JP2009204641A - Photosensitive colored composition for color filter, and color filter - Google Patents
Photosensitive colored composition for color filter, and color filter Download PDFInfo
- Publication number
- JP2009204641A JP2009204641A JP2008043903A JP2008043903A JP2009204641A JP 2009204641 A JP2009204641 A JP 2009204641A JP 2008043903 A JP2008043903 A JP 2008043903A JP 2008043903 A JP2008043903 A JP 2008043903A JP 2009204641 A JP2009204641 A JP 2009204641A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- coloring composition
- photosensitive coloring
- mass
- pigment
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 239000000049 pigment Substances 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 4
- 229920000570 polyether Polymers 0.000 claims abstract description 4
- 238000004040 coloring Methods 0.000 claims description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000003086 colorant Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 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 claims description 8
- 230000001588 bifunctional effect Effects 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 15
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002798 polar solvent Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 description 22
- -1 alkylene glycol ether Chemical compound 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 229920000178 Acrylic resin Polymers 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000037303 wrinkles Effects 0.000 description 6
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000012860 organic pigment Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- 239000004642 Polyimide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- CLDZVCMRASJQFO-UHFFFAOYSA-N 2,5-bis(2,4,4-trimethylpentan-2-yl)benzene-1,4-diol Chemical compound CC(C)(C)CC(C)(C)C1=CC(O)=C(C(C)(C)CC(C)(C)C)C=C1O CLDZVCMRASJQFO-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
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002223 polystyrene 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
- 238000002360 preparation method Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000001057 purple pigment Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RYNQKSJRFHJZTK-UHFFFAOYSA-N (3-methoxy-3-methylbutyl) acetate Chemical compound COC(C)(C)CCOC(C)=O RYNQKSJRFHJZTK-UHFFFAOYSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- DVFAVJDEPNXAME-UHFFFAOYSA-N 1,4-dimethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(C)=CC=C2C DVFAVJDEPNXAME-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- VXVGKMGIPAWMJC-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCC VXVGKMGIPAWMJC-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- BGJQNPIOBWKQAW-UHFFFAOYSA-N 1-tert-butylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)(C)C BGJQNPIOBWKQAW-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- PUABNAWFNOFZPZ-UHFFFAOYSA-N 2,3,5,6,7,8,9,9a-octahydro-1h-benzo[7]annulene Chemical compound C1CCCCC2CCCC=C21 PUABNAWFNOFZPZ-UHFFFAOYSA-N 0.000 description 1
- KPYPNTLKDIYIKB-UHFFFAOYSA-N 2,3-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(Cl)C(Cl)=C2 KPYPNTLKDIYIKB-UHFFFAOYSA-N 0.000 description 1
- ZHUWKKIRCLKYNJ-UHFFFAOYSA-N 2,5-bis(2-methylpentan-2-yl)benzene-1,4-diol Chemical compound CCCC(C)(C)C1=CC(O)=C(C(C)(C)CCC)C=C1O ZHUWKKIRCLKYNJ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- RZRILSWMGXWSJY-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;sulfuric acid Chemical compound OS(O)(=O)=O.OCCN(CCO)CCO RZRILSWMGXWSJY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ICGLGDINCXDWJB-UHFFFAOYSA-N 2-benzylprop-2-enamide Chemical compound NC(=O)C(=C)CC1=CC=CC=C1 ICGLGDINCXDWJB-UHFFFAOYSA-N 0.000 description 1
- YQZHOBBQNFBTJE-UHFFFAOYSA-N 2-chloro-3-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C(Cl)=C2 YQZHOBBQNFBTJE-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- NTZCFGZBDDCNHI-UHFFFAOYSA-N 2-phenylanthracene-9,10-dione Chemical compound C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 NTZCFGZBDDCNHI-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- IWDFHWZHHOSSGR-UHFFFAOYSA-O 3-ethyl-1h-imidazol-3-ium Chemical compound CCN1C=C[NH+]=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-O 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 241000694440 Colpidium aqueous Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- ARNIZPSLPHFDED-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 ARNIZPSLPHFDED-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004027 organic amino compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 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
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、感光性着色組成物に関し、特に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に好適な感光性着色組成物に関する。また、本発明は、該感光性着色組成物を用いて形成されるカラーフィルターに関する。
The present invention relates to a photosensitive coloring composition, and more particularly to a photosensitive coloring composition suitable for a color filter used in a liquid crystal display device or a solid-state imaging device. The present invention also relates to a color filter formed using the photosensitive coloring composition.
カラーフィルターは、通常、ブラックマトリクスを形成したガラス、プラスチックシートなどの透明基板表面に、赤、緑、青の異なる色相を、画素サイズが数１０μｍから数１００μｍの微細なストライプ状あるいはモザイク状等の色パターンによって形成したものからなっている。従来から、カラーフィルタを製造する方法は種々提案されており、中でも顔料分散法を用いた製造方法が広く知られている。その一例として、ネガティブタイプ（露光部硬化型）を取り上げ以下に説明する。
The color filter usually has different red, green and blue hues on a transparent substrate surface such as glass or plastic sheet on which a black matrix is formed, in a fine stripe shape or a mosaic shape with a pixel size of several tens to several hundreds of microns. It is made up of color patterns. Conventionally, various methods for manufacturing a color filter have been proposed, and among them, a manufacturing method using a pigment dispersion method is widely known. As an example, a negative type (exposed portion curing type) will be described and described below.
まず、顔料を分散剤や光重合性ポリマー中で分散させ、さらにアルカリ可溶性樹脂、光重合開始剤、反応性モノマー等を添加して感光性着色組成物を調整する。次いで、該組成物を基板上に塗布、乾燥した後、フォトマスクを介して露光し現像する。このように形成したパターンを加熱焼成して基板に定着させることで画素パターンを形成する。このサイクルを必要色数分繰り返すことで、着色被膜のパターンが得られる。 First, a pigment is dispersed in a dispersant or a photopolymerizable polymer, and an alkali-soluble resin, a photopolymerization initiator, a reactive monomer, or the like is further added to prepare a photosensitive coloring composition. Next, the composition is applied onto a substrate and dried, and then exposed and developed through a photomask. A pixel pattern is formed by heating and baking the pattern thus formed and fixing it to the substrate. By repeating this cycle for the required number of colors, a colored coating pattern can be obtained.
カラーフィルタ用の感光性着色組成物において、アルカリ現像性が良好で、高い露光感度、十分な解像性、基板密着性、耐溶剤性を有することが求められている。特に近年では、カラーフィルタの生産性を向上させるため、オーバーコートレスのカラーフィルタが望まれているが、耐溶剤性などの信頼性についてはまだまだ不十分である。オーバーコートレスでの画素の信頼性向上のためにニ官能性樹脂を用いる例（例えば、特許文献１参照）が提案されている。しかしながら、これらの組成物を使用した場合、画素上のシワやクラックは解消されるものの、感度が低下するため色差が悪化するという問題があった。 Photosensitive coloring compositions for color filters are required to have good alkali developability, high exposure sensitivity, sufficient resolution, substrate adhesion, and solvent resistance. Particularly in recent years, in order to improve the productivity of color filters, an overcoatless color filter is desired, but the reliability such as solvent resistance is still insufficient. An example of using a bifunctional resin to improve pixel reliability without overcoat has been proposed (for example, see Patent Document 1). However, when these compositions are used, although wrinkles and cracks on the pixels are eliminated, there is a problem that the color difference is deteriorated because the sensitivity is lowered.
一方、このようなネガ型感光性組成物からカラーフィルターを形成しようとすると、マスクサイズの設計通りにパターンを形成しようとしても、画素がマスクサイズに対して太るという問題が生じ、露光条件に関わらず高精細な画素アレイを設計通りに得ることは困難であった。露光量の変化に対するパターン形状のばらつきの対策としては、感光性着色組成物にヒンダードフェノール系酸化防止剤が使用されている例（例えば、特許文献２参照）や、リン酸系酸化防止剤が使用されている例（例えば、特許文献３参照）、ハイドロキノン系あるいはカテコール系重合禁止剤が使用されている例（例えば、特許文献４参照）が提案されている。しかしながら、これらの組成物を過剰に用いると、露光条件あるいは露光ギャップに対して十分なマージンは得られるものの、極性溶媒への耐溶剤性は悪化するという問題があった。
本発明は、露光条件に関わらず高精細なパターンを形成でき、Ｎ―メチルピロリドンやγ―ブチロラクトンといった極性溶媒への耐溶剤性に優れたカラーフィルター用着色組成物を提供することである。 An object of the present invention is to provide a coloring composition for a color filter that can form a high-definition pattern regardless of exposure conditions and has excellent solvent resistance to polar solvents such as N-methylpyrrolidone and γ-butyrolactone.
上記課題を解決するため、本発明は次の構成を有する。すなわち、
（１）少なくとも顔料、アルカリ可溶性樹脂、光重合開始剤、反応性モノマー、重合禁止剤および有機溶剤を含有する感光性着色組成物であって、下記一般式（１）または一般式（２）で表されるポリエーテルを有する二官能性モノマーおよび三官能以上の多官能性アクリルモノマーをそれぞれ含有し、該反応性モノマーにしめる二官能性モノマーの含有量が１０〜５０質量％、三官能以上の多官能性アクリルモノマーの含有量が２０〜９０質量％であり、該反応性モノマーの全固形分中にしめる含有量が２０質量％以上であることを特徴とする感光性着色組成物。
In order to solve the above problems, the present invention has the following configuration. That is,
(1) A photosensitive coloring composition containing at least a pigment, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer, a polymerization inhibitor and an organic solvent, which is represented by the following general formula (1) or general formula (2): Each containing a difunctional monomer having a polyether and a trifunctional or higher polyfunctional acrylic monomer, and the content of the bifunctional monomer to be used as the reactive monomer is 10 to 50% by mass. A photosensitive coloring composition, wherein the content of the functional acrylic monomer is 20 to 90% by mass, and the content of the reactive monomer in the total solid content is 20% by mass or more.
（式中、Ｒ１は水素原子、または炭素数１〜６のアルキル基を示す。ｍは２〜８の整数を示し、ｎは１〜２０の整数を示す。） (In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M represents an integer of 2 to 8, and n represents an integer of 1 to 20.)
（式中、Ｒ２は水素原子、または炭素数１〜６のアルキル基を示す。ｐおよびｑはそれぞれ２〜８の整数を示し、ｒおよびｓは２≦（ｒ＋ｓ）≦２０を満たす整数を示す。Ｘは、炭素数１〜１２の直鎖若しくは分岐のアルキル基、または下記一般式（３）で表される基で示される。） (In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. P and q each represents an integer of 2 to 8, and r and s are integers satisfying 2 ≦ (r + s) ≦ 20. X is a linear or branched alkyl group having 1 to 12 carbon atoms or a group represented by the following general formula (3).
（式中、Ｒ３およびＲ４は、水素原子又は炭素数１〜６のアルキル基を示す。）
（２）三官能以上の多官能性アクリルモノマーとして、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、およびその酸変性アクリレートのうちいずれか一種以上を含有することを特徴とする（１）に記載の感光性着色組成物。
（３）前記重合禁止剤の全樹脂分にしめる含有量が０．１〜０．５％であることを特徴とする（１）に記載の感光性着色組成物。
（４）任意の色数で各色別に所望のパターン状に設けられた着色層からなる画素を有するカラーフィルタにおいて、該着色層が請求項（１）〜（３）のいずれかに記載のカラーフィルタ用感光性着色組成により形成される着色膜を含有することを特徴とするカラーフィルタ。
(Wherein, R 3 and R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
(2) A trifunctional or higher polyfunctional acrylic monomer containing at least one of dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and acid-modified acrylate thereof. The photosensitive coloring composition as described in (1).
(3) The photosensitive coloring composition as described in (1), wherein the content of the polymerization inhibitor is 0.1 to 0.5%.
(4) The color filter according to any one of claims (1) to (3), wherein the color layer has a pixel composed of a color layer provided in a desired pattern for each color with an arbitrary number of colors. A color filter comprising a colored film formed by a photosensitive coloring composition for use.
本発明の感光性着色組成物を用いることにより、露光条件に関わらず高精細なパターンを形成でき、かつ耐溶剤性に優れたカラーフィルター用着色組成物を得ることができる。 By using the photosensitive coloring composition of the present invention, it is possible to obtain a coloring composition for a color filter that can form a high-definition pattern regardless of the exposure conditions and is excellent in solvent resistance.
本発明の感光性着色組成物に用いられる顔料としては、有機顔料、無機顔料等を用いることができるが、耐熱性、透明性の面から有機顔料が好ましい。中でも透明性が高く、耐光性、耐熱性、耐薬品性に優れたものが好ましい。代表的な有機顔料の具体的な例をカラ−インデックス（ＣＩ）ナンバ−で示すと、次のようなものが好ましく使用されるが、いずれもこれらに限定されるものではない。 As the pigment used in the photosensitive coloring composition of the present invention, an organic pigment, an inorganic pigment, or the like can be used, but an organic pigment is preferable from the viewpoint of heat resistance and transparency. Among them, those having high transparency and excellent light resistance, heat resistance, and chemical resistance are preferable. When specific examples of typical organic pigments are represented by color index (CI) numbers, the following are preferably used, but they are not limited to these.
黄色顔料の例としては、ピグメントイエロ−（以下ＰＹと略す）１２、１３、１７、２０、２４、８３、８６、９３、９５、１０９、１１０、１１７、１２５、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５３、１５４、１６６、１６８、１８５などが使用される。
また、オレンジ色顔料の例としては、ピグメントオレンジ（以下ＰＯと略す）１３、３６、３８、４３、５１、５５、５９、６１、６４、６５、７１などが使用される。
また、赤色顔料の例としては、ピグメントレッド（以下ＰＲと略す）９、４８、９７、１２２、１２３、１４４、１４９、１６６、１６８、１７７、１７９、１８０、１９２、２０９、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、２５４などが使用される。
また、紫色顔料の例としては、ピグメントバイオレット（以下ＰＶと略す）１９、２３、２９、３０、３２、３７、４０、５０などが使用される。
また、青色顔料の例としては、ピグメントブル−（以下ＰＢと略す）１５、１５：３、１５：４、１５：６、２２、６０、６４などが使用される。
また、緑色顔料の例としては、ピグメントグリ−ン（以下ＰＧと略す）７、１０、３６、などが使用される。
これらの顔料は、必要に応じて、ロジン処理、酸性基処理、塩基性処理などの表面処理がされていてもかまわず、耐光性や耐溶剤性を損なわない程度に染料を含むことができる。
Examples of yellow pigments include pigment yellow (hereinafter abbreviated as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 185, etc. are used.
Examples of orange pigments include pigment orange (hereinafter abbreviated as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, and the like.
Examples of red pigments include pigment red (hereinafter abbreviated as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217. 220, 223, 224, 226, 227, 228, 240, 254, etc. are used.
Examples of purple pigments include pigment violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 32, 37, 40, 50, and the like.
Examples of blue pigments include pigment blue (hereinafter abbreviated as PB) 15, 15: 3, 15: 4, 15: 6, 22, 60, 64, and the like.
Examples of green pigments include pigment green (hereinafter abbreviated as PG) 7, 10, 36, and the like.
These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment and the like, if necessary, and can contain a dye to such an extent that the light resistance and solvent resistance are not impaired.
上記顔料は、例えばカラ−フィルタ−のＲ（レッド）、Ｇ（グリーン）、Ｂ（ブルー）３色の画素が、ＣＲＴ（陰極線管）蛍光体の色度特性、バックライトや液晶ディスプレイに用いる液晶特性に合うように、数色組み合わせて調色され使用することもできる。 The pigment is, for example, a color filter R (red), G (green), or B (blue) three-color pixel, chromaticity characteristics of a CRT (cathode ray tube) phosphor, liquid crystal used in a backlight or a liquid crystal display. To match the characteristics, it is possible to mix and use several colors.
Ｒ（レッド）の場合を例にあげると、ＰＲ−２５４とＰＲ−１７７の組合せ、ＰＲ−２５４とＰＹ−１３８の組合せ、ＰＲ−２５４とＰＹ−１３９の組合せ、ＰＲ−２０９とＰＯ−３８の組合せ等で色度が調色される。
Ｇ（グリーン）の場合は、ＰＧ−７やＰＧ−３６と上記黄色顔料、例えば、ＰＹ−１７、ＰＹ−８３の組合せやＰＹ−１３８の組合せ、ＰＹ−１３９の組合せ、ＰＹ−１５０の組合せ等で色度が調色される。
Ｂ（ブルー）の場合は、ＰＢ１５：３やＰＢ：１５：６と紫色顔料、例えばＰＶ−１９やＰＶ−２３の組み合わせで調色される。
Taking the case of R (red) as an example, a combination of PR-254 and PR-177, a combination of PR-254 and PY-138, a combination of PR-254 and PY-139, a combination of PR-209 and PO-38 The chromaticity is adjusted by combination or the like.
In the case of G (green), PG-7 or PG-36 and the above yellow pigment, for example, PY-17, PY-83 combination, PY-138 combination, PY-139 combination, PY-150 combination, etc. To adjust the chromaticity.
In the case of B (blue), the color is adjusted by a combination of PB15: 3 or PB: 15: 6 and a purple pigment such as PV-19 or PV-23.
また、樹脂ブラックマトリクスに使用される顔料は、使用する有機溶剤および水に不溶であり遮光剤としての役割を果たすものであれば、特に限定されない。有機顔料としてピグメントブラック７の他、カーボンブラック、黒鉛、酸化鉄、酸化マンガン、チタンブラックなどが遮光剤として使用され、さらに表面処理を好ましく行うことができる。また、必要に応じて、これら遮光剤を混合して用いることもでき、他の色の顔料を添加することもできる。これら遮光剤のなかでも、少ない使用量で高い遮光性を得られることから、チタンブラックを含むことが好ましい。 The pigment used in the resin black matrix is not particularly limited as long as it is insoluble in the organic solvent and water used and plays a role as a light shielding agent. In addition to pigment black 7 as an organic pigment, carbon black, graphite, iron oxide, manganese oxide, titanium black and the like are used as a light shielding agent, and surface treatment can be preferably performed. If necessary, these light-shielding agents can be mixed and used, and pigments of other colors can be added. Among these light-shielding agents, titanium black is preferably included because high light-shielding properties can be obtained with a small amount of use.
本発明の感光性着色組成物は顔料を用い、分散機を用いて溶液中に均一に分散することが好ましい。顔料の分散方法に特に限定はなく、ボールミル、サンドグラインダー、３本ロールミル、高速度衝撃ミル、ビーズミルなど、公知の方法が使用できる。メディアを用いたビーズミルは微細な顔料を分散できるため好ましく用いられ、高精細なパターンを形成するのに好適である。 The photosensitive coloring composition of the present invention preferably uses a pigment and is uniformly dispersed in a solution using a disperser. The method for dispersing the pigment is not particularly limited, and known methods such as a ball mill, a sand grinder, a three-roll mill, a high speed impact mill, and a bead mill can be used. A bead mill using media is preferably used because it can disperse fine pigments, and is suitable for forming a high-definition pattern.
分散機を用いて顔料を分散させる工程としては、顔料と、アクリル系ポリマー、反応性モノマー、光重合開始剤、有機溶剤、および重合禁止剤を直接、分散機に投入し感光性着色組成物を得ることもできるが、生産性および設備面の簡便さの観点から、顔料、有機溶剤、好ましくはアクリル系ポリマー、好ましくはさらに分散剤を含有する顔料分散液としてあらかじめ調整しておくことが好ましい。 As a step of dispersing the pigment using a disperser, the pigment, an acrylic polymer, a reactive monomer, a photopolymerization initiator, an organic solvent, and a polymerization inhibitor are directly added to the disperser, and a photosensitive coloring composition is prepared. Although it can be obtained, it is preferable to prepare in advance as a pigment dispersion containing a pigment, an organic solvent, preferably an acrylic polymer, and preferably a dispersant, from the viewpoint of productivity and ease of equipment.
有機溶剤としては、特に限定されるものではなく、例えばメチルセロソルブ、エチルセロソルブ、メチルカルビトール、エチルカルビトール、エチ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エチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールブチルエチルエーテルなどの（ポリ）アルキレングリコールエーテル系溶剤、あるいは、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、アセト酢酸エチル、メチル―３―メトキシプロピオネート、エチル−３−エトキシプロピオネート、メトキシブチルアセテート、３―メチル―３―メトキシブチルアセテートなどの脂肪族エステル類、あるいは、エタノール、ブタノール、イソプロパノール、３―メチル―３―メトキシブタノールなどの脂肪族アルコール類、シクロペンタノン、シクロヘキサノンなどのケトン類を用いることができ、これらの単独、あるいは２種類以上の混合溶剤も好ましく用いることができる。またこれら以外の溶剤との混合も好ましく用いられる。 The organic solvent is not particularly limited, for example, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, (Poly) alkylene glycol ether solvents such as diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl ethyl ether, or propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetoacetate, methyl-3-methoxypropio , Ethyl-3-ethoxypropionate, methoxybut Aliphatic esters such as rubacetate and 3-methyl-3-methoxybutyl acetate, or aliphatic alcohols such as ethanol, butanol, isopropanol and 3-methyl-3-methoxybutanol, and ketones such as cyclopentanone and cyclohexanone These can be used, and these alone or two or more kinds of mixed solvents can also be preferably used. Mixing with other solvents is also preferably used.
ただし、本発明の着色組成物を第コーティング法により基板に塗布する場合には、膜厚の均一性、及び吐出スリット部に顔料凝集物が生じるのを防止する観点から、沸点が比較的高い溶剤を使用するのが好ましい。一方、沸点が高すぎると乾燥性が悪化するので、具体的には、１５０℃以上２２０℃以下の範囲に沸点を有する溶剤を用いるのが好ましい。 However, when the colored composition of the present invention is applied to the substrate by the first coating method, it is a solvent having a relatively high boiling point from the viewpoint of uniformity of film thickness and preventing the formation of pigment aggregates in the discharge slit portion. Is preferably used. On the other hand, if the boiling point is too high, the drying property is deteriorated. Specifically, it is preferable to use a solvent having a boiling point in the range of 150 ° C. or higher and 220 ° C. or lower.
使用できるアクリル系樹脂としては、特に限定はないが、不飽和カルボン酸とエチレン性不飽和化合物の共重合体を好ましく用いることができる。不飽和カルボン酸の例としては、例えばアクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、ビニル酢酸、あるいは酸無水物などがあげられる。 The acrylic resin that can be used is not particularly limited, but a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides.
これらは単独で用いても良いが、他の共重合可能なエチレン性不飽和化合物と組み合わせて用いても良い。共重合可能なエチレン性不飽和化合物としては、具体的には、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸イソプロピル、メタクリル酸ｎープロピル、メタクリル酸イソプロピル、アクリル酸ｎ−ブチル、メタクリル酸ｎ−ブチル、アクリル酸ｓｅｃ−ブチル、メタクリル酸ｓｅｃ−ブチル、アクリル酸イソ−ブチル、メタクリル酸イソ−ブチル、アクリル酸ｔｅｒｔ−ブチル、メタクリル酸ｔｅｒｔ−ブチル、アクリル酸ｎ−ペンチル、メタクリル酸ｎ−ペンチル、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、イソボルニルメタクリレートなどの不飽和カルボン酸アルキルエステル、スチレン、ｐ−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、α−メチルスチレンなどの芳香族ビニル化合物、トリシクロデカニルメタクリレートなどの脂環式基を側差に有するビニル化合物、アミノエチルアクリレートなどの不飽和カルボン酸アミノアルキルエステル、グリシジルアクリレート、グリシジルメタクリレートなどの不飽和カルボン酸グリシジルエステル、酢酸ビニル、プロピオン酸ビニルなどのカルボン酸ビニルエステル、アクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリルなどのシアン化ビニル化合物、１，３−ブタジエン、イソプレンなどの脂肪族共役ジエン、それぞれ末端にアクリロイル基、あるいはメタクリロイル基を有するポリスチレン、ポリメチルアクリレート、ポリメチルメタクリレート、ポリブチルアクリレート、ポリブチルメタクリレート、ポリシリコーンなどのマクロモノマーなどがあげられるが、これらに限定されるものではない。 These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, and methacrylic acid. Isopropyl, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, Unsaturated carboxylic acid alkyl esters such as n-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and isobornyl methacrylate , Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, vinyl compounds having an alicyclic group such as tricyclodecanyl methacrylate on the side, amino Unsaturated carboxylic acid aminoalkyl ester such as ethyl acrylate, Unsaturated carboxylic acid glycidyl ester such as glycidyl acrylate and glycidyl methacrylate, Vinyl acid vinyl ester such as vinyl acetate and vinyl propionate, Acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc. Vinyl cyanide compounds, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, polystyrene, polymethyl acrylate, polymer having an acryloyl group or a methacryloyl group at each end. Methacrylate, polybutyl acrylate, polybutyl methacrylate, but such macromonomers such as polysilicone and the like, but is not limited thereto.
また、側鎖にエチレン性不飽和基を付加したアクリル系樹脂を用いると、加工の際の感度がよくなるので好ましく用いることができる。エチレン性不飽和基としては、ビニル基、アリル基、アクリル基、メタクリル基のようなものがある。このような側鎖をアクリル系（共）重合体に付加させる方法としては、アクリル系（共）重合体のカルボキシル基や水酸基などを有する場合には、これらにエポキシ基を有するエチレン性不飽和化合物やアクリル酸またはメタクリル酸クロライドを付加反応させる方法が一般的である。 Further, when an acrylic resin having an ethylenically unsaturated group added to the side chain is used, it can be preferably used because the sensitivity during processing is improved. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, acrylic groups, and methacrylic groups. As a method for adding such a side chain to an acrylic (co) polymer, when it has a carboxyl group or a hydroxyl group of an acrylic (co) polymer, an ethylenically unsaturated compound having an epoxy group therein In general, an addition reaction of acrylic acid or methacrylic acid chloride is used.
主鎖に対して付加することのできる不飽和基を有するエポキシ化合物としては、グリシジル基あるいは脂環式エポキシ基を有するエチレン性不飽和化合物が挙げられる。特に限定されるわけではないが、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、α−エチルアクリル酸グリシジル、クロトニルグリシジルエーテル、（イソ）クロトン酸グリシジルエーテル、Ｎ−（３，５−ジメチル−４−グリシジル）ベンジルアクリルアミド、（３，４−エポキシシクロヘキシル）メチル（メタ）アクリレートなどがあげられる。特にメタクリル酸および／またはアクリル酸とメタクリル酸メチル、ベンジルメタクリレート、スチレン、トリシクロデカニルメタクリレートから選ばれた３〜４元共重合体にグリシジルメタクリレートを付加したものは、感度および現像性が良好であるため好ましく用いられる。 Examples of the epoxy compound having an unsaturated group that can be added to the main chain include an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group. Although not particularly limited, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-l Glycidyl) benzylacrylamide, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and the like. In particular, those obtained by adding glycidyl methacrylate to a quaternary copolymer selected from methacrylic acid and / or acrylic acid and methyl methacrylate, benzyl methacrylate, styrene, and tricyclodecanyl methacrylate have good sensitivity and developability. Therefore, it is preferably used.
本発明におけるバインダー樹脂の平均分子量Ｍｗ（ゲルパーミエーションクロマトグラフィーで測定し、標準ポリスチレンによる検量線を用いて換算したもの）は、３千〜２０万が好ましく、さらに好ましくは９千〜１０万である。３千未満では十分な硬化膜強度が得られず、また、２０万を超えると現像性が悪化するため、好ましくない。また、適度なアルカリ現像性を得るためには、酸価は５０〜２００（mgKOH/g）であることが好ましく、７０〜１５０（mgKOH/g）がより好ましい。 The average molecular weight Mw (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve) of the binder resin in the present invention is preferably 3,000 to 200,000, more preferably 9000 to 100,000. is there. If it is less than 3,000, sufficient cured film strength cannot be obtained, and if it exceeds 200,000, developability deteriorates, which is not preferable. Moreover, in order to obtain moderate alkali developability, the acid value is preferably 50 to 200 (mgKOH / g), more preferably 70 to 150 (mgKOH / g).
また顔料の分散を安定化させるために、分散剤として、顔料の中間体、誘導体といった低分子分散剤、高分子分散剤など公知のものが使用できる。顔料誘導体としては、例えば顔料骨格のアルキルアミン変性体やカルボン酸誘導体、スルホン酸誘導体などを挙げることができ、顔料の湿潤や微細顔料の安定化に有効である。これら顔料誘導体の中でも、有機顔料のスルホン酸誘導体は微細顔料の安定化に効果が大きく、好ましく用いられる。高分子分散剤としては、通常、カラーフィルター用に使用されるものであれば、特に限定されず、ポリエステル、ポリアルキルアミン、ポリアリルアミン、ポリイミン、ポリアミド、ポリウレタン、ポリアクリレート、ポリイミド、ポリアミドイミド、などのポリマー、またはこれらの共重合体など、種々のものを単独、または混合して用いることができる。 In order to stabilize the dispersion of the pigment, known dispersants such as low molecular dispersants such as pigment intermediates and derivatives, and high molecular dispersants can be used. Examples of the pigment derivative include an alkylamine-modified product of a pigment skeleton, a carboxylic acid derivative, and a sulfonic acid derivative, which are effective for wetting the pigment and stabilizing the fine pigment. Among these pigment derivatives, sulfonic acid derivatives of organic pigments are highly effective for stabilizing fine pigments and are preferably used. The polymer dispersant is not particularly limited as long as it is usually used for a color filter, and is not limited to polyester, polyalkylamine, polyallylamine, polyimine, polyamide, polyurethane, polyacrylate, polyimide, polyamideimide, etc. Various polymers such as these polymers or copolymers thereof can be used alone or in admixture.
かかる方法によって顔料分散液を調整した後、アクリル系樹脂、反応性モノマー、光重合開始剤、重合禁止剤、その他添加剤等を混合した希釈ワニスを用意し、顔料分散液と混合することで、感光性着色組成物を得ることができる。
アクリル系樹脂としては、上記のものが使用でき、また、顔料分散液にあらかじめ含有されている場合は、同じものであっても異なっていても良い。
After preparing the pigment dispersion by such a method, preparing a diluted varnish mixed with an acrylic resin, a reactive monomer, a photopolymerization initiator, a polymerization inhibitor, other additives, etc., and mixing with the pigment dispersion, A photosensitive coloring composition can be obtained.
As the acrylic resin, those described above can be used, and when they are previously contained in the pigment dispersion, they may be the same or different.
反応性モノマーとしては、下記構造式（１）または（２）で表されるものを含有することが好ましい。 As a reactive monomer, it is preferable to contain what is represented by following Structural formula (1) or (2).
（式中、Ｒ１は水素原子、または炭素数１〜６のアルキル基を示す。ｍは２〜８の整数を示し、ｎは１〜２０の整数を示す。） (In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M represents an integer of 2 to 8, and n represents an integer of 1 to 20.)
（式中、Ｒ２は水素原子、または炭素数１〜６のアルキル基を示す。ｐおよびｑはそれぞれ２〜８の整数を示し、ｒおよびｓは２≦（ｒ＋ｓ）≦２０を満たす整数を示す。Ｘは、炭素数１〜１２の直鎖若しくは分岐のアルキル基、または下記一般式（３）で表される基で示される。） (In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. P and q each represents an integer of 2 to 8, and r and s are integers satisfying 2 ≦ (r + s) ≦ 20. X is a linear or branched alkyl group having 1 to 12 carbon atoms or a group represented by the following general formula (3).
（式中、Ｒ３およびＲ４は、水素原子又は炭素数１〜６のアルキル基を示す。）
これら、構造式（１）で表される反応性モノマーとしては、ジエチレングリコールジアクリレートやトリエチレングリコールジアクリレートなどのポリエチレングリコールジ（メタ）アクリレートが、構造式（２）で表される反応性モノマーとしては、ポリテトラメチレングリコールジアクリレート、ビスフェノールＡエチレンオキサイド（メタ）アクリレートなどが挙げられる。
(Wherein, R 3 and R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
As the reactive monomer represented by the structural formula (1), polyethylene glycol di (meth) acrylate such as diethylene glycol diacrylate or triethylene glycol diacrylate is used as the reactive monomer represented by the structural formula (2). Examples thereof include polytetramethylene glycol diacrylate and bisphenol A ethylene oxide (meth) acrylate.
また三官能以上の多官能性アクリルモノマーとしては、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、テトラ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トリ（メタ）アクリレート、トリアクリルホルマール、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ペンタ（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、もしくはこれらのアルキル変性物、アルキルエーテル変性物やアルキルエステル変性物などを用いることができる。中でも、ジペンタエリスリトールペンタ（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、およびその酸変性アクリレートのうちいずれか一種以上を含有することが好ましい。 Trifunctional or higher polyfunctional acrylic monomers include trimethylolpropane triacrylate, pentaerythritol triacrylate, tetratrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra ( It is possible to use (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, an alkyl modified product thereof, an alkyl ether modified product, an alkyl ester modified product, or the like. Among these, it is preferable to contain at least one of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and acid-modified acrylate thereof.
これら反応性モノマーのうち、上記構造式（１）または（２）で表される二官能性モノマーの含有量が１０〜５０質量％、三官能以上の多官能性アクリルモノマーの含有量が２０〜９０質量％であり、反応性モノマーの全固形分中にしめる含有量が２０質量％以上でかつ、全樹脂成分中にしめる含有量が３０％以上であることが好ましい。これらの範囲内で適宜、反応性モノマーを混合することにより、高感度でかつ極性溶媒浸漬時にもクラックやシワなどの発生がほとんどなく、かつ色差の小さい良好なパターンを形成することができる。 Among these reactive monomers, the content of the bifunctional monomer represented by the structural formula (1) or (2) is 10 to 50% by mass, and the content of the trifunctional or higher polyfunctional acrylic monomer is 20 to 20%. It is preferably 90% by mass, the content contained in the total solid content of the reactive monomer is 20% by mass or more, and the content contained in all the resin components is preferably 30% or more. By appropriately mixing the reactive monomer within these ranges, it is possible to form a good pattern with high sensitivity and little occurrence of cracks and wrinkles even when immersed in a polar solvent and having a small color difference.
光重合開始剤としては、ベンゾフェノン系化合物、アセトフェノン系化合物、チオキサントン系化合物、イミダゾール系化合物、ベンゾチアゾール系化合物、ベンゾオキサゾール系化合物、トリアジン系化合物、リン系化合物あるいはチタネート等の無機系光重合開始剤など公知のものが使用できる。 As photopolymerization initiators, inorganic photopolymerization initiators such as benzophenone compounds, acetophenone compounds, thioxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, triazine compounds, phosphorus compounds or titanates A publicly known thing can be used.
例えば、ベンゾフェノン、Ｎ，Ｎ’−テトラエチル−４，４’−ジアミノベンゾフェノン、４−メトキシ−４’−ジメチルアミノベンゾフェノン、２，２−ジエトキシアセトフェノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール、α−ヒドロキシイソブチルフェノン、チオキサントン、２−イソプロピルチオキサントン、２，４−ジエチルチオキサントン、１−ヒドロキシシクロヘキシルフェニルケトン、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−モルフォリノフェニル）−ブタノン−１、２−（４−メチル）ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、ｔ−ブチルアントラキノン、１−クロロアントラキノン、２，３−ジクロロアントラキノン、３−クロル−２−メチルアントラキノン、２−エチルアントラキノン、１，４−ナフトキノン、９，１０−フェナントラキノン、１，２−ベンゾアントラキノン、１，４−ジメチルアントラキノン、２−フェニルアントラキノン、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール２量体、２−メルカプトベンゾチアゾール、２−メルカプトベンゾオキサゾール、４−（ｐ−メトキシフェニル）−２，６−ジ−（トリクロロメチル）−ｓ−トリアジンなどがあげられる。 For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl Ketal, α-hydroxyisobutylphenone, thioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (4-methyl) benzyl-2-dimethylamino-1- (4-morpholinophenyl)- The Non-1, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4 -(P-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine and the like.
また、１−（９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル）チバ・スペシャルティ・ケミカルズ（株）製“ＣＧＩ２４２”などのカルバゾール系化合物が感度向上が見込めるため好ましく用いられる。 Further, carbazole compounds such as 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) Ciba Specialty Chemicals Co., Ltd. “CGI242” are preferable because sensitivity improvement can be expected. Used.
さらに芳香族、脂肪族の第３級アミンなどの増感助剤を添加すると、さらに感度を向上させることができ好ましい。また、これらの光重合開始剤は２種類以上を併用して用いることもできる。光重合開始剤の添加量としては、特に限定はないが、感光性着色組成物全固形分に対して、好ましくは２〜３０質量％、より好ましくは５〜２５質量％である。 Further, it is preferable to add a sensitizing aid such as an aromatic or aliphatic tertiary amine because the sensitivity can be further improved. Moreover, these photoinitiators can also be used in combination of 2 or more types. Although there is no limitation in particular as the addition amount of a photoinitiator, Preferably it is 2-30 mass% with respect to the photosensitive coloring composition total solid, More preferably, it is 5-25 mass%.
本発明で用いる重合禁止剤としては、ヒドロキノン系、およびカテコール系のものである。
より具体的には、ヒドロキノン系のものとしては、ヒドロキノン、ｔｅｒｔ−ブチルヒドロキノン、２，５−ビス（１，１，３，３−テトラメチルブチル）ヒドロキノン、２，５−ビス（１，１−ジメチルブチル）ヒドロキノンなどが挙げられ、カテコール系のものとしては、カテコール、ｔｅｒｔ−ブチルカテコールなどが挙げられる。
As the polymerization inhibitor used in the present invention, hydroquinone-based and catechol-based ones.
More specifically, hydroquinone, hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2,5-bis (1,1- Dimethylbutyl) hydroquinone and the like, and catechol-based ones include catechol and tert-butylcatechol.
これら重合禁止剤の添加量は、全樹脂分に対して、好ましくは０．１〜０．５質量％である。添加量が０．１質量％より少ない場合は、画素の太りを軽減する効果が小さいため好ましくなく、０．５質量％を超える場合は、極性溶媒浸漬時に感度の低下により膜表面が浸食され、色差が悪化し、シミが発生しやすくなるため好ましくない。これら重合禁止剤は、２種類以上を混合して使用こともできる。なお、ここでいう顔料を除く固形分とは、顔料および顔料誘導体を除く固形分であって、有機溶剤を除く、アクリル系樹脂、高分子分散剤、反応性モノマー、光重合開始剤、その他添加剤などを含む、樹脂分および低分子化合物の総量である。具体的には、感光性着色組成物を、２０００〜４０，０００倍の重力加速度を持つ遠心分離機に１〜６０分間、例えば２０，０００倍の重量加速度で１０分間処理し、顔料成分を沈降させた後、沈降分を除いた溶液を常圧中、もしくは減圧中で、４０℃〜２００℃で１０分〜２４時間、例えば１５０℃で６０分間加熱し有機溶媒成分を気化、乾燥させることで測定することができる。 The addition amount of these polymerization inhibitors is preferably 0.1 to 0.5% by mass with respect to the total resin content. When the amount added is less than 0.1% by mass, the effect of reducing the pixel thickness is small, which is not preferable. When the amount exceeds 0.5% by mass, the film surface is eroded due to a decrease in sensitivity when immersed in a polar solvent, This is not preferable because the color difference deteriorates and stains are likely to occur. Two or more of these polymerization inhibitors can be mixed and used. Here, the solid content excluding pigment refers to the solid content excluding pigments and pigment derivatives, excluding organic solvents, acrylic resins, polymer dispersants, reactive monomers, photopolymerization initiators, and other additions It is the total amount of the resin component and the low molecular weight compound including the agent. Specifically, the photosensitive coloring composition is treated in a centrifuge having a gravitational acceleration of 2000 to 40,000 times for 1 to 60 minutes, for example, at a weight acceleration of 20,000 times for 10 minutes, and the pigment component is precipitated. Then, the solution from which the sediment has been removed is heated at 40 ° C. to 200 ° C. for 10 minutes to 24 hours, for example, at 150 ° C. for 60 minutes, to evaporate and dry the organic solvent component under normal pressure or reduced pressure. Can be measured.
上記以外のヒンダードフェノール系や、リン系、イオウ系、アミン系などの重合禁止剤もしくは酸化防止剤は、画素がマスクサイズに対して太り、設計通りの高精細なパターンが形成できない傾向があり、また、分解物や未反応物が塗膜中に残存することに起因すると推定される電気的信頼性の悪化が見られるため好ましくない。 Other hindered phenols, phosphorus-based, sulfur-based, and amine-based polymerization inhibitors or antioxidants tend to be thicker than the mask size and fail to form high-definition patterns as designed. In addition, it is not preferable because degradation of electrical reliability presumed to be caused by decomposition products and unreacted materials remaining in the coating film is observed.
本発明の感光性着色組成物は、その他添加剤を含有していてもよい。例えば、有機溶剤、アクリル系樹脂以外の高分子化合物、密着改良剤や界面活性剤、有機酸、有機アミノ化合物、硬化剤などが挙げられる。
有機溶剤としては、公知のもの、例えば上記顔料分散液に記載のものなど使用でき、顔料分散液に含有されるものと同じものであっても異なっていても良い。
The photosensitive coloring composition of the present invention may contain other additives. Examples thereof include organic solvents, polymer compounds other than acrylic resins, adhesion improvers and surfactants, organic acids, organic amino compounds, and curing agents.
As the organic solvent, known solvents such as those described in the pigment dispersion can be used, and they may be the same as or different from those contained in the pigment dispersion.
高分子化合物としては、アクリル樹脂、アルキド樹脂、メラミン樹脂、ポリビニルアルコール、ポリエステル、ポリエーテル、ポリアミド、ポリアミドイミド、ポリイミド、ポリイミド前駆体など種々のものを用いることができる。 As the polymer compound, various materials such as acrylic resin, alkyd resin, melamine resin, polyvinyl alcohol, polyester, polyether, polyamide, polyamideimide, polyimide, polyimide precursor, and the like can be used.
密着改良剤は、塗膜の基板への密着性を向上させる目的で、好ましく添加することができる。例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシランなどのシランカップリング剤が挙げられる。 The adhesion improving agent can be preferably added for the purpose of improving the adhesion of the coating film to the substrate. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Examples include silane coupling agents such as chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
界面活性剤は、感光性着色組成物の塗布性、および着色層の表面の均一性を良好にする目的で、あるいは、顔料の分散性を良好にする目的で添加することができる。かかる界面活性剤の添加量は、顔料に対して、好ましくは０．００１〜１０質量％、さらに好ましくは０．０１〜１質量％であるのがよい。添加量がこの範囲より少ないと、塗布性、着色膜表面の均一性の改良、あるいは顔料分散性の改良の効果が小さく、多すぎると逆に塗布性が不良となったり、顔料の凝集が起こる場合があるため好ましくない。具体的には、ラウリル硫酸アンモニウム、ポリオキシエチレンアルキルエーテル硫酸トリエタノールアミンなどの陰イオン界面活性剤、ステアリルアミンアセテート、ラウリルトリメチルアンモニウムクロライドなどの陽イオン界面活性剤、ラウリルジメチルアミンオキサイド、ラウリルカルボキシメチルヒドロキシエチルイミダゾリウムベタインなどの両性界面活性剤、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ソルビタンモノステアレートなどの非イオン界面活性剤、フッ素系界面活性剤やシリコン系界面活性剤などがあげられる。
かかる方法により得られた感光性着色組成物は、さらに遠心機、濾過器などを用いて粗大粒子や粉塵などの不純物を除去することも好ましく行われる。
The surfactant can be added for the purpose of improving the coating property of the photosensitive coloring composition and the surface uniformity of the colored layer, or for the purpose of improving the dispersibility of the pigment. The amount of the surfactant added is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, based on the pigment. If the added amount is less than this range, the effect of improving the coating property, the uniformity of the colored film surface, or the pigment dispersibility is small, and if it is too much, the coating property is poor or the pigment is aggregated. Since there are cases, it is not preferable. Specifically, anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, laurylcarboxymethylhydroxy Examples include amphoteric surfactants such as ethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, fluorine-based surfactants, and silicon-based surfactants. .
The photosensitive coloring composition obtained by such a method is also preferably subjected to removal of impurities such as coarse particles and dust using a centrifuge, a filter or the like.
本発明の感光性着色組成物において、顔料は、通常、感光性着色組成物の全固形分中に５〜８０質量％、好ましくは１０〜６０質量％の範囲で用いられる。顔料の量が５％より少ないと色純度が低く好ましくなく、６０質量％より多いと現像不良やパターンの剥がれが起こりやすいため好ましくない。 In the photosensitive coloring composition of the present invention, the pigment is usually used in the range of 5 to 80% by mass, preferably 10 to 60% by mass in the total solid content of the photosensitive coloring composition. If the amount of the pigment is less than 5%, the color purity is unfavorably low, and if the amount is more than 60% by mass, it is not preferable because development failure or pattern peeling tends to occur.
次に、本発明の感光性着色組成物を用いたカラーフィルターの製造方法の例を説明する。感光性着色組成物を基板上に塗布する方法としては、スピンコーター、バーコーター、ブレードコーター、ロールコーター、ダイコーター、スクリーン印刷法などで基板に塗布する方法、基板を着色組成物中に浸漬する方法、着色組成物を基板に噴霧するなどの種々の方法を用いることができる。 Next, the example of the manufacturing method of the color filter using the photosensitive coloring composition of this invention is demonstrated. As a method of applying the photosensitive coloring composition on the substrate, a method of applying to the substrate by a spin coater, a bar coater, a blade coater, a roll coater, a die coater, a screen printing method, or the like, or immersing the substrate in the coloring composition Various methods, such as a method and spraying a coloring composition on a substrate, can be used.
また、かかる基板としては、通常、ソーダガラス、無アルカリガラス、ホウケイ酸ガラス、石英ガラスなどの透明基板や、シリコン、ガリウム−ひ素などの半導体基板などが用いられるが、特にこれらに限定されない。なお、かかる基板上に本発明の感光性着色組成物を塗布する場合、シランカップリング剤などの接着助剤で基板表面を処理しておくと、着色膜と基板の接着力を向上させることができる。 In addition, as such a substrate, a transparent substrate such as soda glass, non-alkali glass, borosilicate glass, or quartz glass, or a semiconductor substrate such as silicon or gallium-arsenide is usually used, but is not particularly limited thereto. When applying the photosensitive coloring composition of the present invention on such a substrate, if the substrate surface is treated with an adhesion aid such as a silane coupling agent, the adhesion between the colored film and the substrate can be improved. it can.
上記により、基板上に本発明の感光性着色組成物を塗布した後、風乾、減圧乾燥、加熱乾燥などにより有機溶剤を除去し、塗膜を形成する。とくに減圧乾燥工程を設けた後、オーブンあるいはホットプレートで追加の加熱乾燥することにより、対流によって生じる塗布欠点が解消され収率が向上する。減圧乾燥は常温〜１００℃、５秒〜１０分、気圧５００〜５Ｐａ、より好ましくは気圧１００〜１０Ｐａの範囲で行うのが好ましい。加熱乾燥はオーブン、ホットプレートなどを使用し、５０〜１２０℃の範囲で１０秒〜３０分行うのが好ましい。この後、必要に応じて塗膜上に酸素遮断膜を設けても良い。 After applying the photosensitive coloring composition of the present invention on the substrate as described above, the organic solvent is removed by air drying, reduced pressure drying, heat drying or the like to form a coating film. In particular, after providing a vacuum drying step, additional heating and drying in an oven or a hot plate eliminates coating defects caused by convection and improves the yield. The drying under reduced pressure is preferably performed in the range of normal temperature to 100 ° C., 5 seconds to 10 minutes, atmospheric pressure 500 to 5 Pa, more preferably atmospheric pressure 100 to 10 Pa. Heat drying is preferably performed using an oven, a hot plate or the like at a temperature of 50 to 120 ° C. for 10 seconds to 30 minutes. Thereafter, an oxygen barrier film may be provided on the coating film as necessary.
次に、露光を行う。該感光性着色組成物の塗膜上にマスクを設置し、超高圧水銀灯、ケミカル灯、高圧水銀灯等を用いて、紫外線等により選択的に露光する。露光量は３６５ｎｍにおける放射照度の時間積分値で表され、特に限定されるわけではないが、好ましくは１０ｍＪ／ｃｍ２〜２００ｍＪ／ｃｍ２、より好ましくは２０ｍＪ／ｃｍ２〜１００ｍＪ／ｃｍ２である。１０ｍＪ／ｃｍ２より小さい場合は透明樹脂層のパターンが硬化不足のために現像時に剥がれてしまうことがあるため好ましくなく、２００ｍＪ／ｃｍ２より大きい場合はタクトタイムが長くなり生産効率が悪いため好ましくない。 Next, exposure is performed. A mask is placed on the coating film of the photosensitive coloring composition and selectively exposed to ultraviolet rays or the like using an ultrahigh pressure mercury lamp, a chemical lamp, a high pressure mercury lamp or the like. Exposure is represented by the time-integrated values of irradiance at 365 nm, but are not particularly limited, is preferably 10mJ / cm 2 ~200mJ / cm 2 , more preferably 20mJ / cm 2 ~100mJ / cm 2 . If it is less than 10 mJ / cm 2, the pattern of the transparent resin layer may be peeled off during development due to insufficient curing, and if it is greater than 200 mJ / cm 2, it is preferable because the tact time becomes long and the production efficiency is poor. Absent.
ついでアルカリ性現像液で現像を行う。アルカリ性現像液に用いるアルカリ性物質としては特に限定はしないが、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ｎ−プロピルアミン等の１級アミン類、ジエチルアミン、ジ−ｎ−プロピルアミン等の２級アミン類、トリエチルアミン、メチルジエチルアミン等の３級アミン類、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）等のテトラアルキルアンモニウムヒドロキシド類、コリン等の４級アンモニウム塩、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、ジメチルアミノエタノール、ジエチルアミノエタノール等のアルコールアミン類、ピロール、ピペリジン、１，８−ジアザビシクロ［５，４，０］−７−ウンデセン、１，５−ジアザビシクロ［４，３，０］−５−ノナン、モルホリン等の環状アミン類などの有機アルカリ類等が挙げられる。 Next, development is performed with an alkaline developer. Although it does not specifically limit as an alkaline substance used for an alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n- Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines, pyrrole, piperidine, 1,8-dia Bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, organic alkalis such as cyclic amines such as morpholine, and the like.
これら現像液のアルカリ性物質の濃度は特に限定されるわけではないが、通常０．０１〜５０質量％、好ましくは０．０５〜５質量％である。また、現像液は作業環境、廃現像液処理の点から、アルカリ水溶液の水系現像液が好ましい。アルカリ水溶液の水系現像液を用いる場合、現像液にエタノール、γーブチロラクトン、ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン等の水溶性有機溶剤を適宜加えても良い。
現像方式は浸漬法、スプレー法、パドル法等を用いるが特に限定しない。また、現像後適宜純水などによる洗浄工程を加えても良い。
The concentration of the alkaline substance in the developer is not particularly limited, but is usually 0.01 to 50% by mass, preferably 0.05 to 5% by mass. The developer is preferably an aqueous aqueous developer in terms of working environment and waste developer treatment. In the case of using an aqueous alkaline aqueous developer, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be appropriately added to the developer.
The development method uses an immersion method, a spray method, a paddle method or the like, but is not particularly limited. Moreover, you may add the washing process by a pure water etc. suitably after image development.
ここで、現像液として非イオン系界面活性剤などの界面活性剤を０．０１〜１質量％添加したアルカリ性現像液を使用すると、より良好なパターンが得られるため好ましい。 Here, it is preferable to use an alkaline developer added with 0.01 to 1% by mass of a surfactant such as a nonionic surfactant as the developer because a better pattern can be obtained.
得られた着色組成物の塗膜パターンは、その後、加熱処理することによってパターンニングされた着色画素となる。加熱処理は通常、空気中、窒素雰囲気中、あるいは、真空中などで、１５０〜３００℃、好ましくは１８０〜２５０℃の温度のもとで、０．２５〜５時間、連続的または段階的に行われる。 The coating film pattern of the obtained colored composition then becomes a colored pixel patterned by heat treatment. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at 150 to 300 ° C, preferably 180 to 250 ° C, continuously or stepwise for 0.25 to 5 hours. Done.
上記方法で任意の色数について逐次着色パターンを形成せしめると、所望のパターン状に設けられた着色層からなる画素を有する液晶表示装置用カラーフィルターが作製できる。ここで着色組成物のパターニング順序は限定されない。また、色数は任意だが、ＲＧＢの３色、もしくは樹脂ブラックマトリクスを加えた４色が好ましい。 When a colored pattern is sequentially formed for an arbitrary number of colors by the above method, a color filter for a liquid crystal display device having a pixel composed of a colored layer provided in a desired pattern can be produced. Here, the patterning order of the coloring composition is not limited. Although the number of colors is arbitrary, three colors of RGB or four colors including a resin black matrix are preferable.
また必要に応じて、ブラックマトリックス、保護膜、透明電導膜等を形成することができる。これらを形成する位置、形成順序、形成方法などは、特に限定されない。一例として、基板上にブラックマトリックスを形成し、その上に着色層、さらにその上に保護膜、さらにその上に透明導電膜を形成するなどの構成が挙げられる。 Moreover, a black matrix, a protective film, a transparent conductive film, etc. can be formed as needed. The position where these are formed, the order of formation, the formation method, and the like are not particularly limited. As an example, a black matrix is formed on a substrate, a colored layer is formed thereon, a protective film is further formed thereon, and a transparent conductive film is formed thereon.
以下、実施例を用いて本発明を更に詳しく説明するが、これによって本発明の範囲は何ら制限されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, the scope of the present invention is not restrict | limited at all by this.
（パターン作製方法）
感光性着色組成物を、無アルカリガラス（日本電気硝子（株）製、ＯＡ１０：５０ｍｍ×７０ｍｍ、厚さ０．７ｍｍ）基板表面上に、スピンコーター（ミカサ（株）製、１Ｈ−Ｄ２型）を用いて塗布したのち、９０℃のイナートオーブン（ダバイエスペック（株）製、ＰＥＲＦＥＣＴＯＶＥＮ ＰＶ−２１０）内で１０分間加熱乾燥（プリベイク）を行い、膜厚２．００μｍの塗膜を形成した。その後、この基板を室温に冷却したのち、露光機（ユニオン光学（株）製、紫外線露光機ＰＥＭ−６Ｍ、コリメーションアングルθ＝２°、ｉ線（３６５ｎｍ）照度＝４０ｍＷ／ｃｍ２）を用い、フォトマスク（ＨＯＹＡ（株）製、ネガマスク、ストライプ設計線幅５０μｍ）を介して、ｊ線：３１３ｎｍ、ｉ線：３６５ｎｍ、ｈ線：４０５ｎｍおよびｇ線：４３６ｎｍの各波長を含む紫外線で所定の露光量で露光した。
(Pattern preparation method)
The photosensitive coloring composition is spin-coated (Mikasa Co., Ltd., 1H-D2 type) on a non-alkali glass (manufactured by Nippon Electric Glass Co., Ltd., OA10: 50 mm × 70 mm, thickness 0.7 mm) substrate surface. Then, the film was dried by heating (prebaking) for 10 minutes in an inert oven (manufactured by Davai Speck Co., Ltd., PERFECTOVEN PV-210) at 90 ° C. to form a coating film having a thickness of 2.00 μm. Then, after cooling this substrate to room temperature, using an exposure machine (Union Optics Co., Ltd., UV exposure machine PEM-6M, collimation angle θ = 2 °, i-line (365 nm) illuminance = 40 mW / cm 2 ), Through a photomask (manufactured by HOYA Co., Ltd., negative mask, stripe design line width 50 μm), predetermined exposure with ultraviolet rays including wavelengths of j-line: 313 nm, i-line: 365 nm, h-line: 405 nm, and g-line: 436 nm Exposed in quantity.
次に、水酸化テトラメチルアンモニウム（三菱ガス化学（株）、ＴＭＡＨ）０．２質量％とエマルゲンＡ−６０（花王（株）製）を０．５質量％含む２３℃の水溶液を現像液に用い、基板を自動現像装置（ミカサ（株）製、ＡＤ−２０００）で所定の時間シャワー現像したのち、純水で洗浄し、風乾した。さらに２３０℃のイナートオーブン（ダバイエスペック（株）製、ＨＩＧＨＴＥＭＰＯＶＥＮ ＰＶ−１１０）内で３０分間加熱乾燥（ポストベイク）を行い、基板上に各色カラーフィルターを作製した。 Next, a 23 ° C. aqueous solution containing 0.2% by mass of tetramethylammonium hydroxide (Mitsubishi Gas Chemical Co., Ltd., TMAH) and 0.5% by mass of Emulgen A-60 (manufactured by Kao Corporation) is used as a developer. The substrate was subjected to shower development for a predetermined time by an automatic developing device (manufactured by Mikasa Co., Ltd., AD-2000), washed with pure water, and air-dried. Furthermore, heat drying (post-baking) was performed for 30 minutes in an inert oven (manufactured by Davai Speck Co., Ltd., HIGHTEMPOVEN PV-110) at 230 ° C., and each color filter was produced on the substrate.
（評価方法）
１．線幅の露光量依存性
上記のパターン作製方法に従って、５０μｍストライプパターンのフォトマスクを介して３０、６０、９０ｍＪ／ｃｍ２の露光量と露光ギャップ１００μｍで露光した。現像時間は５０秒から７０秒とし、形成したカラーフィルターパターンの形状について、光学顕微鏡（オリンパス販売（株）製ＢＨ３−ＭＪＬ、およびケイエスオリンパス（株）製ＸＤ２００）を用いて画素形状の観察および画素幅の測定を行い、マスク設計線幅と得られたパターンの線幅の差を求めた。
○：各露光量で得られた線幅の差が３μｍ以下のもの。
×：各露光量で得られた線幅の差が３μｍより大きいもの。
(Evaluation methods)
1. Dependence on exposure amount of line width In accordance with the above pattern production method, exposure was performed with an exposure amount of 30, 60, 90 mJ / cm 2 and an exposure gap of 100 μm through a photomask having a 50 μm stripe pattern. The development time is 50 seconds to 70 seconds, and the shape of the formed color filter pattern is observed using an optical microscope (BH3-MJL manufactured by Olympus Sales Co., Ltd. and XD200 manufactured by KS Olympus Co., Ltd.) The width was measured, and the difference between the mask design line width and the line width of the obtained pattern was obtained.
A: The difference in line width obtained at each exposure amount is 3 μm or less.
X: The difference of the line | wire width obtained by each exposure amount is larger than 3 micrometers.
２．耐溶剤性試験
上記のパターン作製方法に従って、１００μｍストライプパターンのフォトマスクを介して１２０ｍＪ／ｃｍ２の露光量と露光ギャップ１００μｍで露光した。現像時間は５０秒から７０秒とし、形成したカラーフィルターパターンを顕微分光装置（大塚電子（株）製ＭＣＰＤ−２０００）を用いてＣＩＥＬＡＢ測色値（Ｌ*，ａ*，ｂ*）を測定した。このパターンをＮ―メチルピロリドン（以下ＮＭＰとする）中に５分浸漬させ、エアブローなしに１２０℃のホットプレートで２分乾燥させ、再度顕微分光装置を用いてＣＩＥＬＡＢ測色値を測定し、浸漬前の測色値との間の色差ΔＥａｂ*を求めた。
○：上記色差ΔＥａｂ*が３以内であるもの。
×：上記色差ΔＥａｂ*が３以上であるもの。
2. Solvent Resistance Test According to the above pattern preparation method, exposure was performed with an exposure amount of 120 mJ / cm 2 and an exposure gap of 100 μm through a photomask having a 100 μm stripe pattern. The development time was 50 seconds to 70 seconds, and CIELAB colorimetric values (L *, a *, b *) were measured for the formed color filter pattern using a microspectroscope (MCPD-2000 manufactured by Otsuka Electronics Co., Ltd.). . This pattern is immersed in N-methylpyrrolidone (hereinafter referred to as NMP) for 5 minutes, dried on a hot plate at 120 ° C. for 2 minutes without air blow, and CIELAB colorimetric values are measured again using a microspectrophotometer. The color difference ΔEab * between the previous colorimetric values was determined.
◯: The color difference ΔEab * is within 3
X: The color difference ΔEab * is 3 or more.
また、浸漬後のパターン表面を光学顕微鏡（オリンパス販売（株）製ＢＨ３−ＭＪＬ、およびケイエスオリンパス（株）製ＸＤ２００）を用いて観察した。
○：クラックやシワなどがほとんどないもの。
△：クラックやシワは少ないが、シミが発生しているもの。
×：クラックやシワが多発しているもの。
Moreover, the pattern surface after immersion was observed using the optical microscope (Olympus sales BH3-MJL and KS Olympus XD200).
○: No cracks or wrinkles.
Δ: There are few cracks and wrinkles, but there are spots.
X: A crack and a wrinkle occur frequently.
（アクリル系樹脂の合成例）
１０００ｃｃの４つ口フラスコに３−メトキシ−３−メチル−ブタノール１５０ｇを仕込み、これを９０℃に保ち、窒素シール、撹拌を行いながらメタクリル酸メチル３０ｇ、スチレン３０ｇ、メタクリル酸４０ｇにｎ−ドデシルメルカプタン１．１ｇ、２，２’−アゾビスイソブチロニトリル１．２ｇを混合して滴下ロートで３０分かけて滴下した。この後４時間反応を続けた後、窒素シールをやめ、ハイドロキノンモノメチルエーテル０．１ｇ、ジメチルベンジルアミン０．４ｇを加えた。グリシジルメタクリレート３３ｇを３０分かけて滴下し、さらに９０℃で３時間撹拌することで反応を行った。室温に戻した後、精製水／アセトンの混合溶剤に滴下することで再沈殿させ、濾過、乾燥することにより平均分子量Ｍｗ４万、酸価１１５ｍｇＫＯＨ／ｇの粉末状のアクリル系樹脂（ポリマーＡとする）を得た。
(Synthesis example of acrylic resin)
In a 1000 cc four-necked flask, 150 g of 3-methoxy-3-methyl-butanol was charged, kept at 90 ° C., sealed with nitrogen, stirred and stirred with 30 g of methyl methacrylate, 30 g of styrene, and 40 g of methacrylic acid with n-dodecyl mercaptan. 1.1 g and 1.2 g of 2,2′-azobisisobutyronitrile were mixed and added dropwise using a dropping funnel over 30 minutes. Thereafter, the reaction was continued for 4 hours, then the nitrogen sealing was stopped, and 0.1 g of hydroquinone monomethyl ether and 0.4 g of dimethylbenzylamine were added. Reaction was performed by adding 33 g of glycidyl methacrylate dropwise over 30 minutes and further stirring at 90 ° C. for 3 hours. After returning to room temperature, it is re-precipitated by dropping it into a mixed solvent of purified water / acetone, filtered and dried to obtain a powdery acrylic resin (polymer A) having an average molecular weight Mw of 40,000 and an acid value of 115 mgKOH / g. )
実施例１
顔料としてピグメントレッド２５４とピグメントレッド１７７の６０／４０（重量比）混合物を１３．５重量部、高分子分散剤として“Disperbyk”２００１（ビックケミージャパン（株）製、４６質量％）を１０重量部、ポリマーＡを４．５重量部、有機溶剤として、プロピレングリコールモノメチルエーテルアセテート（以下ＰＧＭＥＡとする）７２重量部を混合した後、ジルコニアビーズが充填されたミル型分散機を用いて分散し、顔料分散液を得た。
Example 1
13.5 parts by weight of a 60/40 (weight ratio) mixture of Pigment Red 254 and Pigment Red 177 as a pigment, and 10 weights of “Disperbyk” 2001 (produced by Big Chemie Japan Co., Ltd., 46% by mass) as a polymer dispersant Part, 4.5 parts by weight of polymer A, and 72 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) as an organic solvent, and then dispersed using a mill type disperser filled with zirconia beads, A pigment dispersion was obtained.
次に、この顔料分散液１００重量部に対し、反応性モノマーとして、構造式（１）で−Ｒ１は−Ｈ、ｍ＝２、ｎ＝９で表される化合物（共栄社油脂（株）製、ライトエステル９ＥＧ）を３．５重量部、ジペンタエリスリトールヘキサアクリレートおよびジペンタエリスリトールペンタアクリレートの混合物（日本化薬（株）製“カヤキュア”ＤＰＨＡ、以下ＤＰＨＡとする）を７．５重量部、光重合開始剤として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（株）製 イルガキュア９０７、以下ＩＣ９０７とする）を２．２重量部、２，４−ジエチルチオキサントン（日本化薬（株）製 、以下ＤＥＴＸ−Ｓとする）を１．１重量部、密着改良剤としてビニルトリメトキシシラン（信越化学（株）製 ＫＢＭ１００３、以下ＫＢＭ１００３とする）を１．２重量部、界面活性剤としてメガファックＲ−０８（大日本化学工業（株）製、以下Ｒ−０８とする）を０．１重量部、重合禁止剤として２，５−ビス（１，１，３，３−テトラメチルブチル）ヒドロキノン（和光純薬工業（株）製、以下ＤＯＨＱとする）０．１重量部（全樹脂分に対して０．５質量％）、および有機溶剤としてＰＧＭＥＡ１００重量部を混合して、感光性着色組成物を調製した。５０μｍ線幅及び耐溶剤性試験の評価結果を表１に示す。全ての評価項目において良好な結果であり、パターン線幅の露光量依存性も小さく高精細でかつ耐溶剤性に優れたパターンが得られた。 Next, with respect to 100 parts by weight of this pigment dispersion, as a reactive monomer, -R 1 in the structural formula (1) is represented by -H, m = 2, and n = 9 (manufactured by Kyoeisha Yushi Co., Ltd.). 3.5 parts by weight of light ester 9EG), 7.5 parts by weight of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (“Kayacure” DPHA manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as DPHA), As a photopolymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter referred to as IC907) was 2.2. Part by weight, 1.1 parts by weight of 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as DETX-S), vinyltoid as adhesion improver 1.2 parts by weight of methoxysilane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as KBM1003) and Megafac R-08 (manufactured by Dainippon Chemical Co., Ltd., hereinafter referred to as R-08) as a surfactant 0.1 part by weight, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as DOHQ) as a polymerization inhibitor 0.1 part by weight ( The photosensitive coloring composition was prepared by mixing 100 parts by weight of PGMEA as an organic solvent and 0.5% by mass with respect to the total resin content. Table 1 shows the evaluation results of the 50 μm line width and the solvent resistance test. Good results were obtained for all the evaluation items, and the pattern line width was small in dependence on the exposure amount, and a pattern with high definition and excellent solvent resistance was obtained.
実施例２
実施例１において、ライトエステル９ＥＧを、構造式（１）で−Ｒ１は−Ｈ、ｍ＝２、ｎ＝１４で表される化合物（共栄社油脂（株）製、ライトエステル１４ＥＧ）に変更した以外は実施例１と同様の操作を行った。評価結果を表１に示す。得られたパターンは耐溶剤性に優れており、パターン線幅の露光量依存性も小さかった。
Example 2
In Example 1, except that the light ester 9EG was changed to a compound represented by the structural formula (1), where -R1 is -H, m = 2, and n = 14 (manufactured by Kyoeisha Yushi Co., Ltd., light ester 14EG). The same operation as in Example 1 was performed. The evaluation results are shown in Table 1. The obtained pattern was excellent in solvent resistance, and the dependency of the pattern line width on the exposure amount was also small.
実施例３
実施例１において、ライトエステル９ＥＧを、構造式（２）で−Ｒ２は−ＣＨ３、ｐ＝ｑ＝２、ｒ＋ｓ＝６でＸが構造式（３）（日本油脂（株）製、ブレンマーＰＤＢＥ−２５０）で表される化合物に変更した以外は実施例１と同様の操作を行った。評価結果を表１に示す。得られたパターンは耐溶剤性に優れており、パターン線幅の露光量依存性も小さかった。
Example 3
In Example 1, the light ester 9EG is represented by the structural formula (2), -R 2 is -CH 3 , p = q = 2, r + s = 6 and X is the structural formula (3) (Nippon Yushi Co., Ltd., Blemmer The same operation as in Example 1 was carried out except that the compound was changed to the compound represented by PDBE-250). The evaluation results are shown in Table 1. The obtained pattern was excellent in solvent resistance, and the dependency of the pattern line width on the exposure amount was also small.
実施例４
実施例１において、重合禁止剤ＤＯＨＱを０．０２重量部（全樹脂分に対して０．１質量％）添加する以外は実施例１と同様の操作を行った。評価結果を表１に示す。得られたパターンは耐溶剤性に優れており、パターン線幅の露光量依存性も小さかった。
Example 4
In Example 1, the same operation as in Example 1 was performed except that 0.02 part by weight of the polymerization inhibitor DOHQ (0.1% by mass relative to the total resin content) was added. The evaluation results are shown in Table 1. The obtained pattern was excellent in solvent resistance, and the dependency of the pattern line width on the exposure amount was also small.
比較例１
反応性モノマーとして、二官能性モノマーを用いず、全てＤＰＨＡを用いた以外は実施例１と同様にして感光性着色組成物を調整した。色差とパターン線幅の露光量依存性は良好であったが、ＮＭＰ浸漬後の膜表面にはクラックやシワが観察された。
Comparative Example 1
A photosensitive coloring composition was prepared in the same manner as in Example 1 except that DPHA was used as the reactive monomer and not all the bifunctional monomer. Although the dependency of the color difference and the pattern line width on the exposure amount was good, cracks and wrinkles were observed on the film surface after NMP immersion.
比較例２
反応性モノマーとして、ライトエステル９ＥＧを１．８重量部、ＤＰＨＡを４．２重量部、ポリマーＡを５．０重量部用いた以外は実施例１と同様にして感光性着色組成物を調整した。実施例１に比べ反応性モノマーの含有量が減り、ＮＭＰ浸漬後の膜にはシミが観察され、色差も３以上と悪化した。
Comparative Example 2
A photosensitive coloring composition was prepared in the same manner as in Example 1 except that 1.8 parts by weight of light ester 9EG, 4.2 parts by weight of DPHA, and 5.0 parts by weight of polymer A were used as reactive monomers. . Compared with Example 1, the content of the reactive monomer decreased, stains were observed in the film after NMP immersion, and the color difference was also deteriorated to 3 or more.
比較例３
実施例１において、重合禁止剤ＤＯＨＱを０．２重量部（全樹脂分に対して１．０質量％）添加する以外は実施例１と同様の操作を行った。パターン線幅の露光量依存性は非常に小さく、ＮＭＰ浸漬後の色差も良好であったが、膜上にシミが観察された。
Comparative Example 3
In Example 1, the same operation as in Example 1 was performed except that 0.2 part by weight of the polymerization inhibitor DOHQ (1.0% by mass relative to the total resin content) was added. The dependence of the pattern line width on the exposure dose was very small, and the color difference after immersion in NMP was good, but spots were observed on the film.
比較例４
重合禁止剤の添加無しである以外は実施例１と同様にして感光性着色組成物を調整した。ＮＭＰ耐性は良好であったが、露光量によって線幅の変換差が大きくなり高精細なパターンを作製することが困難であった。
Comparative Example 4
A photosensitive coloring composition was prepared in the same manner as in Example 1 except that no polymerization inhibitor was added. Although the NMP resistance was good, it was difficult to produce a high-definition pattern because the line width conversion difference increased with the exposure dose.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008043903A JP2009204641A (en) | 2008-02-26 | 2008-02-26 | Photosensitive colored composition for color filter, and color filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008043903A JP2009204641A (en) | 2008-02-26 | 2008-02-26 | Photosensitive colored composition for color filter, and color filter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2009204641A true JP2009204641A (en) | 2009-09-10 |
Family
ID=41147026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008043903A Pending JP2009204641A (en) | 2008-02-26 | 2008-02-26 | Photosensitive colored composition for color filter, and color filter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2009204641A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101082494B1 (en) * | 2009-12-23 | 2011-11-11 | 주식회사 엘지화학 | Photosensitive resin composition with enhanced pattern adhesion and developability |
| JP2012012580A (en) * | 2010-06-01 | 2012-01-19 | Nippon Steel Chem Co Ltd | Thermosetting resin composition containing (meth)acrylate resin, and cured product using the same |
| CN103232603A (en) * | 2013-04-03 | 2013-08-07 | 京东方科技集团股份有限公司 | Alkali-soluble resin and preparation method thereof, and photoresist composition |
| CN103364989A (en) * | 2013-05-22 | 2013-10-23 | 华映视讯（吴江）有限公司 | Manufacturing method of color filter substrate |
| JP7091026B2 (en) | 2017-03-22 | 2022-06-27 | 東洋インキＳｃホールディングス株式会社 | Red coloring composition for organic EL display device, color filter for organic EL display device and organic EL display device |
| WO2023200045A1 (en) * | 2022-04-13 | 2023-10-19 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer prepared using same, and color filter |
-
2008
- 2008-02-26 JP JP2008043903A patent/JP2009204641A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101082494B1 (en) * | 2009-12-23 | 2011-11-11 | 주식회사 엘지화학 | Photosensitive resin composition with enhanced pattern adhesion and developability |
| JP2012012580A (en) * | 2010-06-01 | 2012-01-19 | Nippon Steel Chem Co Ltd | Thermosetting resin composition containing (meth)acrylate resin, and cured product using the same |
| CN103232603A (en) * | 2013-04-03 | 2013-08-07 | 京东方科技集团股份有限公司 | Alkali-soluble resin and preparation method thereof, and photoresist composition |
| CN103232603B (en) * | 2013-04-03 | 2015-03-18 | 京东方科技集团股份有限公司 | Alkali-soluble resin and preparation method thereof, and photoresist composition |
| CN103364989A (en) * | 2013-05-22 | 2013-10-23 | 华映视讯（吴江）有限公司 | Manufacturing method of color filter substrate |
| JP7091026B2 (en) | 2017-03-22 | 2022-06-27 | 東洋インキＳｃホールディングス株式会社 | Red coloring composition for organic EL display device, color filter for organic EL display device and organic EL display device |
| WO2023200045A1 (en) * | 2022-04-13 | 2023-10-19 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer prepared using same, and color filter |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4821206B2 (en) | Photosensitive coloring composition for color filter and color filter | |
| JP2007034119A5 (en) | ||
| TWI719016B (en) | Colored photosensitive resin composition, color filter, and image display apparatus comprising the same | |
| JP2006259716A (en) | Photosensitive coloring composition and color filter | |
| JP5333696B1 (en) | Photosensitive black resin composition and resin black matrix substrate | |
| JP2008122750A (en) | Photosensitive resist composition for color filter, and the color filter | |
| JP2015041104A (en) | Colored photosensitive resin composition, and color filter and display device including the same | |
| TWI612382B (en) | Colored photosensitive resin composition for red pixel, color filter using thereof and display device having the same | |
| JP5540649B2 (en) | Red coloring composition for color filter, color filter substrate for liquid crystal display device, and liquid crystal display device | |
| JP2009204641A (en) | Photosensitive colored composition for color filter, and color filter | |
| KR102335628B1 (en) | Colored photosensitive resin composition, color filter and image display device produced using the same | |
| JP2008249987A (en) | Photosensitive resist composition and color filter | |
| KR102383693B1 (en) | Colored photosensitive composition, color filter and image display device | |
| JP2005338400A (en) | Negative colored photosensitive composition | |
| JP2018173470A (en) | Photosensitive colored resin composition, color filter substrate and display device | |
| JP2012058498A (en) | Photosensitive colored composition for color filter and color filter | |
| KR102179956B1 (en) | Colored photosensitive resin composition, color filter, and liquid crystal display device apparatus comprising the same | |
| KR102243364B1 (en) | Photosensitive resin composition, photosensitive resin layer using the same, color filter and display device | |
| JP2016051176A (en) | Colored photosensitive resin composition | |
| JP6658217B2 (en) | Photosensitive composition for color filter, color filter substrate and method for producing the same, and display device using these | |
| KR20190093915A (en) | Colored photo sensitive resin composition, a color filter comprising the same, and a display devide comprising the color filter | |
| KR20160103279A (en) | Color photosensitive resin composition, color filter manufactured thereby and liquid crystal display comprising the same | |
| JP2009169049A (en) | Photosensitive resist composition for color filter and color filter | |
| JP2012212030A (en) | Photosensitive coloring composition for color filter and color filter | |
| JP2009223097A (en) | Vacuum drying method for resin composition for color filter and manufacturing method for color filter substrate |