattern formation with transparent resist>
The prepared transparent resist is spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the final cured coating thickness is 2.5 μm, and then heated at 90 ° C. for 3 minutes. The solvent was volatilized. Next, the entire surface of the coating film was exposed (exposure amount 50 mJ / cm 2 ), photocured, and then baked at 230 ° C. for 30 minutes to obtain a cured coating film.
<透明レジストから形成された塗膜の評価>
透明レジストから形成された塗膜について、耐熱分解性、耐熱黄変性及び透明性を評価した。
(1)耐熱分解性の評価
ガラス基板上に製膜した塗膜を切り出したサンプルを用い、熱重量分析(TGA)を行うことによって評価した。この分析では、このサンプルと、サンプルを220℃まで加熱して2時間保持したサンプルとの間の重量変化率を求めた。この評価の基準は以下の通りである。
○:−2.0%未満
×:−2.0%以上<Evaluation of coating film formed from transparent resist>
About the coating film formed from the transparent resist, heat-resistant decomposability, heat-resistant yellowing, and transparency were evaluated.
(1) Evaluation of heat decomposability Evaluation was performed by performing thermogravimetric analysis (TGA) using a sample obtained by cutting out a coating film formed on a glass substrate. In this analysis, the rate of weight change between this sample and the sample heated to 220 ° C. and held for 2 hours was determined. The criteria for this evaluation are as follows.
○: Less than −2.0% ×: −2.0% or more
(2)耐熱黄変性の評価
ガラス基板上に製膜した塗膜を230℃の乾燥機中に1時間放置し、加熱処理前後の塗膜の着色を日本電色工業(株)製 色差計SE2000にて比較した。この評価の基準は以下の通りである。
○:ΔE*abが0.3未満
×:ΔE*abが0.3以上(2) Evaluation of heat-resistant yellowing property The coating film formed on the glass substrate was left in a dryer at 230 ° C. for 1 hour, and the coating film before and after the heat treatment was colored by a color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. Compared. The criteria for this evaluation are as follows.
○: ΔE * ab is less than 0.3 ×: ΔE * ab is 0.3 or more
(3)透明性の評価
ガラス基板上に製膜した塗膜を230℃の乾燥機中に1時間放置し、加熱処理前後の塗膜の400nmの光線透過率を(株)島津製作所製 分光光度計UV−1650PCにて測定し、その透過率の変化率を調べることによって評価した。この評価の基準は以下の通りである。
○:透過率の変化率が1%未満
×:透過率の変化率が1%以上
上記の耐熱分解性、耐熱黄変性、透明性の評価結果を表1に示す。(3) Evaluation of transparency The coating film formed on the glass substrate was left in a dryer at 230 ° C. for 1 hour, and the light transmittance at 400 nm of the coating film before and after the heat treatment was measured by Shimadzu Corporation. The measurement was carried out with a total of UV-1650PC, and the change rate of the transmittance was evaluated. The criteria for this evaluation are as follows.
○: Change rate of transmittance is less than 1% ×: Change rate of transmittance is 1% or more Table 1 shows the evaluation results of the above heat decomposition resistance, heat yellowing resistance, and transparency.
表1の結果からわかるように、実施例1〜9の透明レジストは、耐熱分解性、耐熱黄変性、透明性の全てに優れたパターンを与えたのに対し、比較例1、2の透明レジストは、耐熱分解性、耐熱黄変性、透明性のいずれかが十分でないパターンを与えた。 As can be seen from the results in Table 1, the transparent resists of Examples 1 to 9 gave excellent patterns in all of the heat decomposition resistance, heat yellowing resistance and transparency, whereas the transparent resists of Comparative Examples 1 and 2 Gave a pattern with insufficient thermal decomposition, heat yellowing and transparency.
<カラーレジスト(顔料タイプ)の調製>
直径0.5mmのジルコニアビーズ180質量部を充填したSUS容器に、10.00質量部のC.Iピグメントグリーン36、33.75質量部のPGMEA(溶剤)、及び6.25質量部の分散剤(ビックケミー・ジャパン株式会社製Disperbyk−161)を加え、ペイントシェーカーで3時間混合して分散させることにより、緑色顔料分散液を得た。
次に、調製した緑色顔料分散液、試料No.1〜11、及びその他の成分を混合することによって感光性樹脂組成物を調製し、これを用いてカラーレジスト(顔料タイプ)を調製した(実施例10〜18及び比較例3〜4)。このカラーレジスト(顔料タイプ)の配合成分及びその配合量を表2に示す。<Preparation of color resist (pigment type)>
In a SUS container filled with 180 parts by mass of zirconia beads having a diameter of 0.5 mm, 10.00 parts by mass of C.I. Add I Pigment Green 36, 33.75 parts by weight of PGMEA (solvent), and 6.25 parts by weight of a dispersant (Disperbyk-161 manufactured by Big Chemie Japan Co., Ltd.), and mix and disperse in a paint shaker for 3 hours. As a result, a green pigment dispersion was obtained.
Next, the prepared green pigment dispersion, Sample No. The photosensitive resin composition was prepared by mixing 1-11 and another component, and the color resist (pigment type) was prepared using this (Examples 10-18 and Comparative Examples 3-4). Table 2 shows the blending components and blending amounts of this color resist (pigment type).
<カラーレジスト(顔料タイプ)によるパターン形成>
調製されたカラーレジスト(顔料タイプ)を、5cm角ガラス基板(無アルカリガラス基板)上に、露光後の厚さが1.5μmとなるようにスピンコートした後、90℃で3分間加熱することで溶剤を揮発させ、乾燥させた。次に、塗布膜から100μmの距離に所定のパターンのフォトマスクを配置し、このフォトマスクを介して塗布膜を露光(露光量150mJ/cm2)し、露光部分を光硬化させた。次に、0.1質量%の炭酸ナトリウムを含む水溶液を23℃の温度及び0.3MPaの圧力でスプレーすることによって未露光部分を溶解して現像した後、230℃で30分間ベーキングすることで所定のパターンを形成した。<Pattern formation with color resist (pigment type)>
The prepared color resist (pigment type) is spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the thickness after exposure is 1.5 μm, and then heated at 90 ° C. for 3 minutes. The solvent was volatilized and dried. Next, a photomask having a predetermined pattern was disposed at a distance of 100 μm from the coating film, and the coating film was exposed through this photomask (exposure amount 150 mJ / cm 2 ), and the exposed portion was photocured. Next, an unexposed part was dissolved and developed by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23 ° C. and a pressure of 0.3 MPa, and then baked at 230 ° C. for 30 minutes. A predetermined pattern was formed.
<カラーレジスト(顔料タイプ)及びパターンの確認>
カラーレジスト(顔料タイプ)及びパターンについて、アルカリ現像性、感度、耐熱黄変性及び耐溶剤性を確認した。
(4)アルカリ現像性の評価
アルカリ現像性は、アルカリ現像後の残渣、及び現像形態により確認した。
アルカリ現像後の残渣は、アルカリ現像後のパターンを、(株)日立ハイテクノロジーズ製電子顕微鏡S−3400を用いて観察することにより確認した。この評価の基準は以下の通りである。
○:残渣なし
×:残渣あり
現像形態は、アルカリ現像による未露光部分の除去形態を目視にて評価した。ここで、ネガ型レジストの現像工程においては、未硬化の未露光部分がアルカリ現像液により溶解して基板上から離脱していくが、その現像形態としては、離脱していく部分が主に大きな塊となって剥がれる剥離型と、徐々に溶解及び拡散する溶解型とがある。前者の剥離型は、塊が異物となって系内に残留し、他の色の画素を汚染し易いので好まれない。つまり、後者の溶解型が好ましい。
○:溶解型
×:剥離型<Confirmation of color resist (pigment type) and pattern>
The color resist (pigment type) and the pattern were confirmed for alkali developability, sensitivity, heat yellowing and solvent resistance.
(4) Evaluation of alkali developability Alkali developability was confirmed by the residue after alkali development and the development form.
The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The criteria for this evaluation are as follows.
○: No residue ×: Residue With respect to the development form, the removal form of the unexposed part by alkali development was visually evaluated. Here, in the development process of the negative resist, the uncured unexposed part is dissolved by the alkali developer and is detached from the substrate. However, as the development form, the part to be detached is mainly large. There are a peeling type that peels off as a lump and a dissolving type that gradually dissolves and diffuses. The former peeling type is not preferred because the lump becomes a foreign substance and remains in the system and easily contaminates other color pixels. That is, the latter dissolution type is preferable.
○: Dissolution type ×: Peeling type
(5)感度の評価
感度は、上記のスプレーを用いたアルカリ現像を30秒間行い、アルカリ現像前後におけるパターン厚さの減少量を測定した。このパターン厚さは、減少量が少ないほど感度が良好であると言えるため、この評価の基準は以下の通りとした。
○:0.20μm未満
×:0.20μm以上(5) Evaluation of sensitivity For sensitivity, alkali development using the above spray was performed for 30 seconds, and the amount of decrease in pattern thickness before and after alkali development was measured. Since it can be said that the sensitivity of this pattern thickness is better as the amount of decrease is smaller, the criteria for this evaluation were as follows.
○: Less than 0.20 μm ×: 0.20 μm or more
(6)耐熱黄変性の評価
耐熱黄変性は、フォトマスクを使用せずに全面露光し、硬化させた最終塗膜の膜厚を2.5μmに変えること以外は上記と同様にして光硬化させて形成した塗膜を用い、230℃の乾燥機中に1時間放置し、加熱処理前後の塗膜の着色を日本電色工業(株)製 色差計SE2000にて比較した。この評価の基準は以下の通りである。
○:ΔE*abが0.3未満
×:ΔE*abが0.3以上(6) Evaluation of heat-resistant yellowing The heat-resistant yellowing was photocured in the same manner as above except that the entire film was exposed without using a photomask and the film thickness of the cured final coating was changed to 2.5 μm. The coating film formed in this manner was left in a dryer at 230 ° C. for 1 hour, and the coloring of the coating film before and after the heat treatment was compared with a color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. The criteria for this evaluation are as follows.
○: ΔE * ab is less than 0.3 ×: ΔE * ab is 0.3 or more
(7)耐溶剤性の評価
耐溶剤性は、耐熱黄変評価サンプルと同様に作製した塗膜を用い、容量500mLの蓋付きガラス瓶に200mLのn−メチル−2−ピロリドンを入れ、その中にパターンサンプルを浸漬した後、23℃で1時間後の色変化を(株)島津製作所製分光光度計UV−1650PCにて測定した。この評価の基準は以下の通りである。
○:ΔE*abが0.3未満
×:ΔE*abが0.3以上
上記のアルカリ現像性、感度、耐熱黄変性及び耐溶剤性の評価結果を表3に示す。(7) Evaluation of solvent resistance Solvent resistance is obtained by using a coating film prepared in the same manner as the heat-resistant yellowing evaluation sample, putting 200 mL of n-methyl-2-pyrrolidone in a 500 mL lidded glass bottle, After dipping the pattern sample, the color change after 1 hour at 23 ° C. was measured with a spectrophotometer UV-1650PC manufactured by Shimadzu Corporation. The criteria for this evaluation are as follows.
○: ΔE * ab is less than 0.3 ×: ΔE * ab is 0.3 or more Table 3 shows the evaluation results of the above alkali developability, sensitivity, heat yellowing resistance, and solvent resistance.
表3の結果からわかるように、実施例10〜18のカラーレジスト(顔料タイプ)は、アルカリ現像性及び感度が良好であり、耐熱黄変性及び耐溶剤性に優れるパターンを与えたのに対し、比較例3〜4のカラーレジスト(顔料タイプ)は、アルカリ現像性と感度が良好でなく、耐熱黄変性又は耐溶剤性が十分でないパターンを与えた。 As can be seen from the results in Table 3, the color resists (pigment types) of Examples 10 to 18 had good alkali developability and sensitivity, and gave a pattern excellent in heat yellowing and solvent resistance. The color resists (pigment types) of Comparative Examples 3 to 4 gave a pattern with poor alkali developability and sensitivity and insufficient heat yellowing or solvent resistance.
<カラーレジスト(染料タイプ)の調製>
染料(acid green3)、試料No.1〜11、及びその他の成分を混合することによって感光性樹脂組成物を調製し、この組成物を用いてカラーレジスト(染料タイプ)を調製した(実施例19〜27及び比較例5〜6)。このカラーレジスト(染料タイプ)の配合成分及びその配合量を表4に示す。<Preparation of color resist (dye type)>
Dye (acid green 3), sample no. A photosensitive resin composition was prepared by mixing 1 to 11 and other components, and a color resist (dye type) was prepared using this composition (Examples 19 to 27 and Comparative Examples 5 to 6). . Table 4 shows the blending components and blending amounts of this color resist (dye type).
<カラーレジスト(染料タイプ)によるパターン形成>
カラーレジスト(染料タイプ)を用いたこと以外は、カラーレジスト(顔料タイプ)によるパターン形成と同様にして所定のパターンを形成した。
<カラーレジスト(染料タイプ)及びパターンの評価>
カラーレジスト(顔料タイプ)と同様の方法にて、アルカリ現像性、感度、耐熱黄変性及び耐溶剤性を評価した。
上記のアルカリ現像性、感度、耐熱黄変性及び耐溶剤性の評価結果を表5に示す。<Pattern formation with color resist (dye type)>
A predetermined pattern was formed in the same manner as the pattern formation by the color resist (pigment type) except that the color resist (dye type) was used.
<Evaluation of color resist (dye type) and pattern>
Alkali developability, sensitivity, heat yellowing resistance, and solvent resistance were evaluated in the same manner as the color resist (pigment type).
Table 5 shows the evaluation results of the alkali developability, sensitivity, heat-resistant yellowing and solvent resistance.
表5の結果からわかるように、実施例19〜27のカラーレジスト(染料タイプ)は、アルカリ現像性及び感度が良好であり、耐溶剤性に優れるパターンを与えたのに対し、比較例5〜6のカラーレジスト(染料タイプ)は、アルカリ現像性と感度が良好でなく、耐熱黄変性又は耐溶剤性が十分でないパターンを与えた。 As can be seen from the results in Table 5, the color resists (dye types) of Examples 19 to 27 had good alkali developability and sensitivity and gave a pattern excellent in solvent resistance, whereas Comparative Examples 5 to The color resist (dye type) of No. 6 gave a pattern with poor alkali developability and sensitivity and insufficient heat-resistant yellowing or solvent resistance.
以上の結果からわかるように、本発明によれば、感度や現像性が良好であると共に、耐熱分解性、耐熱黄変性及び耐溶剤性に優れた着色パターンを与える感光性樹脂組成物を提供することができる。また、本発明によれば、耐熱分解性及び耐熱黄変性に優れた着色パターンを有するカラーフィルターを提供することができる。 As can be seen from the above results, according to the present invention, there is provided a photosensitive resin composition that has a good sensitivity and developability and gives a colored pattern excellent in heat decomposition resistance, heat yellowing resistance and solvent resistance. be able to. Moreover, according to this invention, the color filter which has a coloring pattern excellent in heat-resistant decomposability and heat-resistant yellowing can be provided.
1 基板、2 画素、3 ブラックマトリックス、4 保護膜。 1 substrate, 2 pixels, 3 black matrix, 4 protective film.
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JP6001877B2 (en) * | 2012-02-28 | 2016-10-05 | 株式会社日本触媒 | Curable resin composition for photospacer and columnar spacer |
JP2014174222A (en) * | 2013-03-06 | 2014-09-22 | Mitsubishi Chemicals Corp | Coloring resin composition, color filter, liquid crystal display device, and organic el display device |
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CN103459443B (en) | 2016-08-24 |
KR101536500B1 (en) | 2015-08-17 |
CN103459443A (en) | 2013-12-18 |
WO2012141000A1 (en) | 2012-10-18 |
KR20130132639A (en) | 2013-12-04 |
TW201302822A (en) | 2013-01-16 |
TWI534161B (en) | 2016-05-21 |
JPWO2012141000A1 (en) | 2014-07-28 |
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