JP4726076B2 - Negative coloring photosensitive composition - Google Patents
Negative coloring photosensitive composition Download PDFInfo
- Publication number
- JP4726076B2 JP4726076B2 JP2006264605A JP2006264605A JP4726076B2 JP 4726076 B2 JP4726076 B2 JP 4726076B2 JP 2006264605 A JP2006264605 A JP 2006264605A JP 2006264605 A JP2006264605 A JP 2006264605A JP 4726076 B2 JP4726076 B2 JP 4726076B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- color filter
- photosensitive composition
- methacrylate
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 42
- 238000004040 coloring Methods 0.000 title description 16
- 239000000178 monomer Substances 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 239000004973 liquid crystal related substance Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000003384 imaging method Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000001459 lithography Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 description 51
- 239000000049 pigment Substances 0.000 description 33
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 25
- 229940048053 acrylate Drugs 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- -1 aromatic vinyl compound Chemical class 0.000 description 16
- 239000000975 dye Substances 0.000 description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000003513 alkali Substances 0.000 description 14
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 239000004793 Polystyrene Substances 0.000 description 12
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 11
- 239000004926 polymethyl methacrylate Substances 0.000 description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000000981 basic dye Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000980 acid dye Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical class OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- QJPPPIFMLKUMEW-UHFFFAOYSA-N 2-ethyl-2-methyloctanoic acid Chemical compound CCCCCCC(C)(CC)C(O)=O QJPPPIFMLKUMEW-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-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
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
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- 239000001056 green pigment Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229940057867 methyl lactate Drugs 0.000 description 2
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- 229920001187 thermosetting polymer Polymers 0.000 description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
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- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
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- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000000206 photolithography Methods 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
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- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000000984 vat dye Substances 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Landscapes
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
Description
本発明は、ネガ型着色感光性組成物、及びその着色硬化膜に関し、特に液晶表示装置、電子表示装置等の表示材料に使用されるカラーフィルターの形成に好適に用いられるネガ型着色感光性組成物に関する。 The present invention relates to a negative colored photosensitive composition and a colored cured film thereof, and in particular, a negative colored photosensitive composition suitably used for forming a color filter used for a display material such as a liquid crystal display device and an electronic display device. Related to things.
ノートパソコンや液晶テレビ等に代表される液晶ディスプレイ(LCD)等の液晶表示素子やデジタルカメラやカラーコピー機等の入力デバイスとして使用される撮像素子(CCD、CMOS)のカラー化にはカラーフィルターが必要である。これら液晶表示装置や固体撮像素子に用いられるカラーフィルターを製造する方法としては、染色法、電着法、印刷法、顔料分散法等がある。 Color filters are used for colorization of liquid crystal display elements such as liquid crystal displays (LCD) typified by notebook computers and liquid crystal televisions, and image sensors (CCD, CMOS) used as input devices for digital cameras and color copiers. is necessary. As a method for producing a color filter used for these liquid crystal display devices and solid-state imaging devices, there are a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method and the like.
これらの方法のうち、染色法によるカラーフィルターは、色特性には優れるものの、耐熱、耐光、耐薬品性等に劣り、又印刷法によるカラーフィルターは、解像性、表面平滑性に劣り、電着法は複雑なパターンの形成が困難という問題がある。 Among these methods, the color filter by the dyeing method has excellent color characteristics but is inferior in heat resistance, light resistance, chemical resistance, etc. The color filter by the printing method is inferior in resolution and surface smoothness, The deposition method has a problem that it is difficult to form a complicated pattern.
一方、顔料分散法によるカラーフィルターは、感光性樹脂に顔料を分散させた着色感光性組成物により画素を形成することにより製造され、染色工程が不要なため製造工程が簡略化でき、また得られた着色画素は、耐光、耐熱性に優れ、高精度の画像を形成できるという利点がある。 On the other hand, a color filter by a pigment dispersion method is manufactured by forming pixels with a colored photosensitive composition in which a pigment is dispersed in a photosensitive resin, and the manufacturing process can be simplified and obtained because a dyeing process is unnecessary. The colored pixels have the advantage of being excellent in light resistance and heat resistance and capable of forming a highly accurate image.
現在一般に行われている顔料分散法による画素の形成方法においては、先ず着色感光性組成物をガラス基板やウェーハのような基板上に塗布し、次いでプリベークを行い膜を形成させた後、所望のマスクを通して紫外線を照射し、照射部分を硬化させ、現像処理により未照射部分を取り除き着色画素を得、更に熱処理を行うことにより、着色した硬化膜(着色画素)を得ている。一般的に現像液にはアルカリ現像液を使用し、アルカリ現像性を出すために、バインダー樹脂にはカルボキシル基含有共重合体が使用される。また、感光性樹脂としてはトリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタ及びヘキサアクリレート等の多官能モノマーが多く用いられる。多官能モノマーの重合反応は、光重合開始剤が活性ラジカルを生成し、これが多官能モノマーの(メタ)アクリロイル基を攻撃し、重合反応を誘発するとう原理を利用している。活性ラジカルの存在があって初めて重合が開始される。 In a pixel forming method that is currently generally performed by a pigment dispersion method, a colored photosensitive composition is first applied on a substrate such as a glass substrate or a wafer, then pre-baked to form a film, and then a desired film is formed. By irradiating with ultraviolet rays through a mask, the irradiated portion is cured, the unirradiated portion is removed by development processing to obtain a colored pixel, and further heat treatment is performed to obtain a colored cured film (colored pixel). In general, an alkali developer is used as the developer, and a carboxyl group-containing copolymer is used as the binder resin in order to obtain alkali developability. As the photosensitive resin, polyfunctional monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol penta and hexaacrylate are often used. The polymerization reaction of the polyfunctional monomer utilizes the principle that the photopolymerization initiator generates an active radical, which attacks the (meth) acryloyl group of the polyfunctional monomer to induce the polymerization reaction. Polymerization is initiated only in the presence of active radicals.
しかしながら、このような顔料分散法のカラーレジストにてカラーフィルターを形成しようとすると、顔料濃度が高いカラーレジストの場合、アルカリ現像液に対する現像性が十分でなく、現像時間が長くなりスループットへの影響が出たり、本来現像される部分に残渣が残り、品質低下を起こす場合があった。特に撮像素子用のカラーフィルターの場合、高画素化とともに、カラーフィルターの薄膜化要求が強く、そのために顔料濃度を上げる必要があり、結果的に、バインダー樹脂の含有率が下がり、現像性が劣化し、残渣が増加するという現象が見られるようになってきた。 However, when trying to form a color filter with a color resist of such a pigment dispersion method, in the case of a color resist having a high pigment concentration, the developability with respect to an alkaline developer is not sufficient, and the development time becomes longer, which affects the throughput. In some cases, a residue is left on the part that is originally developed and the quality is deteriorated. Especially in the case of color filters for image sensors, there is a strong demand for thinning the color filter with an increase in the number of pixels. For this reason, it is necessary to increase the pigment concentration. As a result, the content of the binder resin decreases and the developability deteriorates. However, the phenomenon that the residue increases has been observed.
このような現像性劣化の対策として、多官能モノマーのアルカリ現像液に対する溶解性を上げることが考えられる。特許文献1では、カルボキシル基含有の多官能モノマーが残渣に効果があることが記載されている。 As a countermeasure against such developability deterioration, it is conceivable to increase the solubility of the polyfunctional monomer in an alkaline developer. Patent Document 1 describes that a carboxyl group-containing polyfunctional monomer is effective for residues.
しかしながら、多官能モノマーにカルボキシル基があると、アルカリ現像液に対する耐性も劣化し、画素の表面に荒れが生じるという現象が確認された。これは、表層に発生した活性ラジカルが酸素の影響により消失し、多官能モノマーの重合が不十分となし、更にカルボキシル基含有の多官能モノマーが従来使用されている多官能モノマーと比較し、アルカリ現像液に対して親和性が高いため、表層部がアルカリ現像液に溶解し、膜荒れが生じたと考えられる。
本発明は、感度低下やアルカリ現像液への耐性劣化を引き起こすことなく、現像性や残渣を改善し、高品質なカラーフィルターを製造する方法の実現を目的とする。
However, it has been confirmed that when a polyfunctional monomer has a carboxyl group, the resistance to an alkaline developer is deteriorated, and the pixel surface is roughened. This is because the active radicals generated on the surface layer disappear due to the influence of oxygen, the polymerization of the polyfunctional monomer is insufficient, and the carboxyl group-containing polyfunctional monomer is more alkaline than conventional polyfunctional monomers. Since the affinity for the developer is high, it is considered that the surface layer portion was dissolved in the alkali developer and the film was rough.
An object of the present invention is to realize a method for producing a high-quality color filter by improving developability and residue without causing a decrease in sensitivity and a deterioration in resistance to an alkaline developer.
本発明者は前記課題を解決すべく鋭意研究の結果、特定の構造を有する光重合性モノマーを使用する事により、感度低下やアルカリ現像液への耐性劣化を引き起こすことなく、現像性や残渣が良好なネガ型着色感光性組成物が得られることを見出し、本発明を完成させるに至った。 As a result of diligent research to solve the above problems, the present inventor uses a photopolymerizable monomer having a specific structure, so that developability and residue can be reduced without causing a decrease in sensitivity or deterioration in resistance to an alkaline developer. The inventors have found that a good negative colored photosensitive composition can be obtained, and have completed the present invention.
即ち、本発明は
(1)バインダーポリマー、光重合性モノマー、色素、光重合開始剤、有機溶剤を含有し、該光重合性モノマーが下記式(1)で表わされる化合物であることを特徴とするネガ型着色感光性組成物、
That is, the present invention is characterized in that (1) a binder polymer, a photopolymerizable monomer, a dye, a photopolymerization initiator, and an organic solvent are contained, and the photopolymerizable monomer is a compound represented by the following formula (1). Negative-type coloring photosensitive composition,
(式(1)中、R1は水素原子またはメチル基、R2は下記式(2)で表される基を示し、l,mはそれぞれ0〜10の整数を意味し、aは1〜12までの整数を意味する。) (In the formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a group represented by the following formula (2), l and m each represents an integer of 0 to 10, and a represents 1 to 1 It means an integer up to 12.)
(式(2)中、R1は水素原子またはメチル基、nは0〜10の整数を意味する。)
(2)(1)記載のネガ型着色感光性組成物を用い、リソグラフィー法によりパターニングされてなるカラーフィルター用着色硬化膜、
(3)(2)記載のカラーフィルター用着色硬化膜からなるカラーフイルター、
(4)(3)記載のカラーフィルターを装着してなる液晶表示装置、
(5)(3)記載のカラーフィルターを装着してなる固体撮像素子
に関する。
(In the formula (2), R 1 represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 10.)
(2) A colored cured film for a color filter obtained by patterning by a lithography method using the negative coloring photosensitive composition according to (1),
(3) A color filter comprising the colored cured film for a color filter according to (2),
(4) A liquid crystal display device comprising the color filter according to (3),
(5) The present invention relates to a solid-state imaging device having the color filter described in (3).
本発明のネガ型着色感光性組成物は、感度低下やアルカリ現像液への耐性劣化を引き起こすことなく、顔料濃度が高くなっても現像性や残渣が良好で、高品位なカラーフィルターを提供することができる。 The negative coloring photosensitive composition of the present invention provides a high-quality color filter with good developability and residue even when the pigment concentration is high, without causing a decrease in sensitivity and deterioration in resistance to an alkaline developer. be able to.
本発明のネガ型着色感光性組成物は、バインダーポリマー、特定の光重合性モノマー、色素、光重合開始剤、有機溶剤を含有し、必要に応じて、界面活性剤、熱硬化剤、重合禁止剤、紫外線吸収剤等の各種添加物を含有する。 The negative coloring photosensitive composition of the present invention contains a binder polymer, a specific photopolymerizable monomer, a dye, a photopolymerization initiator, and an organic solvent, and if necessary, a surfactant, a thermosetting agent, and a polymerization prohibition. Contains various additives, such as an agent and an ultraviolet absorber.
本発明で用いられるバインダーポリマーとしては、色素に対してバインダーとして作用し、かつカラーフィルター製造時の現像処理工程において用いられる現像液に可溶である感光性樹脂が好ましく、特に好ましくはアルカリ可溶性樹脂、水溶性樹脂が用いられる。 The binder polymer used in the present invention is preferably a photosensitive resin that acts as a binder for the dye and is soluble in a developer used in the development processing step during the production of a color filter, and particularly preferably an alkali-soluble resin. Water-soluble resin is used.
本発明で使用しうるアルカリ可溶性樹脂としては、現像時のアルカリ又はアルカリと界面活性剤との混合液に可溶なポリマーが使用され、より好ましくはカルボキシル基又はそのエステル基を有するポリマーであり、特に、1個以上のカルボキシル基を有するエチレン性不飽和モノマー(以下、単に「カルボキシル基含有不飽和モノマー」という。)と他の共重合可能なエチレン性不飽和モノマー(以下、単に「他の不飽和モノマー」という。)とを含有するモノマー混合物の共重合体(以下、単に「カルボキシル基含有共重合体」という。)が好ましい。前記カルボキシル基含有不飽和モノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、α−クロルアクリル酸、エタクリル酸、けい皮酸等の不飽和モノカルボン酸類;マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、シトラコン酸、無水シトラコン酸、メサコン酸等の不飽和ジカルボン酸(無水物)類;3価以上の不飽和多価カルボン酸(無水物)類等を挙げることができる。これらのカルボキシル基を有するエチレン性不飽和モノマーは、単独で又は2種以上を混合して使用することができる。 As an alkali-soluble resin that can be used in the present invention, a polymer that is soluble in a mixed solution of an alkali or an alkali and a surfactant during development is used, more preferably a polymer having a carboxyl group or an ester group thereof, In particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”) and other copolymerizable ethylenically unsaturated monomers (hereinafter simply referred to as “other unsaturated monomers”). And a monomer mixture copolymer (hereinafter simply referred to as “carboxyl group-containing copolymer”). Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and fumaric acid. , Unsaturated dicarboxylic acids (anhydrides) such as itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides) . These ethylenically unsaturated monomers having a carboxyl group can be used alone or in admixture of two or more.
また、前記他の不飽和モノマーとしては、例えば、芳香族ビニル化合物、不飽和カルボン酸エステル類、カルボン酸ビニルエステル類、不飽和カルボン酸アミノアルキルエステル類、不飽和カルボン酸グリシジルエステル類、不飽和エーテル類、シアン化ビニル化合物、不飽和アミドあるいは不飽和イミド類、重合体分子鎖の末端にモノアクリロイル基あるいはモノメタクリロイル基を有するマクロモノマー類等を挙げることができる。 Examples of the other unsaturated monomers include aromatic vinyl compounds, unsaturated carboxylic acid esters, carboxylic acid vinyl esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, and unsaturated monomers. Examples thereof include ethers, vinyl cyanide compounds, unsaturated amides or unsaturated imides, and macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain.
芳香族ビニル化合物としては、例えばスチレン、α−メチルスチレン、o−ビニルトルエン、m−ビニルトルエン、p−ビニルトルエン、o−クロルスチレン、m−クロルスチレン、p−クロルスチレン、p−メトキシスチレン等があげられる。不飽和カルボン酸エステル類としては、例えばメチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、n−プロピルアクリレート、i−プロピルアクリレート、n−プロピルメタクリレート、i−プロピルメタクリレート、n−ブチルアクリレート、i−ブチルアクリレート、sec−ブチルアクリレート、t−ブチルアクリレート、n−ブチルメタクリレート、i−ブチルメタクリレート、sec−ブチルメタクリレート、t−ブチルメタクリレート、2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、ベンジルアクリレート、ベンジルメタクリレート等があげられる。カルボン酸ビニルエステル類としては、例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等があげられる。不飽和カルボン酸アミノアルキルエステル類としては、例えば2−アミノエチルアクリレート、2−アミノエチルメタクリレート、2−アミノプロピルアクリレート、2−アミノプロピルメタクリレート、3−アミノプロピルアクリレート、3−アミノプロピルメタクリレート等があげられる。 Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-methoxystyrene, and the like. Can be given. Examples of unsaturated carboxylic acid esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, i-propyl acrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl acrylate, and i-butyl. Acrylate, sec-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, etc. Can be given. Examples of the carboxylic acid vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and the like. Examples of unsaturated carboxylic acid aminoalkyl esters include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, and the like. It is done.
不飽和カルボン酸グリシジルエステル類としては、例えばグリシジルアクリレート、グリシジルメタクリレート等があげられる。不飽和エーテル類としては、例えばビニルメチルエーテル、ビニルエチルエーテル、アリルグリシジルエーテル、メタリルグリシジルエーテル等があげられる。シアン化ビニル化合物としては、例えばアクリロニトリル、メタクリロニトリル、α−クロロアクリロニトリル、シアン化ビニリデン等があげられる。不飽和アミドあるいは不飽和イミド類としては、例えばアクリルアミド、メタクリルアミド、α−クロロアクリルアミド、N−(2−ヒドロキシエチル)アクリルアミド、N−(2−ヒドロキシエチル)メタクリルアミド、マレイミド等があげられる。脂肪族共役ジエン類としては、例えば1,3−ブタジエン、イソプレン、クロロプレン等があげられる。重合体分子鎖の末端にモノアクリロイル基あるいはモノメタクリロイル基を有するマクロモノマー類としては、例えばポリスチレン、ポリメチルアクリレート、ポリメチルメタクリレート、ポリn−ブチルアクリレート、ポリn−ブチルメタクリレート、ポリシリコーン等があげられる。これらの他の不飽和モノマーは、単独で又は2種以上を混合して使用することができる。 Examples of the unsaturated carboxylic acid glycidyl esters include glycidyl acrylate and glycidyl methacrylate. Examples of unsaturated ethers include vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, and methallyl glycidyl ether. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide and the like. Examples of unsaturated amides or unsaturated imides include acrylamide, methacrylamide, α-chloroacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, maleimide and the like. Examples of the aliphatic conjugated dienes include 1,3-butadiene, isoprene, chloroprene and the like. Examples of the macromonomer having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain include polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, and polysilicone. It is done. These other unsaturated monomers can be used alone or in admixture of two or more.
カルボキシル基含有共重合体としては、アクリル酸および/又はメタクリル酸とメチルメタクリレート、2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、ベンジルアクリレート、ベンジルメタクリレート、スチレン、ポリスチレンマクロモノマーおよびポリメチルメタクリレートマクロモノマーの群から選ばれる少なくとも1種の他の不飽和モノマーとの共重合体が好ましい。好ましいカルボキシル基含有共重合体の具体例としては、アクリル酸/ベンジルアクリレート共重合体、アクリル酸/ベンジルアクリレート/スチレン共重合体、アクリル酸/メチルアクリレート/スチレン共重合体、アクリル酸/ベンジルアクリレート/ポリスチレンマクロモノマー共重合体、アクリル酸/ベンジルアクリレート/ポリメチルメタクリレートマクロモノマー共重合体、アクリル酸/メチルアクリレート/ポリスチレンマクロモノマー共重合体、アクリル酸/メチルアクリレート/ポリメチルメタクリレートマクロモノマー共重合体、アクリル酸/ベンジルメタクリレート共重合体、アクリル酸/ベンジルメタクリレート/スチレン共重合体、アクリル酸/メチルメタクリレート/スチレン共重合体、アクリル酸/ベンジルメタクリレート/ポリスチレンマクロモノマー共重合体、アクリル酸/ベンジルメタクリレート/ポリメチルメタクリレートマクロモノマー共重合体、アクリル酸/メチルメタクリレート/ポリスチレンマクロモノマー共重合体、アクリル酸/メチルメタクリレート/ポリメチルメタクリレートマクロモノマー共重合体、アクリル酸/2−ヒドロキシエチルメタクリレート/ベンジルメタクリレート共重合体、アクリル酸/2−ヒドロキシエチルメタクリレート/ベンジルメタクリレート/ポリスチレンマクロモノマー共重合体、アクリル酸/2−ヒドロキシエチルメタクリレート/ベンジルメタクリレート/ポリメチルメタクリレートマクロモノマー共重合体等のアクリル酸共重合体;メタクリル酸/ベンジルアクリレート共重合体、メタクリル酸/ベンジルアクリレート/スチレン共重合体、メタクリル酸/メチルアクリレート/スチレン共重合体、メタクリル酸/ベンジルアクリレート/ポリスチレンマクロモノマー共重合体、メタクリル酸/ベンジルアクリレート/ポリメチルメタクリレートマクロモノマー共重合体、メタクリル酸/メチルアクリレート/ポリスチレンマクロモノマー共重合体、メタクリル酸/メチルアクリレート/ポリメチルメタクリレートマクロモノマー共重合体、メタクリル酸/ベンジルメタクリレート共重合体、メタクリル酸/ベンジルメタクリレート/スチレン共重合体、メタクリル酸/メチルメタクリレート/スチレン共重合体、メタクリル酸/ベンジルメタクリレート/ポリスチレンマクロモノマー共重合体、メタクリル酸/ベンジルメタクリレート/ポリメチルメタクリレートマクロモノマー共重合体、メタクリル酸/メチルメタクリレート/ポリスチレンマクロモノマー共重合体、メタクリル酸/メチルメタクリレート/ポリメチルメタクリレートマクロモノマー共重合体、メタクリル酸/2−ヒドロキシエチルメタクリレート/ベンジルメタクリレート共重合体、メタクリル酸/2−ヒドロキシエチルメタクリレート/ベンジルメタクリレート/ポリスチレンマクロモノマー共重合体、メタクリル酸/2−ヒドロキシエチルメタクリレート/ベンジルメタクリレート/ポリメチルメタクリレートマクロモノマー共重合体等を挙げることができる。 Examples of the carboxyl group-containing copolymer include acrylic acid and / or methacrylic acid and methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer and polymethyl methacrylate macromonomer. A copolymer with at least one other unsaturated monomer selected from the group is preferred. Specific examples of preferred carboxyl group-containing copolymers include acrylic acid / benzyl acrylate copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / Polystyrene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl acrylate / polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, Acrylic acid / benzyl methacrylate copolymer, acrylic acid / benzyl methacrylate / styrene copolymer, acrylic acid / methyl methacrylate / styrene copolymer, acrylic acid / benzyl Tacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer Polymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl Acrylic acid copolymer such as methacrylate macromonomer copolymer; methacrylic acid / benzyl acrylate copolymer, meta Lauric acid / benzyl acrylate / styrene copolymer, methacrylic acid / methyl acrylate / styrene copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, Methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / Methyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate Relate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate Examples thereof include a copolymer, a methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, and a methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer.
また、共重合体の側鎖に更に不飽和二重結合を導入した重合体も有用である。例えば、無水マレイン酸とこれと共重合可能なスチレン、ビニルフェノール、アクリル酸、アクリル酸エステル、アクリルアミド等との共重合物の無水マレイン酸部に、ヒドロキシエチルアクリレート等のアルコール性のヒドロキシル基を有するアクリレートやグリシジルメタクリレート等のエポキシ基を有するアクリレートを反応させハーフエステル化した化合物及びアクリル酸、アクリル酸エステルとヒドロキシエチルアクリレート等のアルコール性のヒドロキシル基を有するアクリレートとの共重合体の−OH基にアクリル酸を反応せしめた化合物等が挙げられる。 A polymer in which an unsaturated double bond is further introduced into the side chain of the copolymer is also useful. For example, the maleic anhydride part of a copolymer of maleic anhydride and a copolymer of styrene, vinylphenol, acrylic acid, acrylic ester, acrylamide, etc. copolymerizable therewith has an alcoholic hydroxyl group such as hydroxyethyl acrylate A compound obtained by reacting an acrylate having an epoxy group such as acrylate or glycidyl methacrylate with a half ester, and a copolymer of acrylic acid, an acrylate ester and an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate. The compound etc. which reacted acrylic acid are mentioned.
前記水溶性樹脂としては、現像時に水又は界面活性剤を含有する水に可溶な樹脂が用いられ、特にアクリル系、メタクリル系、ポリビニルアルコール系、ポリビニルピロリドン系、アクリロイルモルホリン系樹脂等の使用が好ましい。具体的には、アクリル系樹脂としてはアクリル酸、アクリル酸ソーダ、アクリルアミド等の単独重合体及び共重合体等が、メタクリル系樹脂としてはメタクリル酸、メタクリル酸ソーダ、2−ヒドロキシメタクリル酸等の単独重合体及び共重合体がそれぞれ挙げられる。 As the water-soluble resin, a water-soluble resin containing water or a surfactant is used during development, and in particular, use of an acrylic, methacrylic, polyvinyl alcohol, polyvinylpyrrolidone, acryloylmorpholine resin, etc. preferable. Specifically, homopolymers and copolymers such as acrylic acid, sodium acrylate, and acrylamide are used as the acrylic resin, and methacrylic acid, sodium methacrylate, 2-hydroxymethacrylic acid are used alone as the methacrylic resin. A polymer and a copolymer are mentioned, respectively.
本発明において、前記バインダーポリマーは、単独で又は2種以上を混合して使用することができる。本発明におけるバインダーポリマーの含有量は、ネガ型着色感光性組成物の全固形分100重量部に対して、通常、5〜80重量部、好ましくは10〜60重量部である。この場合、バインダーポリマーの含有量が10重量部未満では、例えば、アルカリ現像性が低下したり、画素が形成される部分以外の領域での地汚れや膜残りが発生するおそれがある。 In this invention, the said binder polymer can be used individually or in mixture of 2 or more types. The content of the binder polymer in the present invention is usually 5 to 80 parts by weight, preferably 10 to 60 parts by weight with respect to 100 parts by weight of the total solid content of the negative coloring photosensitive composition. In this case, when the content of the binder polymer is less than 10 parts by weight, for example, alkali developability may be deteriorated or background stains or film residue may occur in a region other than a portion where pixels are formed.
バインダーポリマーの共重合体の重量平均分子量(Mw)としては、2000〜1000000、好ましくは3000〜400000である。重量平均分子量が2000以下の場合、また重量平均分子量が400000以上の場合になると、感度および現像性が悪くなる。 As a weight average molecular weight (Mw) of the copolymer of a binder polymer, it is 2000-1 million, Preferably it is 3000-400000. When the weight average molecular weight is 2,000 or less, and when the weight average molecular weight is 400,000 or more, the sensitivity and developability deteriorate.
本発明で使用する光重合性モノマーとしては、上記式(1)で表される化合物からなる。特に好ましくは、下記式(3)で表されるエチレンオキシド(EO)変性グリセリントリアクリレート(GEA)、下記式(4)で表される(EO)変性ジグリセリンテトラアクリレート(DGEA)が挙げられる。 As a photopolymerizable monomer used by this invention, it consists of a compound represented by the said Formula (1). Particularly preferred are ethylene oxide (EO) -modified glycerin triacrylate (GEA) represented by the following formula (3) and (EO) -modified diglycerin tetraacrylate (DGEA) represented by the following formula (4).
式(3)中のl、m、nは以下の表に示す。 L, m, and n in the formula (3) are shown in the following table.
式(4)中のk、l、m、nは以下の表に示す。 K, l, m and n in the formula (4) are shown in the following table.
GEAの製法は、例えば特表2005−532431号公報に記載されており、またDGEAの製法は、例えば特開平10−321040号公報に記載されている。具体的には、例えば、グリセリンやジグリセリンにエチレンオキサイドを反応させ、その後アクリル酸やメタクリル酸でエステル化することによって得られる。エチレンオキサイドとの反応は、耐圧反応容器を用い、無溶媒、又は水やジメチルスルホキシド、ジメチルアセトアミド、ジメチルホルムアミド、N−メチルピロリドン等の有機溶媒で塩基触媒の存在下、エチレンオキサイドを加圧下で反応させることによって行われる。溶媒量はグリセリンやジグリセリンに対して、0.1〜10倍容量用いられる。塩基触媒としては、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート等が上げられ、(ポリ)グリセリンに対して、0.01〜20重量%使用される。 The method for producing GEA is described, for example, in JP-T-2005-532431, and the method for producing DGEA is described, for example, in JP-A-10-321040. Specifically, for example, it is obtained by reacting ethylene oxide with glycerin or diglycerin and then esterifying with acrylic acid or methacrylic acid. The reaction with ethylene oxide is carried out using a pressure-resistant reaction vessel, with no solvent, or in the presence of a base catalyst in water or an organic solvent such as dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and ethylene oxide. Is done by letting The amount of the solvent is 0.1 to 10 times the volume of glycerin or diglycerin. Examples of the base catalyst include sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, etc., and 0.01 to 20% by weight based on (poly) glycerin.
(メタ)アクリル酸でのエステル化方法としては、n−ヘキサン、n−ヘプタンのような脂肪族炭化水素、ベンゼン、トルエンのような芳香族炭化水素、シクロヘキサン、メチルシクロヘキサンのような脂環式炭化水素等の溶媒中、p−トルエンスルホン酸やメタンスルホン酸のような酸触媒を用い、生成する水を反応系外に除去しながら、上記エトキシ化(ポリ)グリセリンと(メタ)アクリル酸とを加熱下に反応させることによって行われる。溶媒量は反応混合物の5〜300重量%であり、触媒量はアクリル酸、メタクリル酸に対して0.1〜10モル%使用される。反応温度は60〜130℃の範囲がよい。 The esterification method with (meth) acrylic acid includes aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as benzene and toluene, alicyclic carbonization such as cyclohexane and methylcyclohexane. In a solvent such as hydrogen, an acid catalyst such as p-toluenesulfonic acid or methanesulfonic acid is used to remove the generated water from the reaction system, while the ethoxylated (poly) glycerin and (meth) acrylic acid are combined. The reaction is carried out under heating. The amount of solvent is 5 to 300% by weight of the reaction mixture, and the amount of catalyst is 0.1 to 10% by mole based on acrylic acid and methacrylic acid. The reaction temperature is preferably in the range of 60 to 130 ° C.
前記モノマーは、単独でまたは2種以上を混合して使用することができる。本発明におけるモノマーの使用量は、ネガ型着色感光性組成物の全固形分100重量部に対して5〜60重量部、好ましくは10〜50重量部である。 The said monomer can be used individually or in mixture of 2 or more types. The usage-amount of the monomer in this invention is 5-60 weight part with respect to 100 weight part of total solid content of a negative coloring photosensitive composition, Preferably it is 10-50 weight part.
また、本発明においては、前記のモノマーの一部を他の光重合性モノマーに置き換えることもできる。例えば2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、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、トリエチレングリコー(メタ)アクリレート、テトラエチレングリコール(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ジ(メタ)アクリレート、ペンタエリスリトールトリ(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、グリセロール(メタ)アクリレート、ビスフェノール−A型エポキシジ(メタ)アクリレート、ビスフェノール−F型エポキシジ(メタ)アクリレート、ビスフェノール−フルオレン型エポキシジ(メタ)アクリレート等が挙げられる。他の光重合性モノマーは、単独でまたは2種以上使用してもよい。他の光重合性モノマーの使用量は光重合性モノマー合計100重量部に対して0〜200重量部であり、好ましくは0〜100重量部である。 In the present invention, a part of the monomer can be replaced with another photopolymerizable monomer. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethyleneglycol (meth) acrylate, Tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, bisphenol-F type epoxy di (meth) Acrylate, bisphenol - fluorene epoxy di (meth) acrylate. Other photopolymerizable monomers may be used alone or in combination of two or more. The usage-amount of another photopolymerizable monomer is 0-200 weight part with respect to 100 weight part of photopolymerizable monomers total, Preferably it is 0-100 weight part.
本発明に使用する色素は、カラーフィルターに適合する分光特性を有するものが好ましく、有機顔料、無機顔料、染料の中から適宜選択することが出来る。 The pigment used in the present invention preferably has a spectral characteristic suitable for a color filter, and can be appropriately selected from organic pigments, inorganic pigments, and dyes.
本発明に用いることができる有機顔料としては特に制限はなく、例えば、アントラキノン系、フタロシアニン系、ベンゾイミダゾロン系、キナクリドン系、アゾキレート系、アゾ系、イソインドリン系、イソインドリノン系、ピランスロン系、インダスロン系、アンスラピリミジン系、ジブロモアンザンスロン系、フラバンスロン系、ペリレン系、ペリノン系、キノフタロン系、チオインジゴ系、ジオキサジン系、キナクリドン系等の顔料や酸性染料、塩基性染料、直接染料等をそれぞれの沈澱剤で不溶化したレーキ顔料、染付けレーキ顔料が使用できる。これらの顔料は、必要に応じて単独又は2種以上組み合わせて使用することができる。 The organic pigment that can be used in the present invention is not particularly limited. For example, anthraquinone, phthalocyanine, benzimidazolone, quinacridone, azochelate, azo, isoindoline, isoindolinone, pyranthrone, Indanthrone, anthrapyrimidine, dibromoanthanthrone, flavanthrone, perylene, perinone, quinophthalone, thioindigo, dioxazine, quinacridone, pigments, acid dyes, basic dyes, direct dyes, etc. Lake pigments and dyed lake pigments insolubilized with a precipitant can be used. These pigments can be used alone or in combination of two or more as required.
本発明に用いることができる無機顔料の例としては、複合金属酸化物顔料、カーボンブラック、黒色低次酸化チタン、酸化チタン、硫酸バリウム、亜鉛華、硫酸鉛、黄色鉛、ベンガラ、群青、紺青、酸化クロム、アンチモン白、鉄黒、鉛丹、硫化亜鉛、カドニウムエロー、カドニウムレッド、亜鉛、マンガン紫、コバルト紫、硫酸バリウム、炭酸マグネシウム等の金属酸化物、金属硫化物、硫酸塩、金属水酸化物、金属炭酸塩等が挙げられる。これらの顔料は、必要に応じて単独又は2種以上組み合わせて使用することができる。 Examples of inorganic pigments that can be used in the present invention include composite metal oxide pigments, carbon black, black low-order titanium oxide, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, red rose, ultramarine blue, bitumen, Chromium oxide, antimony white, iron black, red lead, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese purple, cobalt purple, barium sulfate, magnesium carbonate, and other metal oxides, metal sulfides, sulfates, metal hydroxides Products, metal carbonates and the like. These pigments can be used alone or in combination of two or more as required.
本発明に顔料を使用する場合は、顔料分散剤を含有する有機溶剤で顔料を分散させ、顔料分散組成物を得、その顔料分散組成物を光硬化性組成物に均一に分散する方法や、ネガ型着色感光性組成物に用いるバインダー樹脂で顔料を分散し、その後、モノマーや光重合開始剤等を加えてネガ型着色感光性組成物を製造する方法等がある。分散する際は、ボールミル、サンドミル、ロールミル、ビーズミル、ディゾルバー、ホモミキサー、高圧分散機等の各種分散機を用いる。 When using a pigment in the present invention, the pigment is dispersed with an organic solvent containing a pigment dispersant to obtain a pigment dispersion composition, and the pigment dispersion composition is uniformly dispersed in the photocurable composition. There is a method of producing a negative colored photosensitive composition by dispersing a pigment with a binder resin used in a negative colored photosensitive composition and then adding a monomer, a photopolymerization initiator, or the like. When dispersing, various dispersers such as a ball mill, a sand mill, a roll mill, a bead mill, a dissolver, a homomixer, and a high-pressure disperser are used.
本発明に用いることができる染料は、有機溶剤に可溶な染料を適宜使用する。それらの染料としては酸性染料、塩基性染料、直接染料、硫化染料、建染染料、ナフトール染料、反応染料、分散染料等が挙げられる。また、染料の有機溶剤への溶解性を上げるために例えば酸性染料、塩基性染料等とアミン、例えばn−プロピルアミン、エチルヘキシルプロピオン酸アミン等の有機アミンを反応させたアミン塩染料や、酸性染料、塩基性染料等のスルホン酸基にアミン、例えばn−プロピルアミン、エチルヘキシルプロピオン酸アミン等の有機アミンを反応させたスルホンアミド基を有する染料等に変性すると有機溶剤への溶解性が増すことが知られている。それらアミン変性した染料も本発明のネガ型着色感光性組成物に使用可能である。 As the dye that can be used in the present invention, a dye that is soluble in an organic solvent is appropriately used. Examples of these dyes include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and disperse dyes. In addition, in order to increase the solubility of the dye in an organic solvent, for example, an acid salt, a basic dye or the like and an amine, for example, an amine salt dye obtained by reacting an organic amine such as n-propylamine or ethylhexylpropionate, or an acid dye Modification to a dye having a sulfonamide group obtained by reacting an organic amine such as n-propylamine or ethylhexylpropionate with a sulfonic acid group such as a basic dye may increase the solubility in an organic solvent. Are known. These amine-modified dyes can also be used in the negative coloring photosensitive composition of the present invention.
これらの色素の含有量としては、ネガ型着色感光性組成物の固形分を100重量部としたとき5〜70重量部、好ましく10〜60重量部である。その含有量は、所望する硬化膜の膜厚、分光特性によって適宜決定される。又、本発明で使用される色素の色相としては赤色、青色、緑色、黒色、黄色、マゼンタ、シアン等が挙げられる。 The content of these dyes is 5 to 70 parts by weight, preferably 10 to 60 parts by weight, when the solid content of the negative coloring photosensitive composition is 100 parts by weight. The content is appropriately determined depending on the desired thickness and spectral characteristics of the cured film. Examples of the hue of the dye used in the present invention include red, blue, green, black, yellow, magenta, and cyan.
本発明に用いる光重合開始剤は、露光光源として一般的に用いられる超高圧水銀灯から出射される紫外線に充分感度を有するものが好ましく、使用しうる光重合開始剤の具体例としては、例えばベンジル、ベンゾインエーテル、ベンゾインブチルエーテル、ベンゾインプロピルエーテル、ベンゾフェノン、3,3'−ジメチル−4−メトキシベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸のエステル化物、4−ベンゾイル−4'−メチルジフェニルスルフィド、ベンジルジメチルケタール、2−ブトキシエチル−4−メチルアミノベンゾエート、クロロチオキサントン、メチルチオキサントン、エチルチオキサントン、イソプロピルチオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、ジイソプロピルチオキサントン、ジメチルアミノメチルベンゾエート、1−(4−ドデシルフェニル)−2−ヒドロキシ−2−メチルプロパン−1−オン、1−ヒドロキシシクロヘキシルフェニルケトン、2−ヒドロキシ−2−メチル−1−フェニルプロパン−1−オン、1−(4−イソプロピルフェニル)−2−ヒドロキシ−2−メチルプロパン−1−オン、メチルベンゾイルフォーメート、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、2,4−ビス(トリクロロメチル)−6−(4−メトキシフェニル)−1,3,5−s−トリアジン、2,4,6−トリス(トリクロロメチル)−1,3,5−s−トリアジン、2,4−ビス(トリブロモメチル)−6−(4'−メトキシフェニル)−1,3,5−s−トリアジン、2,4,6−トリス(トリブロモメチル)−1,3,5−s−トリアジン、2,4−ビス(トリクロロメチル)−6−(1,3−ベンゾジオキソラン−5−イル)−1,3,5−s−トリアジン、ベンゾフェノン、ベンゾイル安息香酸、1−(4−フェニルスルファニルフェニル)ブタン−1,2−ジオン−2−オキシム−O−ベンゾアート、1−(4−メチルスルファニルフェニル)ブタン−1,2−ジオン−2−オキシム−O−アセタート、1−(4−メチルスルファニルフェニル)ブタン−1−オンオキシム−O−アセタート、4,4'−ビス(ジエチルアミノ)ベンゾフェノン、P−ジメチルアミノ安息香酸イソアミルエステル、P−ジメチルアミノ安息香酸エチルエステル、2,2'−ビス(O−クロロフェニル)−4,4',5,5'−テトラフェニル−1,2'−ビイミダゾール等が挙げられる。 The photopolymerization initiator used in the present invention preferably has sufficient sensitivity to ultraviolet rays emitted from an ultrahigh pressure mercury lamp generally used as an exposure light source. Specific examples of the photopolymerization initiator that can be used include benzyl Benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, esterified product of benzoylbenzoic acid, 4-benzoyl-4'-methyldiphenyl sulfide, benzyldimethyl ketal 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone , Dimethylaminomethylbenzoate, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-s Triazine, 2,4,6-tris (trichloromethyl) -1,3,5-s-triazine, 2,4-bis (trib Lomomethyl) -6- (4′-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-s-triazine, 2,4- Bis (trichloromethyl) -6- (1,3-benzodioxolan-5-yl) -1,3,5-s-triazine, benzophenone, benzoylbenzoic acid, 1- (4-phenylsulfanylphenyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butane-1 -Onoxime-O-acetate, 4,4'-bis (diethylamino) benzophenone, P-dimethylaminobenzoic acid isoamyl ester, P-dimethylamino acid Kosan ethyl ester, 2,2'-bis (O-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.
これらはカヤキュアーDMBI、カヤキュアーBDMK、カヤキュアーBP−100、カヤキュアーBMBI、カヤキュアーDETX−S、カヤキュアーEPA(いずれも日本化薬製)、ダロキュアー1173、ダロキュアー1116(いれもメルクジャパン製)、イルガキュアー907、イルガキュアー369(チバ・スペシャルティ・ケミカルズ製)、ビイミダゾール(黒金化成製)、STR−110、STR−1(いずれもレスペケミカル製)等として市場から容易に入手可能である。 These are Kaya Cure DMBI, Kaya Cure BDK, Kaya Cure BP-100, Kaya Cure BMBI, Kaya Cure DETX-S, Kaya Cure EPA (all manufactured by Nippon Kayaku), Daro Cure 1173, Daro Cure 1116 (all from Merck Japan), Irgacure 907, Iruga Cure Cure 369 (manufactured by Ciba Specialty Chemicals), biimidazole (manufactured by Kurokin Kasei), STR-110, STR-1 (all manufactured by Respe Chemical) are easily available from the market.
これらの光重合開始剤は単独又は2種以上組み合わせて使用することができる。これらの含有量は、ネガ型着色感光性組成物の固形分を100重量部としたとき0.5〜30重量部、好ましくは1〜25重量部である。 These photopolymerization initiators can be used alone or in combination of two or more. These contents are 0.5-30 weight part when the solid content of a negative coloring photosensitive composition is 100 weight part, Preferably it is 1-25 weight part.
本発明に用いる有機溶剤は、ネガ型着色感光性組成物の構成成分であるバインダーポリマー、光重合性モノマー、光重合開始剤等に対して十分な溶解力を有するものが使用出来る。使用可能な有機溶剤の具体例としては、例えば、ベンゼン、トルエン、キシレン等のベンゼン類、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ等のセロソルブ類、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート等のセロソルブ酢酸エステル類、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテル酢酸エステル類、メトキシプロピオン酸メチル、メトキシプロピオン酸エチル、エトキシプロピオン酸メチル、エトキシプロピオン酸エチル等のプロピオン酸エステル類、乳酸メチル、乳酸エチル、乳酸ブチル等の乳酸エステル類、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル等のジエチレングリコール類、酢酸メチル、酢酸エチル、酢酸ブチル等の酢酸エステル類、ジメチルエーテル、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類、アセトン、メチルエチルケトン、メチルブチルケトン、シクロヘキサノン等のケトン類等が挙げられる。 As the organic solvent used in the present invention, those having sufficient dissolving power with respect to a binder polymer, a photopolymerizable monomer, a photopolymerization initiator and the like which are constituents of the negative coloring photosensitive composition can be used. Specific examples of usable organic solvents include, for example, benzenes such as benzene, toluene and xylene, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, cellosolve acetate such as methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate. Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate Propionic acid esters such as methyl lactate, methyl lactate, ethyl lactate, lactic acid ester such as butyl lactate , Diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, acetates such as methyl acetate, ethyl acetate and butyl acetate, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone And ketones.
これらは単独もしくは2種以上組み合わせて使用してもよい。また、有機溶剤の含有量は、ネガ型着色感光性組成物の全固形分100重量部に対して50〜2000重量部、好ましくは100〜1000重量部である。 You may use these individually or in combination of 2 or more types. The content of the organic solvent is 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts by weight of the total solid content of the negative coloring photosensitive composition.
本発明のネガ型着色感光性組成物は、前記の、バインダーポリマー、光重合性モノマー、光重合開始剤、色素、2個以上のカルボキシル基を有するヒンダートアミン系ラジカル捕捉剤及び有機溶剤をディゾルバー、ホモミキサー等により、混合撹拌して製造される。又、使用する色素が顔料である場合は、必要なら、前記したような加工が施される。 The negative colored photosensitive composition of the present invention comprises a binder polymer, a photopolymerizable monomer, a photopolymerization initiator, a dye, a hindered amine radical scavenger having two or more carboxyl groups, and an organic solvent as a dissolver. It is produced by mixing and stirring with a homomixer or the like. Further, when the dye used is a pigment, the above-described processing is performed if necessary.
本発明のネガ型着色感光性組成物は、必要に応じて、さらに各種添加剤、例えば、充填剤、界面活性剤、熱重合防止剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤を含有することができる。又、本発明のネガ型着色感光性組成物は、その調製後に異物等を取り除くためフィルター等で精密濾過することも出来る。 The negative coloring photosensitive composition of the present invention may further contain various additives as necessary, for example, fillers, surfactants, thermal polymerization inhibitors, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors. An agent can be contained. In addition, the negative colored photosensitive composition of the present invention can be microfiltered with a filter or the like in order to remove foreign matters after the preparation.
次に本発明のネガ型着色感光性組成物からその硬化物を調製する方法について説明する。先ず、本発明のネガ型着色感光性組成物をガラス基板、シリコン基板等の基板上に、スピンコート法、ロールコート法、バーコート法等の方法で、膜厚が大凡0.1〜5μmになるように塗布し、温度60〜120℃、時間1〜10分というような条件でプリベーク処理を行い製膜する。次にそれ自体公知のフォトリソグラフィー法により所定のマスクパターンを通して放射線(例えば電子線、紫外線、好ましくは紫外線)を照射し、界面活性剤水溶液、アルカリ水溶液又は(界面活性剤+アルカリ剤)水溶液で現像し、未照射部を取り除き、水でリンスした後、ポストベーク等の処理(例えば、温度150〜250℃、時間1〜30分というような条件)を行い、本発明の着色硬化膜からなる画素を得る。 Next, a method for preparing the cured product from the negative colored photosensitive composition of the present invention will be described. First, the negative colored photosensitive composition of the present invention is formed on a substrate such as a glass substrate or a silicon substrate by a spin coating method, a roll coating method, a bar coating method or the like so that the film thickness is about 0.1 to 5 μm. Then, a pre-bake treatment is performed to form a film under conditions such as a temperature of 60 to 120 ° C. and a time of 1 to 10 minutes. Next, radiation (for example, electron beam, ultraviolet rays, preferably ultraviolet rays) is irradiated through a predetermined mask pattern by a photolithography method known per se, and development is performed with a surfactant aqueous solution, an alkali aqueous solution, or a (surfactant + alkali agent) aqueous solution. Then, after removing the non-irradiated portion and rinsing with water, a process such as post-baking (for example, conditions such as a temperature of 150 to 250 ° C. and a time of 1 to 30 minutes) is performed, and the pixel comprising the colored cured film of the present invention Get.
上記において界面活性剤としてはポリオキシエチレンアルキルエーテル、ポリオキシアルキレンアルキルエーテル等が使用出来、通常それらの0.05〜1.0重量%の水溶液が使用される。又アルカリとしては、炭酸ナトリウム、炭酸カリウム、水酸化ナトリウム、水酸化カリウム、ジエタノールアミン、テトラメチルアンモニウムハイドロオキサイド等が使用され、通常それらの0.05〜1.0重量%の水溶液が使用される。本発明においては、アルカリと界面活性剤の両方を含む水溶液の使用が好ましい。又現像は、温度が通常10〜50℃、好ましくは20〜40℃、時間が通常30〜180秒、好ましくは30〜120秒というような条件で行われる。 In the above, as the surfactant, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether and the like can be used, and usually 0.05 to 1.0% by weight of an aqueous solution thereof is used. As the alkali, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide or the like is used, and an aqueous solution of 0.05 to 1.0% by weight thereof is usually used. In the present invention, it is preferable to use an aqueous solution containing both an alkali and a surfactant. The development is performed under such conditions that the temperature is usually 10 to 50 ° C., preferably 20 to 40 ° C., and the time is usually 30 to 180 seconds, preferably 30 to 120 seconds.
本発明のネガ型着色感光性組成物の硬化物は液晶表示装置に好適なカラーフィルターあるいはデジタルカメラ等に使用される固体撮像素子に好適なカラーフィルターとして有用である。本発明のカラーフイルターは前記のようにして調製された本発明のネガ型着色感光性組成物の硬化物からなるパターン化された複数色の着色画素を有する。 The cured product of the negative coloring photosensitive composition of the present invention is useful as a color filter suitable for a liquid crystal display device or a color filter suitable for a solid-state imaging device used in a digital camera or the like. The color filter of the present invention has a plurality of patterned colored pixels made of a cured product of the negative coloring photosensitive composition of the present invention prepared as described above.
本発明の液晶表示装置は、例えば、バックライト、偏光フィルム、表示電極、液晶、配向膜、共通電極、本発明のカラーフィルター、偏光フィルム等がこの順に積層した構造で作製される。 The liquid crystal display device of the present invention is produced, for example, with a structure in which a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, a polarizing film, and the like are laminated in this order.
又、本発明の固体撮像素子は、例えば、転送電極、フォトダイオードを設けたシリコンウエーハーの上に、本発明のカラーフィルター層を設け、ついでマイクロレンズを積層することにより作製される。 The solid-state imaging device of the present invention is produced, for example, by providing the color filter layer of the present invention on a silicon wafer provided with transfer electrodes and photodiodes, and then laminating microlenses.
以下実施例により本発明を更に詳細に説明する。実施例中、%は重量%を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. In the examples,% means% by weight.
実施例1
バインダーポリマーとしてメタクリル酸/ベンジルメタクリレート共重合体(20/80 重量比、重量平均分子量22,000)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(以下 PGMEAと略記)20%溶液 20g、光重合性モノマーとしてGEA−3E 6g、光重合開始剤としてイルガキュアー369(2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)ーブタノン−1、チバ・スペシャルティ・ケミカルズ製) 1g、カヤキュアーDETX−S(2,4−ジエチルチオキサントン、日本化薬製)0.5g、EAB(4,4'−ビス(ジエチルアミノ)ベンゾフェノン、保土ヶ谷化学工業製)0.1g、顔料として赤色顔料分散液(C.I.ピグメントレッド177/C.I.ピグメントイエロー139/分散剤/PGMEA=14.2/3.6/5.3/76.9 重量比)50g、溶剤としてPGMEA 45gを混合し、赤色の本発明のネガ型着色感光性組成物を得た。
又、上記で得られたネガ型着色感光性組成物をシリコンウエーハー上に熱硬化性下地膜を形成した基板上に塗布し、80℃×100秒の条件でプレベークしたのち、露光による硬化後、界面活性剤を含有するアルカリ水溶液で現像し、水でリンス後、200℃にて加熱し赤色パターンを得た。得られた赤色パターンは、ラインアンドスペースにて3μmの解像性を持ち、残渣、画素の剥がれ等は確認されなかった。
Example 1
20 g of a 20% solution of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) of methacrylic acid / benzyl methacrylate copolymer (20/80 weight ratio, weight average molecular weight 22,000) as a binder polymer, GEA-3E as a photopolymerizable monomer 6 g, Irgacure 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, manufactured by Ciba Specialty Chemicals) 1 g, Kayacure DETX-S (2,4- Diethylthioxanthone (Nippon Kayaku) 0.5g, EAB (4,4'-bis (diethylamino) benzophenone, Hodogaya Chemical Co., Ltd.) 0.1g, red pigment dispersion (CI Pigment Red 177 / C) as a pigment I. Pigment Yellow 13 / Dispersants /PGMEA=14.2/3.6/5.3/76.9 weight ratio) 50 g, the PGMEA 45 g as a solvent were mixed to obtain a negative type colored photosensitive composition of red present invention.
In addition, after applying the negative coloring photosensitive composition obtained above on a substrate having a thermosetting base film formed on a silicon wafer, prebaking under conditions of 80 ° C. × 100 seconds, and after curing by exposure The film was developed with an aqueous alkali solution containing a surfactant, rinsed with water, and then heated at 200 ° C. to obtain a red pattern. The obtained red pattern had a resolution of 3 μm in line and space, and no residue or peeling of pixels was confirmed.
実施例2
バインダーポリマーとしてメタクリル酸/2−ヒドロキシエチルメタクリレート/ベンジルメタクリレート共重合体(31/9/60 重量比、重量平均分子量16500)のPGMEA20%溶液 20g、光重合性モノマーとしてGEA−3E 6g 、光重合開始剤としてイルガキュアー907(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、チバ・スペシャルティ・ケミカルズ製) 2g、カヤキュアーDETX−S(日本化薬製)1g、EAB(4,4'−ビス(ジエチルアミノ)ベンゾフェノン、保土ヶ谷化学工業製)0.2g、顔料として青色顔料分散液(C.I.ピグメントブルー15:6/ピグメントバイオレット23/分散剤/PGMEA=9.6/2.4/8.2/79.8 重量比)72g、溶剤としてPGMEA 46gを混合し、青色の本発明のネガ型着色感光性組成物を得た。
又、上記で得られたネガ型着色感光性組成物を前記基板上に塗布し、80℃×100秒の条件でプレベークしたのち、露光による硬化後、界面活性剤を含有するアルカリ水溶液で現像し、水でリンス後、200℃にて加熱し緑色パターンを得た。得られた青色パターンは、ラインアンドスペースにて3μmの解像性を持ち、残渣、画素の剥がれ等は確認されなかった。
Example 2
20 g of PGMEA 20% solution of methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (31/9/60 weight ratio, weight average molecular weight 16500) as binder polymer, 6 g of GEA-3E as photopolymerizable monomer, start of photopolymerization Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, Ciba Specialty Chemicals) 2 g, Kayacure DETX-S (Nippon Kayaku) 1 g, EAB (4,4′-bis (diethylamino) benzophenone, manufactured by Hodogaya Chemical Co., Ltd.) 0.2 g, blue pigment dispersion as pigment (CI Pigment Blue 15: 6 / Pigment Violet 23 / Dispersant / PGMEA = 9.6) /2.4/8.2/79.8 weight ratio) 7 2 g and 46 g of PGMEA as a solvent were mixed to obtain a blue colored negative photosensitive composition of the present invention.
Also, the negative colored photosensitive composition obtained above is applied onto the substrate, pre-baked at 80 ° C. for 100 seconds, cured by exposure, and then developed with an aqueous alkali solution containing a surfactant. After rinsing with water, heating at 200 ° C. gave a green pattern. The obtained blue pattern had a resolution of 3 μm in line and space, and no residue or peeling of pixels was confirmed.
実施例3
バインダーポリマーとしてメタクリル酸/ベンジルメタクリレート共重合体(20/80 重量比、重量平均分子量22,000)のPGMEA20%溶液 20g、光重合性モノマーとしてGEA−3E 6g 、光重合開始剤として、イルガキュアー369(チバ・スペシャルティ・ケミカルズ製) 1.2g、カヤキュアーDETX−S(日本化薬製)0.6g、EAB(4,4'−ビス(ジエチルアミノ)ベンゾフェノン、保土ヶ谷化学工業製)0.1g、顔料として緑色顔料分散液(C.I.ピグメントグリーン17/C.I.ピグメントイエロー83/分散剤/PGMEA=12.1/5.2/7.4/75.3重量比)48g、溶剤としてPGMEA 48gを混合し、緑色の本発明のネガ型着色感光性組成物を得た。
又、上記で得られたネガ型着色感光性組成物を前記基板上に塗布し、80℃×100秒の条件でプレベークしたのち、露光による硬化後、界面活性剤を含有するアルカリ水溶液で現像し、水でリンス後、200℃にて加熱し緑色パターンを得た。得られた緑色パターンは、ラインアンドスペースにて3μm角の解像性を持ち、残渣、画素の剥がれ等は確認されなかった。
Example 3
20 g of PGMEA 20% solution of methacrylic acid / benzyl methacrylate copolymer (20/80 weight ratio, weight average molecular weight 22,000) as binder polymer, GEA-3E 6 g as photopolymerizable monomer, Irgacure 369 as photopolymerization initiator (Ciba Specialty Chemicals) 1.2g, Kayacure DETX-S (Nippon Kayaku) 0.6g, EAB (4,4'-bis (diethylamino) benzophenone, Hodogaya Chemical Co., Ltd.) 0.1g, as pigment 48 g of green pigment dispersion (CI Pigment Green 17 / CI Pigment Yellow 83 / Dispersant / PGMEA = 12.1 / 5.2 / 7.4 / 75.3 weight ratio), 48 g of PGMEA as a solvent Were mixed to obtain a green colored negative photosensitive composition of the present invention.
Also, the negative colored photosensitive composition obtained above is applied onto the substrate, pre-baked at 80 ° C. for 100 seconds, cured by exposure, and then developed with an aqueous alkali solution containing a surfactant. After rinsing with water, heating at 200 ° C. gave a green pattern. The obtained green pattern had a resolution of 3 μm square in line and space, and no residue or peeling of pixels was confirmed.
実施例4
バインダーポリマーとしてメタクリル酸/2−ヒドロキシエチルメタクリレート/ベンジルメタクリレート共重合体(15/13/72 重量比、重量平均分子量17,000)のPGMEA20%溶液 20g、光重合性モノマーとしてDGEA−4E 6g 、光重合開始剤として、イルガキュアー369(チバ・スペシャルティ・ケミカルズ製) 1.2g、カヤキュアーDETX−S(日本化薬製)0.6g、EAB(4,4'−ビス(ジエチルアミノ)ベンゾフェノン、保土ヶ谷化学工業製)0.1g、顔料として緑色顔料分散液(C.I.ピグメントグリーン17/C.I.ピグメントイエロー83/分散剤/PGMEA=12.1/5.2/7.4/75.3重量比)48g、溶剤としてPGMEA 48gを混合し、緑色の本発明のネガ型着色感光性組成物を得た。
又、上記で得られたネガ型着色感光性組成物を前記基板上に塗布し、80℃×100秒の条件でプレベークしたのち、露光による硬化後、界面活性剤を含有するアルカリ水溶液で現像し、水でリンス後、200℃にて加熱し緑色パターンを得た。得られた緑色パターンは、ラインアンドスペースにて3μm角の解像性を持ち、残渣、画素の剥がれ等は確認されなかった。
Example 4
20 g of PGMEA 20% solution of methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (15/13/72 weight ratio, weight average molecular weight 17,000) as binder polymer, 6 g of DGEA-4E as photopolymerizable monomer, light As a polymerization initiator, Irgacure 369 (Ciba Specialty Chemicals) 1.2g, Kayacure DETX-S (Nippon Kayaku) 0.6g, EAB (4,4'-bis (diethylamino) benzophenone, Hodogaya Chemical Industry 0.1 g, green pigment dispersion as pigment (CI Pigment Green 17 / CI Pigment Yellow 83 / dispersant / PGMEA = 12.1 / 5.2 / 7.4 / 75.3 weight) 48 g) and 48 g of PGMEA as a solvent were mixed, A ga-type colored photosensitive composition was obtained.
Also, the negative colored photosensitive composition obtained above is applied onto the substrate, pre-baked at 80 ° C. for 100 seconds, cured by exposure, and then developed with an aqueous alkali solution containing a surfactant. After rinsing with water, heating at 200 ° C. gave a green pattern. The obtained green pattern had a resolution of 3 μm square in line and space, and no residue or peeling of pixels was confirmed.
Claims (5)
(式(2)中、R1は水素原子またはメチル基、nは0〜10の整数を意味する。) A negative color for forming a color filter , comprising a binder polymer, a photopolymerizable monomer, a dye, a photopolymerization initiator, and an organic solvent, wherein the photopolymerizable monomer is a compound represented by the following formula (1): Photosensitive composition .
(In the formula (2), R 1 represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 10.)
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