JP5991040B2 - Black photosensitive resin composition, black matrix and color filter - Google Patents
Black photosensitive resin composition, black matrix and color filter Download PDFInfo
- Publication number
- JP5991040B2 JP5991040B2 JP2012140753A JP2012140753A JP5991040B2 JP 5991040 B2 JP5991040 B2 JP 5991040B2 JP 2012140753 A JP2012140753 A JP 2012140753A JP 2012140753 A JP2012140753 A JP 2012140753A JP 5991040 B2 JP5991040 B2 JP 5991040B2
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- JP
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- Prior art keywords
- black
- photosensitive resin
- resin composition
- group
- dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 79
- 239000011159 matrix material Substances 0.000 title claims description 55
- 239000007787 solid Substances 0.000 claims description 66
- 239000006229 carbon black Substances 0.000 claims description 41
- 239000000975 dye Substances 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000001044 red dye Substances 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 239000001043 yellow dye Substances 0.000 claims description 4
- 239000001045 blue dye Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001047 purple dye Substances 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 30
- 239000000049 pigment Substances 0.000 description 30
- -1 alkyl methacrylates Chemical class 0.000 description 26
- 239000000758 substrate Substances 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 20
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 18
- 239000003822 epoxy resin Substances 0.000 description 17
- 229920000647 polyepoxide Polymers 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- 230000035945 sensitivity Effects 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- RLUCXJBHKHIDSP-UHFFFAOYSA-N propane-1,2-diol;propanoic acid Chemical compound CCC(O)=O.CC(O)CO RLUCXJBHKHIDSP-UHFFFAOYSA-N 0.000 description 11
- 239000004973 liquid crystal related substance Substances 0.000 description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 10
- 229930185605 Bisphenol Natural products 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 9
- INXWLSDYDXPENO-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CO)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C INXWLSDYDXPENO-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 239000010959 steel Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000012860 organic pigment Substances 0.000 description 6
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 4
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001046 green dye Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001048 orange dye Substances 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000000206 photolithography Methods 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
- 239000001054 red pigment Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- CQNUMTMWJRSIRY-UHFFFAOYSA-N 1,1'-biphenyl;diphenylmethanone Chemical class C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 CQNUMTMWJRSIRY-UHFFFAOYSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- NLXFWUZKOOWWFD-UHFFFAOYSA-N 1-(2-hydroxyethylamino)-4-(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCO)=CC=C2NC NLXFWUZKOOWWFD-UHFFFAOYSA-N 0.000 description 1
- WSPPHHAIMCTKNN-UHFFFAOYSA-N 1-amino-4-hydroxy-2-methoxyanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(OC)=CC(O)=C3C(=O)C2=C1 WSPPHHAIMCTKNN-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-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
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QAMCXJOYXRSXDU-UHFFFAOYSA-N 2,4-dimethoxy-n-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]aniline;chloride Chemical compound [Cl-].COC1=CC(OC)=CC=C1NC=CC1=[N+](C)C2=CC=CC=C2C1(C)C QAMCXJOYXRSXDU-UHFFFAOYSA-N 0.000 description 1
- QIRUERQWPNHWRC-UHFFFAOYSA-N 2-(1,3-benzodioxol-5-ylmethyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(CC=2C=C3OCOC3=CC=2)=N1 QIRUERQWPNHWRC-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- CKCGJBFTCUCBAJ-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propyl acetate Chemical compound CCOC(C)COC(C)COC(C)=O CKCGJBFTCUCBAJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
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- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Landscapes
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、カラーテレビ、液晶カラーテレビ、カメラ等に使用される光学的カラーフィルターに用いる黒色感光性樹脂組成物、ブラックマトリックス及びカラーフィルタに関する。 The present invention relates to a black photosensitive resin composition, a black matrix, and a color filter used for an optical color filter used in a color television, a liquid crystal color television, a camera and the like.
カラーフィルタは、近年様々な分野に応用が進んでいる液晶表示装置のカラー化に必要不可欠な部品であり、カラーフィルタは、ガラスなどの透明基板上に、例えば赤色、緑色、青色などの着色画素を設けたものである。各着色画素の間には、コントラストを向上させるため、また、液晶表示装置において対向基板上に設けられるＴＦＴ素子の光による誤動作を防ぐため、一般的に遮光部（ブラックマトリックス）が設けられる。 The color filter is an indispensable component for colorization of liquid crystal display devices that have been applied in various fields in recent years. The color filter is a colored pixel such as red, green, or blue on a transparent substrate such as glass. Is provided. In general, a light-shielding portion (black matrix) is provided between the colored pixels in order to improve contrast and to prevent malfunction caused by light of TFT elements provided on the counter substrate in the liquid crystal display device.
ブラックマトリックスの形成法としては、金属クロム薄膜をエッチングする方法が用いられてきたが、コスト並びに環境負荷の問題から、遮光材を含有した黒色感光性樹脂組成物を用いるフォトリソグラフィー法への置き換えが進んでいる。 As a method for forming a black matrix, a method of etching a metal chromium thin film has been used. However, due to cost and environmental load problems, replacement with a photolithography method using a black photosensitive resin composition containing a light shielding material is possible. Progressing.
黒色感光性樹脂組成物を用いたフォトリソグラフィー法によるブラックマトリックスの形成は以下のように行う。最初に、スピンコートあるいはスリットコート法等により黒色感光性樹脂組成物の塗膜を形成する。必要に応じて乾燥、加熱処理を施した後、所定のパターンを有するフォトマスクを介して露光処理を行う。続いて、現像処理により未露光部を除去し、加熱硬膜処理を施すことでブラックマトリックスを形成することができる。 Formation of the black matrix by the photolithography method using the black photosensitive resin composition is performed as follows. First, a black photosensitive resin composition coating film is formed by spin coating or slit coating. After drying and heat treatment as necessary, exposure processing is performed through a photomask having a predetermined pattern. Subsequently, a black matrix can be formed by removing an unexposed portion by a development process and performing a heat hardening process.
黒色感光性樹脂組成物に用いられる遮光材としては、遮光性並びにコスト性能に優れたカーボンブラックが広く用いられている。黒色感光性樹脂組成物の固形分中におけるカーボンブラックの顔料濃度を一定以上に保つことにより、カラーフィルタの平坦性を損なわない実用的な膜厚範囲で金属クロム同等の遮光性を有するブラックマトリックスを形成することが可能である。 As a light shielding material used in the black photosensitive resin composition, carbon black having excellent light shielding properties and cost performance is widely used. By maintaining the pigment concentration of carbon black in the solid content of the black photosensitive resin composition at a certain level or higher, a black matrix having a light shielding property equivalent to that of metal chromium in a practical film thickness range that does not impair the flatness of the color filter. It is possible to form.
ブラックマトリックスに求められる遮光性以外の特性の一つとして絶縁性が挙げられる。これは、ブラックマトリックスが透明電極と導通し、意図せぬ電界が生じ表示不良が発生するのを防ぐためである。 One of the characteristics other than the light shielding property required for the black matrix is insulation. This is to prevent the black matrix from being electrically connected to the transparent electrode and causing an unintended electric field to cause display defects.
しかしながら、カーボンブラックは導体であるため、ブラックマトリックスの遮光性を保つのに必要な水準まで顔料濃度を高くした場合は絶縁性が著しく低くなってしまう。すなわち、遮光性と絶縁性がトレードオフになるという問題がある。 However, since carbon black is a conductor, when the pigment concentration is increased to a level necessary to maintain the light shielding property of the black matrix, the insulating property is remarkably lowered. That is, there is a problem that the light shielding property and the insulating property are traded off.
遮光性と絶縁性のトレードオフを解決するための施策として、カーボンブラックを樹脂で被覆し、更には酸化処理を施すことにより絶縁性を付与する提案がなされている（特許文献１、特許文献２）。 As measures for solving the trade-off between light shielding properties and insulating properties, proposals have been made to provide insulating properties by coating carbon black with a resin and further performing an oxidation treatment (Patent Documents 1 and 2). ).
しかしながら該手法では樹脂被覆によりブラックマトリックス中の遮光剤、すなわちカーボンブラック顔料の密度が低くなるため、同一顔料濃度で比較した場合の遮光性は被覆のないものと比して劣るという問題がある。黒色感光性樹脂組成物の顔料濃度を高くすることで遮光性を補うことが出来るが、この場合樹脂被覆の効果が薄れ絶縁性が低下してしまう。 However, in this method, since the density of the light-shielding agent in the black matrix, that is, the carbon black pigment is lowered by the resin coating, there is a problem that the light-shielding property when compared at the same pigment concentration is inferior to that without the coating. Increasing the pigment concentration of the black photosensitive resin composition can supplement the light shielding property, but in this case, the effect of the resin coating is reduced and the insulating property is lowered.
一方、カーボンブラックの分散液とカラーフィルタの着色画素形成に用いられる有機顔
料の分散液を混合してなる黒色感光性樹脂組成物を用いることにより、遮光性と絶縁性を両立する提案がなされている（特許文献３、特許文献４）。
On the other hand, by using a black photosensitive resin composition obtained by mixing a dispersion of carbon black and a dispersion of an organic pigment used for forming colored pixels of a color filter, a proposal has been made to achieve both light shielding properties and insulating properties. (Patent Literature 3, Patent Literature 4).
しかしながら、これらの有機顔料はカーボンブラックと比して遮光性が低いため、遮光性を向上させるには添加量を増やす必要がある。この場合有機顔料の分散液中に含まれる分散剤、分散助剤といった成分も増えてしまうため、黒色感光性樹脂組成物中に一定量の感光性成分が必要であることを考慮すると遮光性向上には自ずと限界がある。また、分散液同士の相溶性が悪く、異物が発生する恐れもある。 However, these organic pigments have a low light shielding property compared to carbon black, so that the amount added needs to be increased in order to improve the light shielding property. In this case, components such as dispersants and dispersion aids contained in the dispersion liquid of the organic pigment also increase. Therefore, considering that a certain amount of the photosensitive component is necessary in the black photosensitive resin composition, the light shielding property is improved. Has its own limits. Further, the compatibility between the dispersions is poor, and foreign matter may be generated.
これに対し、カーボンブラックと有機顔料を同時に均一分散させた顔料分散液を用いた黒色感光性樹脂組成物が提案されている（特許文献５）。この場合上記の問題は解消されるものの、カーボンブラックと有機顔料の双方を均一分散させることが可能な分散剤の選定には非常な困難を伴う。また、カーボンブラック分散液の絶縁性能は分散剤依存性が大きく、有機顔料との均一分散を優先することで肝心の絶縁性能が損なわれる恐れもある。 In contrast, a black photosensitive resin composition using a pigment dispersion in which carbon black and an organic pigment are simultaneously uniformly dispersed has been proposed (Patent Document 5). In this case, although the above problem is solved, it is very difficult to select a dispersant capable of uniformly dispersing both carbon black and organic pigment. Further, the insulating performance of the carbon black dispersion is highly dependent on the dispersant, and priority may be given to uniform dispersion with the organic pigment, which may impair the essential insulating performance.
このように、ブラックマトリックスにおける遮光性と絶縁性の両立を目指した開発は未だ発展途上の段階である。近年精力的に検討が進められている高精細化に伴うカラーフィルタの平坦性悪化を補うため、ブラックマトリックスの薄膜化が求められている。こうした要望に応えるためには従来より高次元で遮光性と絶縁性を両立させる必要があるが、それを可能にする材料は得られていないのが現状である。 In this way, development aimed at achieving both light shielding and insulating properties in the black matrix is still in the developing stage. In order to compensate for the deterioration of the flatness of the color filter due to high definition, which has been studied energetically in recent years, it is required to make the black matrix thinner. In order to meet these demands, it is necessary to achieve both a light shielding property and an insulating property at a higher level than in the past. However, at present, no material has been obtained.
本発明はかかる事情を鑑みてなされたものであり、高次元で遮光性と絶縁性を両立したブラックマトリックスを形成することが可能な、黒色感光性樹脂組成物を提供し、それを用いたブラックマトリックス及びカラーフィルタを提供することにある。 The present invention has been made in view of the above circumstances, and provides a black photosensitive resin composition capable of forming a black matrix having both high light shielding properties and insulating properties, and a black using the same. It is to provide a matrix and a color filter.
上記の課題を解決するための手段として、請求項１に記載の発明は、少なくとも遮光材、樹脂、重合性モノマー、光重合開始剤および溶剤を含有する黒色感光性樹脂組成物であって、前記遮光材としてカーボンブラックと染料を含有し、前記カーボンブラックの含有量が前記黒色感光性樹脂組成物の固形分中４０〜５０重量パーセントであり、前記染料の含有量が前記黒色感光性樹脂組成物の固形分中１〜２０重量パーセントであることを特徴とする黒色感光性樹脂組成物である。 As a means for solving the above problems, the invention according to claim 1 is a black photosensitive resin composition containing at least a light shielding material, a resin, a polymerizable monomer, a photopolymerization initiator, and a solvent, It contains carbon black and a dye as a light shielding material, the carbon black content is 40 to 50 weight percent in the solid content of the black photosensitive resin composition, and the dye content is the black photosensitive resin composition. 1 to 20 percent by weight in the solid content of the black photosensitive resin composition.
また、請求項２に記載の発明は、前記染料として赤色染料と青色染料を含有することを特徴とする請求項１記載の黒色感光性樹脂組成物である。 Moreover, invention of Claim 2 contains a red dye and a blue dye as said dye, It is a black photosensitive resin composition of Claim 1 characterized by the above-mentioned.
また、請求項３に記載の発明は、前記赤色染料としてＣ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ１２４、前記青色染料としてＣ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ８７を含有することを特徴とする請求項２記載の黒色感光性樹脂組成物である。 In the invention according to claim 3, C.I. I. Solvent Red 124, C.I. I. The black photosensitive resin composition according to claim 2, comprising Solvent Blue 87.
また、請求項４に記載の発明は、前記染料として黄色染料と紫色染料を含有することを特徴とする請求項１記載の黒色感光性樹脂組成物である。 Moreover, invention of Claim 4 contains the yellow dye and the purple dye as said dye, It is a black photosensitive resin composition of Claim 1 characterized by the above-mentioned.
また、請求項５に記載の発明は、前記黄色染料としてＣ．Ｉ．ＳｏｌｖｅｎｔＹｅｌｌｏｗ８３を、前記紫色染料としてＣ．Ｉ．ＳｏｌｖｅｎｔＶｉｏｌｅｔ３６を含有することを特徴とする請求項４記載の黒色感光性樹脂組成物である。 In the invention according to claim 5, C.I. I. Solvent Yellow 83 is C.I. I. The black photosensitive resin composition according to claim 4, comprising SolventViolet 36.
また、請求項６に記載の発明は、前記光重合開始剤として化式（１）で表される化合物を含有することを特徴とする請求項１〜５のいずれか一項に記載の黒色感光性樹脂組成物。 Further, the invention described in claim 6 contains the compound represented by the chemical formula (1) as the photopolymerization initiator, and the black photosensitivity according to any one of claims 1 to 5. Resin composition.
〔化式（１）において、Ｘ１、Ｘ３、Ｘ６は、それぞれ独立にＲ１１、ＯＲ１１、ＣＯＲ１１、ＳＲ１１、ＣＯＮＲ１２Ｒ１３又はＣＮを表し、Ｘ２は置換基を有していてもよい炭素原子数１〜２０のアルキル基、置換基を有していてもよい炭素原子数６〜３０のアリール基、置換基を有していてもよい炭素原子数７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数２〜２０の複素環基を表し、Ｘ４及びＸ５は、それぞれ独立に、Ｒ１１、ＯＲ１１、ＳＲ１１、ＣＯＲ１１、ＣＯＮＲ１２Ｒ１３、ＮＲ１２ＣＯＲ１１、ＯＣＯＲ１１、ＣＯＯＲ１１、ＳＣＯＲ１１、ＣＯＳＲ１１、ＣＯＳＲ１１、ＣＳＯＲ１１、ＣＮ、ハロゲン原子又は水酸基を表す。Ｒ１１、Ｒ１２及びＲ１３は、それぞれ独立に、水素原子、置換基を有していてもよい炭素原子数１〜２０のアルキル基、置換基を有していてもよい炭素原子数６〜３０のアリール基、置換基を有していてもよい炭素原子数７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数２〜２０の複素環基を表す。ａ及びｂはそれぞれ独立に、０〜３である。〕
また、請求項７に記載の発明は、請求項１〜６のいずれか１項に記載の黒色感光性樹脂組成物を用いて形成され、膜厚１．０μｍ当たりの光学濃度（ＯＤ値）が４．０／μｍ以上であり、体積抵抗率が１．０×１０１２Ω・ｃｍ以上であることを特徴とするブラックマトリックスである。
[In the chemical formula (1), X 1 , X 3 and X 6 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN, and X 2 has a substituent. An optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and an optionally substituted aryl having 7 to 30 carbon atoms Represents an alkyl group or an optionally substituted heterocyclic group having 2 to 20 carbon atoms, and X 4 and X 5 each independently represent R 11 , OR 11 , SR 11 , COR 11 , CONR 12. R 13, NR 12 COR 11, OCOR 11, COOR 11, SCOR 11, COSR 11, COSR 11, CSOR 11, CN, a halogen atom or a hydroxyl group. R 11 , R 12 and R 13 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 6 to 6 carbon atoms. It represents a 30 aryl group, an optionally substituted arylalkyl group having 7 to 30 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. a and b are each independently 0-3. ]
The invention described in claim 7 is formed using the black photosensitive resin composition described in any one of claims 1 to 6 , and has an optical density (OD value) per 1.0 μm film thickness. The black matrix is 4.0 / μm or more and has a volume resistivity of 1.0 × 10 12 Ω · cm or more.
また、請求項８に記載の発明は、請求項７記載のブラックマトリックスを具備することを特徴とするカラーフィルタである。 The invention according to claim 8 is a color filter comprising the black matrix according to claim 7.
本発明の黒色感光性樹脂組成物を用いることにより、カラーフィルタの平坦性を損ねることのない薄膜においても十分な遮光性を有し、かつ絶縁性も良好なブラックマトリックスを効率よく製造することが出来る。本発明のカラーフィルタは前記のように遮光性と絶縁性を兼ね備えたブラックマトリックスを具備しているため、液晶表示装置の高コントラスト化と信頼性向上が可能である。 By using the black photosensitive resin composition of the present invention, it is possible to efficiently produce a black matrix having sufficient light shielding properties and good insulating properties even in a thin film that does not impair the flatness of the color filter. I can do it. Since the color filter of the present invention includes the black matrix having both light shielding properties and insulating properties as described above, the contrast of the liquid crystal display device can be increased and the reliability can be improved.
（黒色感光性樹脂組成物）
本発明の黒色感光性樹脂組成物は、少なくとも遮光材、樹脂、重合性モノマー、光重合開始剤及び溶剤を含み、前記遮光材としてカーボンブラックと染料を含み、前記カーボンブラックの含有量が前記黒色感光性樹脂組成物の固形分中４０重量パーセント以上であり、前記染料の含有量が前記黒色感光性樹脂組成物の固形分中１〜２０重量パーセントであることを特徴とする。以下、本発明の黒色感光性樹脂組成物を構成する各成分について説明する。
(Black photosensitive resin composition)
The black photosensitive resin composition of the present invention includes at least a light shielding material, a resin, a polymerizable monomer, a photopolymerization initiator, and a solvent, and includes carbon black and a dye as the light shielding material, and the carbon black content is the black color. It is 40 weight percent or more in the solid content of the photosensitive resin composition, and the content of the dye is 1 to 20 weight percent in the solid content of the black photosensitive resin composition. Hereinafter, each component which comprises the black photosensitive resin composition of this invention is demonstrated.
＜遮光材＞
＜カーボンブラック＞
本発明に用いられるカーボンブラックとしては、ランプブラック、アセチレンブラック、サーマルブラック、チャンネルブラック、ファーネスブラック等のいずれのものを用いても良い。
<Shading material>
<Carbon black>
As the carbon black used in the present invention, any of lamp black, acetylene black, thermal black, channel black, furnace black and the like may be used.
カーボンブラックの含有量は黒色感光性樹脂組成物の固形分中４０〜５０重量パーセント以上であり、好ましくは４２〜４８重量パーセントである。含有量が４０重量パーセント以下である場合、黒色感光性樹脂組成物を用いて形成されるブラックマトリックスの遮光性が不足する。一方、含有量が５０重量パーセント以上である場合、ブラックマトリックスの絶縁性が不足する。 The content of carbon black is 40 to 50 weight percent or more, preferably 42 to 48 weight percent in the solid content of the black photosensitive resin composition. When the content is 40% by weight or less, the black matrix formed using the black photosensitive resin composition has insufficient light shielding properties. On the other hand, when the content is 50 weight percent or more, the black matrix lacks insulation.
＜染料＞
本発明の黒色感光性樹脂組成物は、カーボンブラックの顔料濃度を前記の範囲に抑えつつ遮光性を向上させるために染料が用いられる。染料は単独でも使用することができるが、液晶表示装置における黒表示の色味付きを避けるために赤色系と青色系、あるいは黄色系と紫色系といった補色関係にある色を混合して用いるのが望ましい。
<Dye>
In the black photosensitive resin composition of the present invention, a dye is used to improve the light shielding property while suppressing the pigment concentration of carbon black within the above range. Dyes can be used alone, but in order to avoid the black display in the liquid crystal display device, it is necessary to use a mixture of complementary colors such as red and blue, or yellow and purple. desirable.
赤色染料の具体例としては、Ｃ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ１、２、３、４、８、１６、１７、１８、１９、２３、２４、２５、２６、２７、３０、３３、３５、４１、４３、４５、４８、４９、５２、６８、６９、７２、７３、８３：１、８４：１、８９、９０、９０：１、９１、９２、１０６、１０９、１１０、１１８、１１９、１２２、１２４、１２５、１２７、１３０、１３２、１３５、１４１、１４３、１４５、１４６、１４９、１５０、１５１、１５５、１６０、１６１、１６４、１６４：１、１６５、１６６、１６８、１６９、１７２、１７５、１７９、１８０、１８１、１８２、１９５、１９６、１９７、１９８、２０７、２０８、２１０、２１２、２１４、２１５、２１８、２２２、２２３、２２５、２２７、２２９、２３０、２３３、２３４、２３５、２３６、２３８、２３９、２４０、２４１、２４２、２４３、２４４、２４５、２４７、２４８、Ｃ．Ｉ．ＡｃｉｄＲｅｄ６、１１、２６、６０、８８、１１１、１８６、２１５、Ｃ．Ｉ．ＢａｓｉｃＲｅｄ１、２、１３、１４、２２、２７、２９、３９、Ｃ．Ｉ．ＤｉｒｅｃｔＲｅｄ４、２３、３１、７５、７６、７９、８０、８１、８３、８４、１４９、２２４、Ｃ．Ｉ．ＳｕｌｐｈｕｒＲｅｄ５、６、７、Ｃ．Ｉ．ＲｅａｃｔｉｖｅＲｅｄ８、２２、４６、１２０、Ｃ．Ｉ．ＤｉｓｐｅｒｓｅＲｅｄ４、１１、５４、５５、５８、６５、７３、１２７、１２９、１４１、１９６、２１０、２２９、３５４、３５６等が挙げられる。中でも、溶解性、耐熱性に優れたＣ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ８３、９２、１２４を使用するのが好ましく、Ｃ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ１２４を使用するのが最も好ましい。 Specific examples of the red dye include C.I. I. SolventRed 1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30, 33, 35, 41, 43, 45, 48, 49, 52, 68, 69, 72, 73, 83: 1, 84: 1, 89, 90, 90: 1, 91, 92, 106, 109, 110, 118, 119, 122, 124, 125, 127, 130, 132, 135, 141, 143, 145, 146, 149, 150, 151, 155, 160, 161, 164, 164: 1, 165, 166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197, 198, 207, 208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234, 235, 23 , 238,239,240,241,242,243,244,245,247,248, C. I. Acid Red 6, 11, 26, 60, 88, 111, 186, 215, C.I. I. Basic Red 1, 2, 13, 14, 22, 27, 29, 39, C.I. I. DirectRed 4, 23, 31, 75, 76, 79, 80, 81, 83, 84, 149, 224, C.I. I. SulfurRed 5, 6, 7, C.I. I. Reactive Red 8, 22, 46, 120, C.I. I. Disperse Red 4, 11, 54, 55, 58, 65, 73, 127, 129, 141, 196, 210, 229, 354, 356, and the like. Among them, C.I. excellent in solubility and heat resistance. I. Solvent Red 83, 92, 124 are preferably used, and C.I. I. Most preferably, SolventRed 124 is used.
青色染料の具体例としては、Ｃ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ２、３、４、５、７、１８、２５、２６、３５、３６、３７、３８、４３、４４、４５、４８、５１、５８、５９、５９：１、６３、６４、６７、６８、６９、７０、７８、７９、８３、９４、９７、９８、１００、１０１、１０２、１０４、１０５、１１１、１１２、１２２、１２４、１２８、１２９、１３２、１３６、１３７、１３８、１３９、１４３、Ｃ．Ｉ．ＡｃｉｄＢｌｕｅ２２、２５、４０、７８、９２、１１３、１２９、１６７、２３０、Ｃ．Ｉ．ＢａｓｉｃＢｌｕｅ３、７、９、１７、４１、６６、Ｃ．Ｉ．ＤｉｒｅｃｔＢｌｕｅ７１、７８、９８、１０６、１０８、１９２、２０１、Ｃ．Ｉ．ＤｉｒｅｃｔＢｌｕｅ７１、７８、９８、１０６、１０８、１９２、２０１、Ｃ．Ｉ．ＳｕｌｐｈｕｒＢｌｕｅ２、３、７、９、１３、１５、Ｃ．Ｉ．ＶａｔＢｌｕｅ６、１４、２６、３０、Ｃ．Ｉ．ＲｅａｃｔｉｖｅＢｌｕｅ１、２、７、１９、Ｃ．Ｉ．ＤｉｓｐｅｒｓｅＢｌｕｅ３、２４、７９、８２、８７、１０６、１２５、１６５、１８３等が挙げられる。中でも、耐熱性に優れたＣ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ７０、８７、９４あるいは着色力に優れたＣ．Ｉ．ＢａｓｉｃＢｌｕｅ７を使用するのが好ましく、Ｃ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ８７を使用するのが最も好ましい。 Specific examples of blue dyes include C.I. I. Solvent Blue 2, 3, 4, 5, 7, 18, 25, 26, 35, 36, 37, 38, 43, 44, 45, 48, 51, 58, 59, 59: 1, 63, 64, 67, 68, 69, 70, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 129, 132, 136, 137, 138, 139, 143, C. I. Acid Blue 22, 25, 40, 78, 92, 113, 129, 167, 230, C.I. I. BasicBlue 3, 7, 9, 17, 41, 66, C.I. I. DirectBlue 71, 78, 98, 106, 108, 192, 201, C.I. I. DirectBlue 71, 78, 98, 106, 108, 192, 201, C.I. I. SulfurBlue 2, 3, 7, 9, 13, 15, C.I. I. VatBlue 6, 14, 26, 30, C.I. I. Reactive Blue 1, 2, 7, 19, C.I. I. DisperseBlue 3, 24, 79, 82, 87, 106, 125, 165, 183 and the like can be mentioned. Among these, C.I. excellent in heat resistance. I. Solvent Blue 70, 87, 94 or C.I. I. Preferably, BasicBlue 7 is used, and C.I. I. Most preferably, SolventBlue 87 is used.
黄色染料の具体例としては、Ｃ．Ｉ．ＳｏｌｖｅｎｔＹｅｌｌｏｗ２、３、７、１２、１３、１４、１６、１８、１９、２１、２５、２５：１、２７、２８、２９、３０、３３、３４、３６、４２、４３、４４、４７、５６、６２、７２、７３、７７、７９、８１、８２、８３、８３：１、８８、８９、９０、９３、９４、９６、９８、１０４、１０７、１１４、１１６、１１７、１２４、１３０、１３１、１３３、１３５、１４１、１４３、１４５、１４６、１５７、１６０：１、１６１、１６２、１６３、１６７、１６９、１７２、１７４、１７５、１７６、１７９、１８０、１８１、１８２、１８３、１８４、１８５、１８６、１８７、１８９、１９０、１９１、Ｃ．Ｉ．ＡｃｉｄＹｅｌｌｏｗ１７、２３、２５、３６、３８、４２、４４、７２、７８、Ｃ．Ｉ．ＢａｓｉｃＹｅｌｌｏｗ１１、２３、２５、２８、４１、Ｃ．Ｉ．ＤｉｒｅｃｔＹｅｌｌｏｗ２６、２７、２８、３３、４４、５０、８６、１４２、Ｃ．Ｉ．ＳｕｌｐｈｕｒＹｅｌｌｏｗ４、Ｃ．Ｉ．ＶａｔＹｅｌｌｏｗ２、１２、２０、３３、Ｃ．Ｉ．ＲｅａｃｔｉｖｅＹｅｌｌｏｗ１、２、４、１４、１６、Ｃ．Ｉ．ＤｉｓｐｅｒｓｅＹｅｌｌｏｗ３、４、５、７、２３、３３、４２、６０、６４等が挙げられる。中でも、溶解性、耐熱性に優れたＣ．Ｉ．ＳｏｌｖｅｎｔＹｅｌｌｏｗ８３を使用するのが好ましい。 Specific examples of yellow dyes include C.I. I. Solvent Yellow 2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25: 1, 27, 28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56, 62, 72, 73, 77, 79, 81, 82, 83, 83: 1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 141, 143, 145, 146, 157, 160: 1, 161, 162, 163, 167, 169, 172, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 186, 187, 189, 190, 191, C.I. I. Acid Yellow 17, 23, 25, 36, 38, 42, 44, 72, 78, C.I. I. Basic Yellow 11, 23, 25, 28, 41, C.I. I. Direct Yellow 26, 27, 28, 33, 44, 50, 86, 142, C.I. I. Sulfur Yellow 4, C.I. I. Vat Yellow 2, 12, 20, 33, C.I. I. Reactive Yellow 1, 2, 4, 14, 16, C.I. I. Disperse Yellow 3, 4, 5, 7, 23, 33, 42, 60, 64 etc. are mentioned. Among them, C.I. excellent in solubility and heat resistance. I. Solvent Yellow 83 is preferably used.
紫色染料の具体例としては、Ｃ．Ｉ．ＳｏｌｖｅｎｔＶｉｏｌｅｔ２、８、９、１１、１３、１４、２１、２１：１、２６、３１、３６、３７、３８、４５、４６、４７、４８、４９、５０、５１、５５、５６、５７、５８、５９、６０、６１、Ｃ．Ｉ．ＢａｓｉｃＶｉｏｌｅｔ１、３、１８、３９、６６、Ｃ．Ｉ．ＤｉｒｅｃｔＶｉｏｌｅｔ５１、Ｃ．Ｉ．ＳｕｌｐｈｕｒＶｉｏｌｅｔ２、３、４、Ｃ．Ｉ．ＶａｔＶｉｏｌｅｔ１、３、９、１３、１５、１６、Ｃ．Ｉ．ＲｅａｃｔｉｖｅＶｉｏｌｅｔ２、４、Ｃ．Ｉ．ＤｉｓｐｅｒｓｅＶｉｏｌｅｔ１、６、１２、２６、２７、２８等が挙げられる。中でも、溶解性、耐熱性に優れたＣ．Ｉ．ＳｏｌｖｅｎｔＶｉｏｌｅｔ３６を使用するのが好ましい。 Specific examples of the purple dye include C.I. I. SolventViolet 2, 8, 9, 11, 13, 14, 21, 21: 1, 26, 31, 36, 37, 38, 45, 46, 47, 48, 49, 50, 51, 55, 56, 57, 58, 59, 60, 61, C.I. I. BasicViolet 1, 3, 18, 39, 66, C.I. I. DirectViolet 51, C.I. I. Sulfur Violet 2, 3, 4, C.I. I. VatViolet 1, 3, 9, 13, 15, 16, C.I. I. Reactive Violet 2, 4, C.I. I. DisperseViolet 1, 6, 12, 26, 27, 28 etc. are mentioned. Among them, C.I. excellent in solubility and heat resistance. I. SolventViolet 36 is preferably used.
遮光性向上あるいは黒表示の色味付き改善のため上記に加えて橙色染料、緑色染料等を併せ用いることも可能である。 In addition to the above, an orange dye, a green dye, or the like can be used in combination in order to improve the light-shielding property or improve the color tone of black display.
橙色染料の具体例としては、Ｃ．Ｉ．ＳｏｌｖｅｎｔＯｒａｎｇｅ１、２、３、４、５、７、１１、１４、２０、２３、２５、３１、４０：１、４１、４５、５４、５６、５８、６０、６２、６３、７０、７５、７７、８０、８１、８６、９９、１０２、１０３、１０５、１０６、１０７、１０８、１０９、１１０、１１１、１１２、１１３、Ｃ．Ｉ．ＤｉｒｅｃｔＯｒａｎｇｅ２６、２９、３４、３７、７２、Ｃ．Ｉ．ＶａｔＯｒａｎｇｅ２、５、１１、１５、１８、２０、Ｃ．Ｉ．ＲｅａｃｔｉｖｅＯｒａｎｇｅ１、４、７、１３、１６、２０、Ｃ．Ｉ．ＤｉｓｐｅｒｓｅＯｒａｎｇｅ１３、２９、３０等が挙げられる。 Specific examples of the orange dye include C.I. I. Solvent Orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31, 40: 1, 41, 45, 54, 56, 58, 60, 62, 63, 70, 75, 77, 80, 81, 86, 99, 102, 103, 105, 106, 107, 108, 109, 110, 111, 112, 113, C.I. I. Direct Orange 26, 29, 34, 37, 72, C.I. I. Vat Orange 2, 5, 11, 15, 18, 20, C.I. I. Reactive Orange 1, 4, 7, 13, 16, 20, C.I. I. Disperse Orange 13, 29, 30 etc. are mentioned.
緑色染料の具体例としては、Ｃ．Ｉ．ＳｏｌｖｅｎｔＧｒｅｅｎ１、３、４、５、７、２８、２９、３２、３３、３４、３５、Ｃ．Ｉ．ＡｃｉｄＧｒｅｅｎ２５、２７、Ｃ．Ｉ．ＢａｓｉｃＧｒｅｅｎ３、４、Ｃ．Ｉ．ＤｉｒｅｃｔＧｒｅｅｎ２６、２８、Ｃ．Ｉ．ＳｕｌｐｈｕｒＧｒｅｅｎ２、３、６、Ｃ．Ｉ．ＶａｔＧｒｅｅｎ３、５、８等が挙げられる。 Specific examples of the green dye include C.I. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, C.I. I. AcidGreen 25, 27, C.I. I. BasicGreen 3, 4, C.I. I. DirectGreen 26, 28, C.I. I. SulfurGreen 2, 3, 6, C.I. I. VatGreen 3, 5, 8 etc. are mentioned.
染料の含有量は黒色感光性樹脂組成物の固形分中１〜２０重量パーセント以上であり、好ましくは２〜１５重量パーセントである。含有量が１重量パーセント以下である場合、染料添加による遮光性向上効果が得られない。一方、含有量が２０重量パーセント以上である場合、染料の溶解性が不足し結晶析出の恐れが生じる。 The content of the dye is 1 to 20 weight percent or more, preferably 2 to 15 weight percent in the solid content of the black photosensitive resin composition. When the content is 1% by weight or less, the effect of improving the light shielding property due to the addition of the dye cannot be obtained. On the other hand, when the content is 20% by weight or more, the solubility of the dye is insufficient, and crystal precipitation may occur.
＜樹脂＞
樹脂としては、アクリル酸、メタクリル酸、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、ブチルメタクリレートなどのアルキルアクリレートまたはアルキルメタクリレート、環状のシクロヘキシルアクリレートまたはメタクリレート、ヒドロキシエチルアクリレートまたはメタクリレート、スチレンなどの内から３〜５種類程度のモノマーを用いて合成した、分子量５０００〜１０００００程度の樹脂を好ましく用いることができる。
<Resin>
Resins include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and other alkyl acrylates or alkyl methacrylates, cyclic cyclohexyl acrylate or methacrylate, hydroxyethyl acrylate or methacrylate, styrene, etc. Among these, a resin having a molecular weight of about 5000 to 100,000, which is synthesized using about 3 to 5 types of monomers, can be preferably used.
また、アクリル系樹脂の一部に不飽和二重結合を付加させた樹脂として、上記のアクリル樹脂、イソシアネート基と少なくとも１個以上のビニル基を有するイソシアネートエチルアクリレート、メタクリロイルイソシアネートなどの化合物を反応させて得られる、酸価５０〜１５０の感光性共重合体が、耐熱性、現像性等の点から好ましく使用できる。 In addition, as a resin in which an unsaturated double bond is added to a part of an acrylic resin, a compound such as the above acrylic resin, isocyanate ethyl acrylate having at least one vinyl group and an isocyanate group, or methacryloyl isocyanate is reacted. The photosensitive copolymer having an acid value of 50 to 150 can be preferably used from the viewpoints of heat resistance, developability and the like.
更に、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹脂、ポリカルボン酸グリシジルエステル、ポリオールポリグリシジルエステル、脂肪族又は脂環式エポキシ樹脂、アミンエポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ジヒドロキシベンゼン型エポキシ樹脂などのエポキシ樹脂と（メタ）アクリル酸を反応させて得られるエポキシ（メタ）アクリレート等の通常の光重合可能な樹脂等やカルド樹脂も使用できる。 Furthermore, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, Ordinary photopolymerizable resins such as epoxy (meth) acrylate obtained by reacting an epoxy resin such as a dihydroxybenzene type epoxy resin and (meth) acrylic acid, or a cardo resin can also be used.
＜重合性モノマー＞
光重合性モノマーとしては、例えば、エチレングリコール（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ヘキサンジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、グリセリンテトラ（メタ）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、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）アクリレート等が挙げられ、これらの成分は単独又は混合物として使用される。
<Polymerizable monomer>
Examples of the photopolymerizable monomer include ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol. Di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Data) acrylate, dipentaerythritol hexa (meth) acrylate and the like, these components are used alone or as a mixture.
また、各種変性（メタ）アクリレート、ウレタン（メタ）アクリレート等を用いることも可能である。中でも、二重結合当量が小さく高感度化が達成できる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）アクリレートが好適に用いられる。 Various modified (meth) acrylates, urethane (meth) acrylates, and the like can also be used. Among these, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, which have a small double bond equivalent and can achieve high sensitivity, are preferably used.
光重合性モノマーの含有量としては、黒色感光性樹脂組成物の固形分中５〜２０重量％であることが好ましく、より好ましくは１０〜１５重量％の範囲である。光重合性モノマーの含有量がこの範囲である場合、黒色感光性樹脂組成物の感度、現像速度を生産上好適な水準に調整することができる。光重合性モノマーの含有量が５重量％以下である場合、黒色感光性樹脂組成物の感度が不足する。 As content of a photopolymerizable monomer, it is preferable that it is 5 to 20 weight% in solid content of a black photosensitive resin composition, More preferably, it is the range of 10 to 15 weight%. When the content of the photopolymerizable monomer is within this range, the sensitivity and development speed of the black photosensitive resin composition can be adjusted to a level suitable for production. When the content of the photopolymerizable monomer is 5% by weight or less, the sensitivity of the black photosensitive resin composition is insufficient.
＜光重合開始剤＞
染料添加による感度低下を補うため、光重合開始剤としては高感度化を達成することができるオキシムエステル化合物を用いることが好ましい。
<Photopolymerization initiator>
In order to compensate for the decrease in sensitivity due to the addition of the dye, it is preferable to use an oxime ester compound that can achieve high sensitivity as the photopolymerization initiator.
前記オキシムエステル系化合物の具体例としては２‐（Ｏ‐ベンゾイルオキシム）‐１‐［４‐（フェニルチオ）フェニル］‐１，２‐オクタンジオン、１‐（Ｏ‐アセチルオキシム）‐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］エタノン（共にＢＡＳＦジャパン社製）等が挙げられるが、とりわけ少量添加で高感度化を達成できる下式（１）の化合物を用いることが好ましい。 Specific examples of the oxime ester compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9. -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone (both manufactured by BASF Japan Ltd.), and the like. It is preferable to use a compound.
Ｘ１は、合成の容易さ、感度、溶解性、感光性着色組成物に含有したときの保存安定性の観点から、特に好ましくはメチル基、エチル基、ｎ‐プロピル基、イソプロピル基、ｎ‐ブチル基、イソブチル基、ｔ‐ブチル基、ｎ‐アミル基、イソアミル基、ｔ‐アミル基、ｎ‐ヘキシル基、２‐エチルヘキシル基等の炭素数１０以下のアルキル基、シクロペンチル基、シクロヘキシル基等の炭素数１０以下の側鎖を有しても良い環状アルキル基、メトキシメチル基、エトキシメチル基、エトキシエチル基、２‐（１‐メトキシプロピル）基、２‐（１‐エトキシプロピル）基等の炭素数１０以下でありメチレン鎖中にエーテル結合を１個有するアルキル基である。 X 1 is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-group, from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. Such as butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group, 2-ethylhexyl group and other alkyl groups having 10 or less carbon atoms, cyclopentyl group, cyclohexyl group, etc. Such as cyclic alkyl group, methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2- (1-methoxypropyl) group, 2- (1-ethoxypropyl) group, etc. It is an alkyl group having 10 or less carbon atoms and having one ether bond in the methylene chain.
Ｘ３は、合成の容易さ、感度、溶解性、感光性着色組成物に含有したときの保存安定性の観点から、特に好ましくは水素、またはメチル基、エチル基、ｎ‐プロピル基、イソプロピル基、ｎ‐ブチル基、イソブチル基、ｔ‐ブチル基、ｎ‐アミル基、イソアミル基、ｔ‐アミル基、ｎ‐ヘキシル基等の炭素数６以下のアルキル基、シクロペンチル基、シクロヘキシル基等の炭素数６以下の環状アルキル基、メトキシメチル基、エトキシメチル基、エトキシエチル基、２‐（１‐メトキシプロピル）基、２‐（１‐エトキシプロピル）基等の炭素数６以下でありメチレン鎖中にエーテル結合を１個有するアルキル基である。 X 3 is particularly preferably hydrogen, or a methyl group, an ethyl group, an n-propyl group, or an isopropyl group from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. , N-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and the like, such as alkyl groups having 6 or less carbon atoms, cyclopentyl group, cyclohexyl group, etc. 6 or less cyclic alkyl groups, methoxymethyl groups, ethoxymethyl groups, ethoxyethyl groups, 2- (1-methoxypropyl) groups, 2- (1-ethoxypropyl) groups, etc., which have 6 or less carbon atoms and are in the methylene chain An alkyl group having one ether bond.
Ｘ６は、合成の容易さ、感度、溶解性、感光性着色組成物に含有したときの保存安定性の観点から、特に好ましくはメチル基、エチル基、ｎ‐プロピル基、イソプロピル基、ｎ‐ブチル基、イソブチル基、ｔ‐ブチル基、ｎ‐アミル基、イソアミル基、ｔ‐アミル基、ｎ‐ヘキシル基等の炭素数６以下のアルキル基、シクロペンチル基、シクロヘキシル基等の炭素数６以下の環状アルキル基、メトキシメチル基、エトキシメチル基、エトキシエチル基、２‐（１‐メトキシプロピル）基、２‐（１‐エトキシプロピル）基等の炭素数６以下でありメチレン鎖中にエーテル結合を１個有するアルキル基である。 X 6 is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-group, from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. C 6 or less alkyl group such as butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group, etc., C 6 or less carbon group such as cyclopentyl group, cyclohexyl group, etc. A cyclic alkyl group, a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2- (1-methoxypropyl) group, a 2- (1-ethoxypropyl) group, etc. having 6 or less carbon atoms and an ether bond in the methylene chain It is an alkyl group having one.
Ｘ２は、合成の容易さ、感度、溶解性、感光性着色組成物に含有したときの保存安定性の観点から、特に好ましくはメチル基、エチル基、ｎ‐プロピル基、イソプロピル基、ｎ‐ブチル基、イソブチル基、ｔ‐ブチル基、ｎ‐アミル基、イソアミル基、ｔ‐アミル基、ｎ‐ヘキシル基等の炭素数６以下のアルキル基、シクロペンチル基、シクロヘキシル基等の炭素数６以下の環状アルキル基、メトキシメチル基、エトキシメチル基、エトキシエチル基、２‐（１‐メトキシプロピル）基、２‐（１‐エトキシプロピル）基等の炭素数６以下でありメチレン鎖中にエーテル結合を１個有するアルキル基である。 X 2 is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-group, from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. C 6 or less alkyl group such as butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group, etc., C 6 or less carbon group such as cyclopentyl group, cyclohexyl group, etc. A cyclic alkyl group, a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2- (1-methoxypropyl) group, a 2- (1-ethoxypropyl) group, etc. having 6 or less carbon atoms and an ether bond in the methylene chain It is an alkyl group having one.
Ｘ４及びＸ５は、合成の容易さ、感度、溶解性、感光性着色組成物に含有したときの保存安定性の観点から、特に好ましくは水素、またはメチル基、エチル基、ｎ‐プロピル基、イソプロピル基、ｎ‐ブチル基、イソブチル基、ｔ‐ブチル基、ｎ‐アミル基、イソアミル基、ｔ‐アミル基、ｎ‐ヘキシル基等の炭素数６以下のアルキル基である。 X 4 and X 5 are particularly preferably hydrogen, a methyl group, an ethyl group, or an n-propyl group from the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. , An isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group, an n-hexyl group and the like.
化式（１）で表される光重合開始剤の具体例としては、例えば化式（２）の化合物が挙げられる。 Specific examples of the photopolymerization initiator represented by the chemical formula (1) include a compound represented by the chemical formula (2).
本発明の黒色感光性樹脂組成物には、化式（１）で表される光重合開始剤と共に、他の光重合開始剤を併用することができる。他の光重合開始剤としては、４‐フェノキシジクロロアセトフェノン、４‐ｔ‐ブチル‐ジクロロアセトフェノン、ジエトキシアセトフェノン、１‐（４‐イソプロピルフェニル）‐２‐ヒドロキシ‐２‐メチルプロパン‐１‐オン、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‐モルフォリノプロパン‐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）‐ブタン‐１‐オン等のアセトフェノン系化合物、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジメチルケタール等のベンゾイン系化合物、ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４‐フェニルベンゾフェノン、ヒドロキシベンゾフェノン、アクリル化ベンゾフェノン、４‐ベンゾイル‐４’‐メチルジフェニルサルファイド、３，３’，４，４’‐テトラ（ｔ‐ブチルパーオキシカルボニル）ベンゾフェノン等のベンゾフェノン系化合物、チオキサントン、２‐クロルチオキサントン、２‐メチルチオキサントン、イソプロピルチオキサントン、２，４‐ジイソプロピルチオキサントン、２，４‐ジエチルチオキサントン等のチオキサントン系化合物、２，４，６‐トリクロロ‐ｓ‐トリアジン、２‐フェニル‐４，６‐ビス（トリクロロメチル）‐ｓ‐トリアジン、２‐（ｐ‐メトキシフェニル）‐４，６‐ビス（トリクロロメチル）‐ｓ‐トリアジン、２‐（ｐ‐トリル）‐４，６‐ビス（トリクロロメチル）‐ｓ‐トリアジン、２‐ピペロニル‐４，６‐ビス（トリクロロメチル）‐ｓ‐トリアジン、２，４‐ビス（トリクロロメチル）‐６‐スチリル‐ｓ‐トリアジン、２‐（ナフト‐１‐イル）‐４，６‐ビス（トリクロロメチル）‐ｓ‐トリアジン、２‐（４‐メトキシ‐ナフト‐１‐イル）‐４，６‐ビス（トリクロロメチル）‐ｓ‐トリアジン、２，４‐トリクロロメチル‐（ピペロニル）‐６‐トリアジン、２，４‐トリクロロメチル（４’‐メトキシスチリル）‐６‐トリアジン等のトリアジン系化合物、ビス（２，４，６‐トリメチルベンゾイル）フェニルホスフィンオキサイド、２，４，６‐トリメチルベンゾイルジフェニルホスフィンオキサイド等のホスフィン系化合物、９，１０‐フェナンスレンキノン、カンファーキノン、エチルアントラキノン等のキノン系化合物、ボレート系化合物、カルバゾール系化合物、イミダゾール系化合物、チタノセン系化合物等が用いられる。これらの光重合開始剤は１種または必要に応じて任意の比率で２種以上混合して用いることができる。他の光重合開始剤の含有量は、前記黒色感光性樹脂組成物の固形分中０．１〜５重量％であることが好ましく、より好ましくは０．２〜１重量％の範囲である。 In the black photosensitive resin composition of the present invention, other photopolymerization initiators can be used in combination with the photopolymerization initiator represented by the chemical formula (1). Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Acetophenone compounds such as butan-1-one, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzene Benzophenone compounds such as zophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2- Thioxanthone compounds such as chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2 -Piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6- Triazines such as triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine compounds such as oxide, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquino Quinone compounds such as borate compounds, carbazole compounds, imidazole compounds, titanocene compounds and the like. These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. The content of the other photopolymerization initiator is preferably 0.1 to 5% by weight, more preferably 0.2 to 1% by weight in the solid content of the black photosensitive resin composition.
＜溶剤＞
溶剤としては、メタノール、エタノール、エチルセロソルブ、エチルセロソルブアセテート、ジグライム、シクロヘキサノン、エチルベンゼン、キシレン、酢酸イソアミル、酢酸ｎアミル、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、プロピレングリコールモノエチルエーテルアセテート、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチ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エチルエーテルアセテート、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテルアセテート、液体ポリエチレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノエチルエーテルアセテート、乳酸エステル、エチルエトキシプロピオネートなどが挙げられる。
<Solvent>
Solvents include methanol, ethanol, ethyl cellosolve, ethyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n amyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono Ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, triethylene glycol, Liethylene glycol monomethyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monoethyl ether acetate, lactic acid ester, ethyl ethoxypropionate and the like.
＜その他添加剤＞
本発明の黒色感光性樹脂組成物には、更に塗布性を向上させるための界面活性剤、基板との密着性を向上させるためのシランカップリング剤等を併用することができる。
<Other additives>
The black photosensitive resin composition of the present invention can be used in combination with a surfactant for further improving the coating property, a silane coupling agent for improving the adhesion to the substrate, and the like.
上記界面活性剤としては、パーフルオロアルキルリン酸エステル、パーフルオロアルキルカルボン酸塩等のフッ素界面活性剤、高級脂肪酸アルカリ塩、アルキルスルホン酸塩、アルキル硫酸塩等のアニオン系界面活性剤、高級アミンハロゲン酸塩、第四級アンモニウム塩等のカチオン系界面活性剤、ポリエチレングリコールアルキルエーテル、ポリエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、脂肪酸モノグリセリド等の非イオン界面活性剤、両性界面活性剤、シリコーン系界面活性剤等の界面活性剤を用いることができ、これらは組み合わせて用いてもよい。 Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.
シランカップリング剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン等のビニルシラン類、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‐グリシドキシプロピルジメトキシシラン等のエポキシシラン類、３‐メタクリロキシプロピルメチルジメトキシシラン、３‐メタクリロキシプロピルトリメトキシシラン等のメタクリルシラン類、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、３‐アミノプロピルトリメトキシシラン、Ｎ‐フェニル‐３‐アミノプロピルトリメトキシシラン類等のアミノシラン類、３‐メルカプトプロピルメチルジメトキシシラン、３‐メルカプトプロピルトリメトキシシラン等のメルカプトシラン類、３‐イソシアネートプロピルトリエトキシシラン等のイソシアネートシラン類等が挙げられる。（ブラックマトリックス）
本発明のブラックマトリックスは、前記黒色感光性樹脂組成物を用いて形成され、膜厚１．０μｍ当たりの光学濃度（ＯＤ値）が４．０／μｍ以上であり、体積抵抗率が１．０×１０１２Ω・ｃｍ以上であることを特徴とする。本発明のブラックマトリックスは１．０μｍ程度の薄膜においてもＯＤ値が高いため、十分な遮光性能を保ちつつかつカラーフィルタの平坦性を損ねることがない。また、体積抵抗率が１．０×１０１２Ω・ｃｍ以上と高い絶縁性能を有するため、ブラックマトリックスと透明電極が導通することにより生じる液晶の配向不良を防ぐことができる。
As silane coupling agents, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, epoxy silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyldimethoxysilane, Methacrylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N- Aminosilanes such as phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrieth Isocyanate silanes such as Shishiran like. (Black matrix)
The black matrix of the present invention is formed using the black photosensitive resin composition, has an optical density (OD value) per film thickness of 1.0 μm of 4.0 / μm or more, and has a volume resistivity of 1.0. × 1012 Ω · cm or more. Since the black matrix of the present invention has a high OD value even in a thin film of about 1.0 μm, it does not impair the flatness of the color filter while maintaining sufficient light shielding performance. In addition, since the volume resistivity is as high as 1.0 × 10 12 Ω · cm or higher, it is possible to prevent liquid crystal alignment defects caused by conduction between the black matrix and the transparent electrode.
ブラックマトリックスを形成する基板としては、可視光に対してある程度の透過率を有するものが好ましく、より好ましくは８０％以上の透過率を有するものが好ましい。例えば、石英ガラス、ホウケイ酸ガラス、アルミノケイ酸ガラスなどの各種ガラス基板、ポリエステル系樹脂、ポリオレフィン系樹脂などの各種プラスチック基板が挙げられる。 As a board | substrate which forms a black matrix, what has a certain amount of transmittance | permeability with respect to visible light is preferable, More preferably, what has the transmittance | permeability of 80% or more is preferable. Examples thereof include various glass substrates such as quartz glass, borosilicate glass, and aluminosilicate glass, and various plastic substrates such as polyester resin and polyolefin resin.
ブラックマトリックスの形成は以下のようにして行う。基板に、スプレーコートやスピンコート、スリットコート、ロールコート等の塗布方法により、前記黒色感光性樹脂組成物の塗膜を形成する。 The black matrix is formed as follows. A coating film of the black photosensitive resin composition is formed on the substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating.
ブラックマトリックスの膜厚は０．８〜１．２μｍであることが好ましく、より好ましくは０．９〜１．１μｍである。ブラックマトリックスの膜厚が０．８μｍ以下である場合、遮光性が不足する。一方、ブラックマトリックスの膜厚が１．２μｍ以上である場合、カラーフィルタの平坦性が損なわれ液晶の配向不良が発生しやすくなる。 The film thickness of the black matrix is preferably 0.8 to 1.2 μm, more preferably 0.9 to 1.1 μm. When the thickness of the black matrix is 0.8 μm or less, the light shielding property is insufficient. On the other hand, when the film thickness of the black matrix is 1.2 μm or more, the flatness of the color filter is impaired, and liquid crystal alignment defects are likely to occur.
減圧乾燥、プレベーク処理により塗膜中の残留溶剤を除去した後、所定のパターンを有するフォトマスクを介して露光する。露光光源としては、超高圧水銀灯、キセノン灯、カーボンアーク灯等従来公知の光源を用いることができる。 After removing the residual solvent in the coating film by drying under reduced pressure and pre-baking treatment, exposure is performed through a photomask having a predetermined pattern. As the exposure light source, a conventionally known light source such as an ultrahigh pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used.
次に、アルカリ性水溶液からなる現像液を用いて現像を行う。このアルカリ性水溶液からなる現像液の例としては、炭酸カリウム水溶液、炭酸ナトリウム水溶液、または炭酸水
素ナトリウム水溶液、更に、これらの水溶液に適当な海面活性剤などを加えたものが挙げられる。現像後、水洗、乾燥してベークすることにより、基板上に所定のブラックマトリックスパターンを形成することができる。
Next, it develops using the developing solution which consists of alkaline aqueous solution. Examples of the developer comprising the alkaline aqueous solution include a potassium carbonate aqueous solution, a sodium carbonate aqueous solution, or a sodium hydrogen carbonate aqueous solution, and those obtained by adding an appropriate sea surface activator to these aqueous solutions. A predetermined black matrix pattern can be formed on the substrate by washing with water, drying and baking after development.
＜カラーフィルタ＞
本発明のカラーフィルタは、前記ブラックマトリックスを具備することを特徴とする。
本発明のカラーフィルタはブラックマトリックスが薄膜であるため、着色画素を形成した後の平坦性が良好である。このため、液晶表示装置に用いた際に液晶の配向不良を生じることが無く良好な表示特性が得られる。
<Color filter>
The color filter of the present invention comprises the black matrix.
In the color filter of the present invention, since the black matrix is a thin film, the flatness after forming colored pixels is good. For this reason, when used in a liquid crystal display device, good display characteristics can be obtained without causing liquid crystal alignment failure.
本発明のカラーフィルタの形成は以下のようにして行う。ブラックマトリックスを形成した基板上に、カラーフィルタの各着色画素に対応する色材を含有した着色感光性樹脂組成物の塗膜を形成する。乾燥後、ブラックマトリックスの開口部に対応したパターンを有するフォトマスクを介して露光する。現像処理により未露光部を除去した後、ベークすることでブラックマトリックスの開口部に着色画素を形成することが出来る。一連の操作を例えば赤色、緑色、青色色材を含有した着色感光性樹脂組成物を用いて行うことにより、赤色、緑色、青色画素を有するカラーフィルタを製造することができる。 The color filter of the present invention is formed as follows. On the substrate on which the black matrix is formed, a coating film of a colored photosensitive resin composition containing a color material corresponding to each colored pixel of the color filter is formed. After drying, exposure is performed through a photomask having a pattern corresponding to the opening of the black matrix. After the unexposed portion is removed by development processing, the colored pixels can be formed in the opening portion of the black matrix by baking. By performing a series of operations using a colored photosensitive resin composition containing, for example, red, green, and blue color materials, a color filter having red, green, and blue pixels can be manufactured.
以下、実施例等を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.
次のようにして実施例、比較例に用いた黒色感光性樹脂組成物Ｎｏ．１〜Ｎｏ．９を調整した。色材の配合比率を表１に示す。 The black photosensitive resin composition No. used in the examples and comparative examples as follows. 1-No. 9 was adjusted. Table 1 shows the blending ratio of the color materials.
＜黒色感光性樹脂組成物Ｎｏ．１の調整＞
ビスフェノールフルオレン型エポキシ樹脂 ３．６１ｇ
（新日鐵化学社製「Ｖ２５９‐ＭＥ」固形分５６．１％）
ジペンタエリスリトールペンタ／ヘキサアクリレート混合物 １．０５ｇ
（日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＨＡ」）
光重合開始剤 化式（２） ０．７０ｇ
カーボンブラック ３２．３１ｇ
プロピレングリコールモノメチルアセテート分散液
（固形分２６．０％、固形分中の顔料濃度７５．０重量％）
Ｃ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ１２４ ９．１３ｇ
（クラリアントジャパン社製「Ｓａｖｉｎｙｌ Ｆｉｒｅ Ｒｅｄ ３ＧＬＳ」）
シクロヘキサノン溶液（固形分１０．０％）
Ｃ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ８７ ３６．２１ｇ
（有本化学工業社製「Ｐｌａｓｔ Ｂｌｕｅ ８５８０」）
シクロヘキサノン溶液（固形分２．５％）
プロピレングリコールモノメチルエーテルアセテート １６．９９ｇを加えてよく攪拌し、
黒色感光性樹脂組成物Ｎｏ．１の １００．００ｇ
（固形分１４．０％、カーボンブラック顔料濃度４５．０重量％、
染料濃度１３．０重量％）を得た。
<Black photosensitive resin composition No. Adjustment of 1>
Bisphenol fluorene type epoxy resin 3.61g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1%)
Dipentaerythritol penta / hexaacrylate mixture 1.05g
(“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator Chemical formula (2) 0.70 g
Carbon black 32.31g
Propylene glycol monomethyl acetate dispersion (solid content: 26.0%, pigment concentration in solid content: 75.0% by weight)
C. I. SolventRed124 9.13g
("Savinyl Fire Red 3GLS" manufactured by Clariant Japan)
Cyclohexanone solution (solid content 10.0%)
C. I. SolventBlue87 36.21g
("Plast Blue 8580" manufactured by Arimoto Chemical Industry Co., Ltd.)
Cyclohexanone solution (solid content 2.5%)
Add 16.99 g of propylene glycol monomethyl ether acetate and stir well.
Black photosensitive resin composition No. 1 of 100.00g
(Solid content 14.0%, carbon black pigment concentration 45.0% by weight,
A dye concentration of 13.0% by weight) was obtained.
＜黒色感光性樹脂組成物Ｎｏ．２の調整＞
ビスフェノールフルオレン型エポキシ樹脂 ２．７１ｇ
（新日鐵化学社製「Ｖ２５９‐ＭＥ」固形分５６．１％）
ジペンタエリスリトールペンタ／ヘキサアクリレート混合物 １．０５ｇ
日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＨＡ」）
光重合開始剤 化式（２） ０．７０ｇカーボンブラック ３５．９０ｇ
プロピレングリコールモノメチルアセテート分散液
(固形分２６．０％、固形分中の顔料濃度７５．０重量％)
Ｃ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ１２４ ７．００ｇ
（クラリアントジャパン社製「Ｓａｖｉｎｙｌ Ｆｉｒｅ Ｒｅｄ ３ＧＬＳ」）
シクロヘキサノン溶液（固形分１０．０％）
Ｃ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ８７ ２７．９９ｇ
（有本化学工業社製「Ｐｌａｓｔ Ｂｌｕｅ ８５８０」）
シクロヘキサノン溶液（固形分２．５％）
プロピレングリコールモノメチルエーテルアセテート ２４．６５ｇを加えてよく攪拌し、
黒色感光性樹脂組成物Ｎｏ．２ １００ｇ（固形分１４．０％、カーボンブラック顔料濃度５０．０重量％、染料濃度１０．０重量％）を得た。
<Black photosensitive resin composition No. Adjustment of 2>
Bisphenol fluorene type epoxy resin 2.71 g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1%)
Dipentaerythritol penta / hexaacrylate mixture 1.05g
“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator Chemical formula (2) 0.70 g Carbon black 35.90 g
Propylene glycol monomethyl acetate dispersion
(Solid content 26.0%, pigment concentration in solid content 75.0% by weight)
C. I. SolventRed124 7.00g
("Savinyl Fire Red 3GLS" manufactured by Clariant Japan)
Cyclohexanone solution (solid content 10.0%)
C. I. SolventBlue87 27.99g
("Plast Blue 8580" manufactured by Arimoto Chemical Industry Co., Ltd.)
Cyclohexanone solution (solid content 2.5%)
Add 24.65 g of propylene glycol monomethyl ether acetate and stir well.
Black photosensitive resin composition No. 2 100 g (solid content 14.0%, carbon black pigment concentration 50.0% by weight, dye concentration 10.0% by weight) was obtained.
＜黒色感光性樹脂組成物Ｎｏ．３の調整＞
ビスフェノールフルオレン型エポキシ樹脂 ４．５４ｇ
（新日鐵化学社製「Ｖ２５９‐ＭＥ」固形分５６．１％）
ジペンタエリスリトールペンタ／ヘキサアクリレート混合物 １．０５ｇ
（日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＨＡ」）
光重合開始剤 化式（２） ０．７０ｇカーボンブラック ２８．７２ｇ
プロピレングリコールモノメチルアセテート分散液(固形分２６．０％、
固形分中の顔料濃度７５．０重量％)
Ｃ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ１２４ １１．２０ｇ
（クラリアントジャパン社製「Ｓａｖｉｎｙｌ Ｆｉｒｅ Ｒｅｄ ３ＧＬＳ」）
シクロヘキサノン溶液（固形分１０．０％）
Ｃ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ８７ ４４．７８ｇ
（有本化学工業社製「Ｐｌａｓｔ Ｂｌｕｅ ８５８０」）
シクロヘキサノン溶液（固形分２．５％）
プロピレングリコールモノメチルエーテルアセテート ９．０１ｇを加えてよく攪拌し、
黒色感光性樹脂組成物Ｎｏ．３ １００ｇ（固形分１４．０％、カーボンブラック顔料濃度４０．０重量％、染料濃度１６．０重量％）を得た。
<Black photosensitive resin composition No. Adjustment of 3>
Bisphenol fluorene type epoxy resin 4.54g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1%)
Dipentaerythritol penta / hexaacrylate mixture 1.05g
(“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator Chemical formula (2) 0.70 g Carbon black 28.72 g
Propylene glycol monomethyl acetate dispersion (solid content 26.0%,
(Pigment concentration in solid content: 75.0% by weight)
C. I. SolventRed124 11.20g
("Savinyl Fire Red 3GLS" manufactured by Clariant Japan)
Cyclohexanone solution (solid content 10.0%)
C. I. SolventBlue87 44.78g
("Plast Blue 8580" manufactured by Arimoto Chemical Industry Co., Ltd.)
Cyclohexanone solution (solid content 2.5%)
Add 9.01 g of propylene glycol monomethyl ether acetate and stir well.
Black photosensitive resin composition No. 3 100 g (solid content 14.0%, carbon black pigment concentration 40.0% by weight, dye concentration 16.0% by weight) was obtained.
＜黒色感光性樹脂組成物Ｎｏ．４の調整＞
ビスフェノールフルオレン型エポキシ樹脂 ３．６１ｇ
（新日鐵化学社製「Ｖ２５９‐ＭＥ」固形分５６．１％）
ジペンタエリスリトールペンタ／ヘキサアクリレート混合物 １．０５ｇ
（日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＨＡ」）
光重合開始剤 化式（２） ０．７０ｇカーボンブラック ３２．３１ｇ
のプロピレングリコールモノメチルアセテート分散液
(固形分２６．０％、固形分中の顔料濃度７５．０重量％)
Ｃ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ８３ ９．１３ｇ
（保土ヶ谷化学工業社製「Ａｉｚｅｎ Ｓｐｉｌｏｎ Ｒｅｄ ＢＥＨ
Ｓｐｅｃｉａｌ」）のシクロヘキサノン溶液（固形分１０．０％）
Ｃ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ８７ ３６．２１ｇ
（有本化学工業社製「Ｐｌａｓｔ Ｂｌｕｅ ８５８０」）
シクロヘキサノン溶液（固形分２．５％）
プロピレングリコールモノメチルエーテルアセテート １６．９９ｇを加えてよく攪拌し、
黒色感光性樹脂組成物Ｎｏ．４ １００ｇ（固形分１４．０％、カーボンブラック顔料濃度４５．０重量％、染料濃度１３．０重量％）を得た。
<Black photosensitive resin composition No. Adjustment of 4>
Bisphenol fluorene type epoxy resin 3.61 g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1%)
Dipentaerythritol penta / hexaacrylate mixture 1.05g
(“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator Chemical formula (2) 0.70 g Carbon black 32.31 g
Propylene glycol monomethyl acetate dispersion
(Solid content 26.0%, pigment concentration in solid content 75.0% by weight)
C. I. SolventRed83 9.13g
("Aizen Spiron Red BEH made by Hodogaya Chemical Co., Ltd."
Special ") cyclohexanone solution (solid content 10.0%)
C. I. SolventBlue87 36.21g
("Plast Blue 8580" manufactured by Arimoto Chemical Industry Co., Ltd.)
Cyclohexanone solution (solid content 2.5%)
Add 16.99 g of propylene glycol monomethyl ether acetate and stir well.
Black photosensitive resin composition No. 4 100 g (solid content 14.0%, carbon black pigment concentration 45.0% by weight, dye concentration 13.0% by weight) was obtained.
＜黒色感光性樹脂組成物Ｎｏ．５の調整＞
ビスフェノールフルオレン型エポキシ樹脂 ３．５９ｇ
（新日鐵化学社製「Ｖ２５９‐ＭＥ」固形分５６．１％）
ジペンタエリスリトールペンタ／ヘキサアクリレート混合物 １．０５ｇ
（日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＨＡ」）
光重合開始剤 化式（２） ０．７０ｇカーボンブラック ３２．３１ｇ
プロピレングリコールモノメチルアセテート分散液
(固形分２６．０％、固形分中の顔料濃度７５．０重量％)
Ｃ．Ｉ．ＳｏｌｖｅｎｔＹｅｌｌｏｗ８３ ９．１３ｇ
（クラリアントジャパン社製「Ｓａｖｉｎｙｌ Ｙｅｌｌｏｗ ＲＬＳＮ」）
シクロヘキサノン溶液（固形分１０．０％）
Ｃ．Ｉ．ＳｏｌｖｅｎｔＶｉｏｌｅｔ３６ １８．２６ｇ
（日本化薬社製「Ｋａｙｓｅｔ Ｖｉｏｌｅｔ Ａ‐Ｒ」）
シクロヘキサノン溶液（固形分５．０％）
プロピレングリコールモノメチルエーテルアセテート ３４．９６ｇを加えてよく攪拌し、
黒色感光性樹脂組成物Ｎｏ．５ １００ｇ（固形分１４．０％、カーボンブラック顔料濃度４５．０重量％、染料濃度１３．０重量％）を得た。
<Black photosensitive resin composition No. Adjustment of 5>
Bisphenol fluorene type epoxy resin 3.59g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1%)
Dipentaerythritol penta / hexaacrylate mixture 1.05g
(“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator Chemical formula (2) 0.70 g Carbon black 32.31 g
Propylene glycol monomethyl acetate dispersion
(Solid content 26.0%, pigment concentration in solid content 75.0% by weight)
C. I. Solvent Yellow 83 9.13g
("Savinyl Yellow RLSN" manufactured by Clariant Japan)
Cyclohexanone solution (solid content 10.0%)
C. I. SolventViolet 36 18.26g
(“Kayset Violet AR” manufactured by Nippon Kayaku Co., Ltd.)
Cyclohexanone solution (solid content 5.0%)
Add 34.96 g of propylene glycol monomethyl ether acetate and stir well.
Black photosensitive resin composition No. 5 100 g (solid content 14.0%, carbon black pigment concentration 45.0 wt%, dye concentration 13.0 wt%) was obtained.
＜黒色感光性樹脂組成物Ｎｏ．６の調整＞
ビスフェノールフルオレン型エポキシ樹脂 ４．８４ｇ
（新日鐵化学社製「Ｖ２５９‐ＭＥ」固形分５６．１％）
ジペンタエリスリトールペンタ／ヘキサアクリレート混合物 ０．９８ｇ
（日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＨＡ」）
光重合開始剤 化式（２） ０．６５ｇカーボンブラック ２３．３３ｇ
のプロピレングリコールモノメチルアセテート分散液
(固形分２６．０％、固形分中の顔料濃度７５．０重量％)
Ｃ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ１２４ １２．９６ｇ
（クラリアントジャパン社製「Ｓａｖｉｎｙｌ Ｆｉｒｅ Ｒｅｄ ３ＧＬＳ」）
シクロヘキサノン溶液（固形分１０．０％）
Ｃ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ８７ ５１．８５ｇ
（有本化学工業社製「Ｐｌａｓｔ Ｂｌｕｅ ８５８０」）
シクロヘキサノン溶液（固形分２．５％）
プロピレングリコールモノメチルエーテルアセテート ５．３９ｇを加えてよく攪拌し、
黒色感光性樹脂組成物Ｎｏ．６ １００ｇ（固形分１３．０％、カーボンブラック顔料濃度３５．０重量％、染料濃度２０．０重量
％）を得た。
<Black photosensitive resin composition No. Adjustment of 6>
Bisphenol fluorene type epoxy resin 4.84g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1%)
Dipentaerythritol penta / hexaacrylate mixture 0.98g
(“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator Chemical formula (2) 0.65 g Carbon black 23.33 g
Propylene glycol monomethyl acetate dispersion
(Solid content 26.0%, pigment concentration in solid content 75.0% by weight)
C. I. SolventRed124 12.96g
("Savinyl Fire Red 3GLS" manufactured by Clariant Japan)
Cyclohexanone solution (solid content 10.0%)
C. I. SolventBlue87 51.85g
("Plast Blue 8580" manufactured by Arimoto Chemical Industry Co., Ltd.)
Cyclohexanone solution (solid content 2.5%)
Add 5.39 g of propylene glycol monomethyl ether acetate and stir well.
Black photosensitive resin composition No. 6 100 g (solid content 13.0%, carbon black pigment concentration 35.0% by weight, dye concentration 20.0% by weight) was obtained.
＜黒色感光性樹脂組成物Ｎｏ．７の調整＞
ビスフェノールフルオレン型エポキシ樹脂 １．５４ｇ
（新日鐵化学社製「Ｖ２５９‐ＭＥ」固形分５６．１％）
ジペンタエリスリトールペンタ／ヘキサアクリレート混合物 １．０５ｇ
（日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＨＡ」）
光重合開始剤 化式（２） ０．７０ｇカーボンブラック ３９．４９ｇ
プロピレングリコールモノメチルアセテート分散液
(固形分２６．０％固形分中の顔料濃度７５．０重量％)
Ｃ．Ｉ．ＳｏｌｖｅｎｔＲｅｄ１２４ ５．６２ｇ
（クラリアントジャパン社製「Ｓａｖｉｎｙｌ Ｆｉｒｅ Ｒｅｄ ３ＧＬＳ」）
シクロヘキサノン溶液（固形分１０．０％）
Ｃ．Ｉ．ＳｏｌｖｅｎｔＢｌｕｅ８７ ２２．３２ｇ
（有本化学工業社製「Ｐｌａｓｔ Ｂｌｕｅ ８５８０」）
シクロヘキサノン溶液（固形分２．５％）
プロピレングリコールモノメチルエーテルアセテート ２９．２８ｇを加えてよく攪拌し、
黒色感光性樹脂組成物Ｎｏ．７ １００ｇ（固形分１４．０％、カーボンブラック顔料濃度５５．０重量％、染料濃度８．０重量％）を得た。
<Black photosensitive resin composition No. 7 adjustment>
Bisphenol fluorene type epoxy resin 1.54g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1%)
Dipentaerythritol penta / hexaacrylate mixture 1.05g
(“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator Chemical formula (2) 0.70 g Carbon black 39.49 g
Propylene glycol monomethyl acetate dispersion
(Pigment concentration in solid content 26.0% solid content 75.0% by weight)
C. I. SolventRed124 5.62g
("Savinyl Fire Red 3GLS" manufactured by Clariant Japan)
Cyclohexanone solution (solid content 10.0%)
C. I. SolventBlue87 22.32g
("Plast Blue 8580" manufactured by Arimoto Chemical Industry Co., Ltd.)
Cyclohexanone solution (solid content 2.5%)
Add 29.28 g of propylene glycol monomethyl ether acetate and stir well.
Black photosensitive resin composition No. 7 100 g (solid content 14.0%, carbon black pigment concentration 55.0% by weight, dye concentration 8.0% by weight) was obtained.
＜黒色感光性樹脂組成物Ｎｏ．８の調整＞
ビスフェノールフルオレン型エポキシ樹脂 ４．５３ｇ
（新日鐵化学社製「Ｖ２５９‐ＭＥ」固形分５６．１％）
ジペンタエリスリトールペンタ／ヘキサアクリレート混合物 １．０５ｇ
（日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＨＡ」）
光重合開始剤 化式（２） ０．７０ｇカーボンブラック ３７．３３ｇ
プロピレングリコールモノメチルアセテート分散液
(固形分２６．０％、固形分中の顔料濃度７５．０重量％)
プロピレングリコールモノメチルエーテルアセテート ５６．４２ｇを加えてよく攪拌し、
黒色感光性樹脂組成物Ｎｏ．８ １００ｇ（固形分１４．０％、カーボンブラック顔料濃度５２．０重量％）を得た。
<Black photosensitive resin composition No. Adjustment of 8>
Bisphenol fluorene type epoxy resin 4.53g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1%)
Dipentaerythritol penta / hexaacrylate mixture 1.05g
(“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator Chemical formula (2) 0.70 g Carbon black 37.33 g
Propylene glycol monomethyl acetate dispersion
(Solid content 26.0%, pigment concentration in solid content 75.0% by weight)
Add 56.42 g of propylene glycol monomethyl ether acetate and stir well.
Black photosensitive resin composition No. 8 100 g (solid content 14.0%, carbon black pigment concentration 52.0% by weight) was obtained.
＜黒色感光性樹脂組成物Ｎｏ．９の調整＞
ビスフェノールフルオレン型エポキシ樹脂 ２．２５ｇ
（新日鐵化学社製「Ｖ２５９‐ＭＥ」固形分５６．１％）
ジペンタエリスリトールペンタ／ヘキサアクリレート混合物 １．０５ｇ
（日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＨＡ」）
光重合開始剤 化式（２） ０．７０ｇカーボンブラック ３２．３１ｇ
プロピレングリコールモノメチルアセテート分散液
(固形分２６．０％、固形分中の顔料濃度７５．０重量％)
Ｃ．Ｉ．ＰｉｇｍｅｎｔＲｅｄ２５４ ６．４６ｇ
プロピレングリコールモノメチルアセテート分散液
（固形分２０．０％、固形分中の顔料濃度７０．０重量％）
Ｃ．Ｉ．ＰｉｇｍｅｎｔＢｌｕｅ１５：６ ６．４６ｇ
プロピレングリコールモノメチルアセテート分散液
（固形分２０．０％、固形分中の顔料濃度７０．０重量％）
プロピレングリコールモノメチルエーテルアセテート ５０．７８ｇを加えてよく攪拌し、
黒色感光性樹脂組成物Ｎｏ．９ １００ｇ（固形分１４．０％、カーボンブラック顔料濃度４５．０重量％、赤色／青色顔料濃度１３．０重量％）を得た。
<Black photosensitive resin composition No. 9 adjustment>
Bisphenol fluorene type epoxy resin 2.25g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1%)
Dipentaerythritol penta / hexaacrylate mixture 1.05g
(“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator Chemical formula (2) 0.70 g Carbon black 32.31 g
Propylene glycol monomethyl acetate dispersion
(Solid content 26.0%, pigment concentration in solid content 75.0% by weight)
C. I. PigmentRed254 6.46g
Propylene glycol monomethyl acetate dispersion (solid content 20.0%, pigment concentration in solid content 70.0% by weight)
C. I. PigmentBlue 15: 6 6.46g
Propylene glycol monomethyl acetate dispersion (solid content 20.0%, pigment concentration in solid content 70.0% by weight)
Add 50.78 g of propylene glycol monomethyl ether acetate and stir well.
Black photosensitive resin composition No. 9 100 g (solid content 14.0%, carbon black pigment concentration 45.0 wt%, red / blue pigment concentration 13.0 wt%) was obtained.
＜ブラックマトリックスの形成＞
＜ブラックマトリックス基板１ａ〜９ａの作製＞
ガラス基板（コーニング社製「ＥＡＧＬＥ ＸＧ」）上にスピンコート法により、上記黒色感光性樹脂組成物Ｎｏ．１の塗膜を形成した。乾燥後、９０℃のホットプレートで１分間プリベイクした。次に、超高圧水銀ランプ（照度２６ｍＷ/ｃｍ２）を用いて黒色感光性樹脂組成物の塗膜に紫外光を照射した。露光後、２．５重量％炭酸ナトリウム水溶液で現像し、２００℃のクリーンオーブンで２０分間ベークすることでブラックマトリックス基板１ａを作製した。同様の操作を黒色感光性樹脂組成物Ｎｏ．２〜Ｎｏ．９を用いて行い、ブラックマトリックス基板２ａ〜９ａを作製した。
<Formation of black matrix>
<Preparation of Black Matrix Substrates 1a-9a>
The above black photosensitive resin composition No. 1 was spin-coated on a glass substrate (“EAGLE XG” manufactured by Corning). 1 coating film was formed. After drying, it was pre-baked on a hot plate at 90 ° C. for 1 minute. Next, the ultraviolet light was irradiated to the coating film of the black photosensitive resin composition using the ultra high pressure mercury lamp (illuminance 26mW / cm < 2 >). After the exposure, development was performed with a 2.5 wt% aqueous sodium carbonate solution, and baking was performed in a clean oven at 200 ° C. for 20 minutes to prepare a black matrix substrate 1a. The same operation was repeated for the black photosensitive resin composition No. 2-No. 9, black matrix substrates 2a to 9a were produced.
＜ブラックマトリックス基板１ｂ〜７ｂの作製＞
ガラス基板（コーニング社製「ＥＡＧＬＥ ＸＧ」）上に蒸着法により、金属クロム薄膜を形成した。ＵＶ洗浄装置を用いて乾式洗浄した後、上記クロム基板上に黒色感光性樹脂組成物Ｎｏ．１の塗膜を形成した。乾燥後、９０℃のホットプレートで１分間プリベイクした。次に、超高圧水銀ランプ（照度２６ｍＷ/ｃｍ２）を用いて一部クロムが露出するように露光、現像し、２００℃のクリーンオーブンで２０分間ベークすることでクロム電極を有するブラックマトリックス基板を得た。該基板上に蒸着法によりアルミ電極を形成し、クロム電極、アルミ電極にブラックマトリックスがサンドイッチされた構造を有するブラックマトリックス基板１ｂを得た。同様の操作を黒色感光性樹脂組成物Ｎｏ．２〜Ｎｏ．９を用いて行い、ブラックマトリックス基板２ｂ〜９ｂを作製した。
<Preparation of Black Matrix Substrates 1b-7b>
A metal chromium thin film was formed on a glass substrate (Corning “EAGLE XG”) by vapor deposition. After dry-cleaning using a UV cleaning apparatus, the black photosensitive resin composition No. 1 was formed on the chromium substrate. 1 coating film was formed. After drying, it was pre-baked on a hot plate at 90 ° C. for 1 minute. Next, using a super high pressure mercury lamp (illuminance of 26 mW / cm 2 ), exposure and development are performed so that the chromium is partially exposed, and baking is performed in a clean oven at 200 ° C. for 20 minutes to form a black matrix substrate having a chromium electrode. Obtained. An aluminum electrode was formed on the substrate by vapor deposition to obtain a black matrix substrate 1b having a structure in which a black matrix was sandwiched between a chromium electrode and an aluminum electrode. The same operation was repeated for the black photosensitive resin composition No. 2-No. 9, black matrix substrates 2b to 9b were produced.
得られたブラックマトリックス基板１ａ〜９ａについて外観、ＯＤ値の評価を行った。また、ブラックマトリックス基板１ｂ〜９ｂについて体積抵抗率の評価を行った。結果を表1に示す。 Appearance and OD value of the obtained black matrix substrates 1a to 9a were evaluated. Further, the volume resistivity of the black matrix substrates 1b to 9b was evaluated. The results are shown in Table 1.
＜外観評価＞
ブラックマトリックス基板１ａ〜７ａを光学顕微鏡で観察し、外観異常がなかったものを○、外観異常が発生したものを○とした。
<Appearance evaluation>
The black matrix substrates 1a to 7a were observed with an optical microscope, and those with no appearance abnormality were marked with ◯ and those with appearance abnormality were marked with ◯.
＜ＯＤ値評価＞
ブラックマトリックス基板１ａ〜７ａのＯＤ値を光学濃度計（マクベス社製「Ｄ２００‐II」）で測定した。接触式膜厚計で測定した膜厚で除することで膜厚１．０μｍ当たりのＯＤ値を算出した。
<OD value evaluation>
The OD values of the black matrix substrates 1a to 7a were measured with an optical densitometer (“D200-II” manufactured by Macbeth). By dividing by the film thickness measured with a contact-type film thickness meter, the OD value per 1.0 μm film thickness was calculated.
＜体積抵抗率評価＞
ブラックマトリックス基板１ｂ〜７ｂのクロム電極、アルミ電極間に微小電流測定装置（ケースレーインスツルメンツ社製「２３７型ソース・メジャーユニット」）を用いて直流５Ｖの電圧を印加し、電流値を測定した。得られた電流値より、体積抵抗率を算出した。
<Volume resistivity evaluation>
A voltage of DC 5 V was applied between the chromium electrodes and the aluminum electrodes of the black matrix substrates 1b to 7b using a minute current measuring device (“237 type source / measure unit” manufactured by Keithley Instruments Co., Ltd.), and the current value was measured. The volume resistivity was calculated from the obtained current value.
本発明の黒色感光性樹脂組成物を用いた実施例１〜５では、外観不良なく、１μｍ当たりのＯＤ値が４．０／μｍ以上であり、体積抵抗率も１．０Ｅ＋１２Ω・ｃｍ以上であった。これに対し、カーボンブラック顔料濃度が低い比較例１はＯＤ値が４．０／μｍより
低く、逆にカーボンブラック顔料濃度が高い比較例２は体積抵抗率が１．０Ｅ＋１２Ω・ｃｍ以下であった。また、染料を用いずにカーボンブラック顔料濃度を高くすることでＯＤ値を高めた比較例３は顕著に体積抵抗率が低かった。さらに、赤色／青色顔料分散液の混合により高ＯＤ化を試みた比較例４は外観異常が認められた。
In Examples 1 to 5 using the black photosensitive resin composition of the present invention, there was no poor appearance, the OD value per 1 μm was 4.0 / μm or more, and the volume resistivity was 1.0E + 12 Ω · cm or more. It was. On the other hand, Comparative Example 1 with a low carbon black pigment concentration had an OD value lower than 4.0 / μm, whereas Comparative Example 2 with a high carbon black pigment concentration had a volume resistivity of 1.0E + 12 Ω · cm or less. . Further, Comparative Example 3 in which the OD value was increased by increasing the carbon black pigment concentration without using a dye had a significantly low volume resistivity. Furthermore, abnormal appearance was observed in Comparative Example 4 where high OD was attempted by mixing the red / blue pigment dispersion.
本発明の黒色感光性樹脂組成物を用いることにより、１μｍ当たりのＯＤ値が４．０／μｍ以上であり、かつ体積抵抗率も１．０Ｅ＋１２Ω・ｃｍ以上である、遮光性と絶縁性を両立したブラックマトリックスを形成することができる。該ブラックマトリックスを具備したカラーフィルタを用いることにより、高コントラストでかつ信頼性良好な液晶表示装置を製造することが可能である。 By using the black photosensitive resin composition of the present invention, the OD value per 1 μm is 4.0 / μm or more and the volume resistivity is 1.0E + 12 Ω · cm or more. A black matrix can be formed. By using a color filter provided with the black matrix, a liquid crystal display device with high contrast and good reliability can be manufactured.
Claims (8)
〔化式（１）において、Ｘ１、Ｘ３、Ｘ６は、それぞれ独立にＲ１１、ＯＲ１１、ＣＯＲ１１、ＳＲ１１、ＣＯＮＲ１２Ｒ１３又はＣＮを表し、Ｘ２は置換基を有していてもよい炭素原子数１〜２０のアルキル基、置換基を有していてもよい炭素原子数６〜３０のアリール基、置換基を有していてもよい炭素原子数７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数２〜２０の複素環基を表し、Ｘ４及びＸ５は、それぞれ独立に、Ｒ１１、ＯＲ１１、ＳＲ１１、ＣＯＲ１１、ＣＯＮＲ１２Ｒ１３、ＮＲ１２ＣＯＲ１１、ＯＣＯＲ１１、ＣＯＯＲ１１、ＳＣＯＲ１１、ＣＯＳＲ１１、ＣＯＳＲ１１、ＣＳＯＲ１１、ＣＮ、ハロゲン原子又は水酸基を表す。Ｒ１１、Ｒ１２及びＲ１３は、それぞれ独立に、水素原子、置換基を有していてもよい炭素原子数１〜２０のアルキル基、置換基を有していてもよい炭素原子数６〜３０のアリール基、置換基を有していてもよい炭素原子数７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数２〜２０の複素環基を表す。ａ及びｂはそれぞれ独立に、０〜３である。〕 The black photosensitive resin composition according to any one of claims 1 to 5, comprising a compound represented by the chemical formula (1) as the photopolymerization initiator.
[In the chemical formula (1), X 1 , X 3 and X 6 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN, and X 2 has a substituent. An optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and an optionally substituted aryl having 7 to 30 carbon atoms Represents an alkyl group or an optionally substituted heterocyclic group having 2 to 20 carbon atoms, and X 4 and X 5 each independently represent R 11 , OR 11 , SR 11 , COR 11 , CONR 12. R 13, NR 12 COR 11, OCOR 11, COOR 11, SCOR 11, COSR 11, COSR 11, CSOR 11, CN, a halogen atom or a hydroxyl group. R 11 , R 12 and R 13 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 6 to 6 carbon atoms. It represents a 30 aryl group, an optionally substituted arylalkyl group having 7 to 30 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. a and b are each independently 0-3. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10025183B2 (en) * | 2014-01-22 | 2018-07-17 | Macdermid Graphics Solutions, Llc | Photosensitive resin composition |
| TWI659265B (en) * | 2014-03-07 | 2019-05-11 | 日商日鐵化學材料股份有限公司 | Black resin composition for light shielding film, substrate with light shielding film color filter and touch panel |
| JP6708365B2 (en) * | 2014-03-07 | 2020-06-10 | 日鉄ケミカル＆マテリアル株式会社 | Black photosensitive resin composition for light-shielding film, cured product using the same, and color filter and touch panel using the cured product as a light-shielding film |
| JP2016071244A (en) * | 2014-09-30 | 2016-05-09 | 富士フイルム株式会社 | Photosensitive resin composition, cured product and production method of the same, production method of resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device |
| JP2016071245A (en) * | 2014-09-30 | 2016-05-09 | 富士フイルム株式会社 | Photosensitive resin composition, cured product and production method of the same, production method of resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device |
| JP6607682B2 (en) * | 2015-03-05 | 2019-11-20 | 日鉄ケミカル＆マテリアル株式会社 | Black resin composition for light-shielding film, substrate with light-shielding film having light-shielding film obtained by curing said composition, and color filter and touch panel having said substrate with light-shielding film |
| JP2017090799A (en) | 2015-11-16 | 2017-05-25 | 株式会社ジャパンディスプレイ | Display device |
| JP6630222B2 (en) * | 2016-04-08 | 2020-01-15 | 富士フイルム株式会社 | Transfer film, decorative material, touch panel, and method of manufacturing decorative material |
| JP6914807B2 (en) * | 2017-10-30 | 2021-08-04 | サカタインクス株式会社 | Black coloring composition and black colored resist composition containing it |
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| JP3346647B2 (en) * | 1993-05-12 | 2002-11-18 | 富士写真フイルム株式会社 | Light-shielding photosensitive resin composition and light-shielding image forming method |
| JPH09302265A (en) * | 1996-05-16 | 1997-11-25 | Toppan Printing Co Ltd | Colored resin composition for light-screening film formation, arraying substrate element, and liquid crystal display |
| JPH09328618A (en) * | 1996-06-11 | 1997-12-22 | Toray Ind Inc | Light-shielding material, black paste, color filter and liquid crystal display device |
| JP4601267B2 (en) * | 2003-06-20 | 2010-12-22 | 東洋インキ製造株式会社 | Photosensitive black composition, black matrix substrate and color filter using the same |
| JP4752650B2 (en) * | 2006-04-13 | 2011-08-17 | 日立化成工業株式会社 | Photosensitive resin composition |
| JP4994923B2 (en) * | 2007-04-06 | 2012-08-08 | 太陽ホールディングス株式会社 | Black solder resist composition and cured product thereof |
| JP2010209203A (en) * | 2009-03-10 | 2010-09-24 | Tomoegawa Paper Co Ltd | Double-sided pressure-sensitive adhesive tape and medical drape using the same |
| JP2010256891A (en) * | 2009-04-01 | 2010-11-11 | Toyo Ink Mfg Co Ltd | Photosensitive coloring composition and color filter |
| TWI585527B (en) * | 2012-02-29 | 2017-06-01 | 新日鐵住金化學股份有限公司 | A photosensitive composition for black matrix and a method for producing the same |
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