CN116736632A - 着色感光性树脂组合物、使用其制造的滤色器及包括该滤色器的显示装置 - Google Patents
着色感光性树脂组合物、使用其制造的滤色器及包括该滤色器的显示装置 Download PDFInfo
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- CN116736632A CN116736632A CN202210426380.XA CN202210426380A CN116736632A CN 116736632 A CN116736632 A CN 116736632A CN 202210426380 A CN202210426380 A CN 202210426380A CN 116736632 A CN116736632 A CN 116736632A
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- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NAPRALPCJATWGJ-UHFFFAOYSA-N hydroxymethyl 3-sulfanylpropanoate Chemical compound OCOC(=O)CCS.OCOC(=O)CCS.OCOC(=O)CCS NAPRALPCJATWGJ-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940057867 methyl lactate Drugs 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
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- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
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- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 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
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- KRGGVEDZUSPSAC-UHFFFAOYSA-N oxetan-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CCO1 KRGGVEDZUSPSAC-UHFFFAOYSA-N 0.000 description 1
- AMUUFLNQHMIHRP-UHFFFAOYSA-N oxetan-3-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1COC1 AMUUFLNQHMIHRP-UHFFFAOYSA-N 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000001062 red colorant Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229960004599 sodium borate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- AXMCIYLNKNGNOT-UHFFFAOYSA-M sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfonatophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].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 AXMCIYLNKNGNOT-UHFFFAOYSA-M 0.000 description 1
- FJBHGWADYLMEJG-UHFFFAOYSA-M sodium;3-[[4-[[4-(diethylamino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C(C=C1)C=CC1=[N+](CC)CC1=CC=CC(S([O-])(=O)=O)=C1 FJBHGWADYLMEJG-UHFFFAOYSA-M 0.000 description 1
- MWZFQMUXPSUDJQ-KVVVOXFISA-M sodium;[(z)-octadec-9-enyl] sulfate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCCOS([O-])(=O)=O MWZFQMUXPSUDJQ-KVVVOXFISA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- WNQPPENQFWLADQ-UHFFFAOYSA-J tetrasodium;4-hydroxy-5-[[4-[[4-[(8-hydroxy-3,6-disulfonatonaphthalen-1-yl)diazenyl]-2-methoxy-5-methylphenyl]carbamoylamino]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(O)=C2C(N=NC3=C(C)C=C(C(=C3)OC)NC(=O)NC3=CC(C)=C(N=NC=4C5=C(O)C=C(C=C5C=C(C=4)S([O-])(=O)=O)S([O-])(=O)=O)C=C3OC)=CC(S([O-])(=O)=O)=CC2=C1 WNQPPENQFWLADQ-UHFFFAOYSA-J 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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Abstract
本发明涉及包括(A)色料;(B)碱溶性树脂;(C)光聚合性化合物;(D)光聚合引发剂和(E)溶剂,所述(A)色料包括选自由红色色料、蓝色色料和紫色色料组成的组中的一种以上的色料和黑色颜料,形成厚度0.5至3μm的膜时,在光谱波长380至780nm的总透射率为80%以上的着色感光性树脂组合物、使用其制造的滤色器及包括所述滤色器的显示装置。
Description
技术领域
本发明涉及着色感光性树脂组合物、使用其制造的滤色器以及包括该滤色器的显示装置。
背景技术
近年来,通过在作为柔性材料的塑料等柔软基板上形成显示部和布线等,即使像纸一样弯曲也能够显示图像的柔性显示装置近来受到关注。
柔性显示装置的应用范围很广,不仅适用于电脑显示器和电视,还适用于个人便携设备。特别是有机发光显示器(Organic Light Emitting Display;OLED)与液晶显示器(Liquid Crystal Display;LCD)不同,由于不需要额外的光源,它可以以相对较薄的厚度实现,由于这一点,关于柔性显示装置,正在积极地进行对有机发光装置的研究。
另一方面,柔性显示装置若要实际应用,与目前的各种显示产品相比,需要能够实现全彩、低功耗、而且在户外也易于阅读。
从这个意义上说,有机发光装置由于具有全彩的实现可能性、低功耗、响应速度快的优点,因此成为柔性显示装置最有用的资源。当前的有机发光装置需要封装阻挡层(encapsulation barrier)和偏光板(polarizer),其中封装阻挡层用于保护有机发光装置免受氧气和湿气影响,偏光板保持高对比度(contrast ratio)以实现户外可读性。
然而,由于上述偏光板具有不弯曲且坚硬的特性,因此当其应用于柔性显示装置时,可能会出现柔性降低的问题。另一方面,如果不使用偏光板,由于外部光透过柔性显示装置进入后再次反射出去,与原本从有机发光装置发出的光混合,在外部光源下的对比度会大大降低。
因此,最近正在积极地进行改善偏光板特性或开发用于替代偏光板的组合物的研究。
另一方面,以往的显示器为了使用宽的前置屏幕的同时安装相机会制造为将显示器的一部分切除并钻孔以安装相机的缺口设计或开孔显示器的形式,从而屏幕以不完整的形式体现。因此,最近,为了在不单独配置这样的缺口或开孔的情况下实现全面屏的同时安装摄像头,不设置缺口或开孔而将摄像头安装在显示器下方的屏下摄像头(UDC)的需求正在增加。这样的屏下摄像头(UDC)为了提高摄像头质量,需考虑使用高透明和低反射的材料作为绝缘膜。
此外,与先前的使用高温工艺制造的显示器相比,使用低温工艺制造的显示器具有更大的特性。通常,为了提高材料的可靠性,通常通过高温工艺来提高图案的可靠性,但在最近开发的显示器的情况下,由于它们对热敏感,很难执行高温工艺。因此,对即使在低温工艺中也没有工艺问题的树脂组合物的要求不断增长。
韩国专利公开第10-2013-0134498号公开了一种包含色料、粘合剂树脂和嵌段异氰酸酯基的油墨组合物,该色料包括红色色料和绿色色料。但是,在实现高色料再现性的过程中,存在色料选择范围有限、各种色域的实现不足、另外图案形成时线撕裂、底切等工艺性不足的问题。
因此,需要开发一种适用于绝缘膜的树脂组合物,以取代偏光板的同时实现低温固化性特性优异的屏下摄像头。
【现有技术文献】
【专利文献】
(专利文献1)大韩民国专利公开第10-2013-0134498号(2013年12月10日公开)
发明内容
【发明要解决的技术问题】
本发明解决了以往的固色(灰色)再现性和工艺性不足的问题,其目的在于,提供一种可替代偏光板的同时,具有优异的低温固化性和防止外部光反射效果,适合实现屏下摄像头(UDC)的着色感光性树脂组合物。
本发明的另一个目的是,提供一种使用该着色感光性树脂组合物制造的滤色器和包括该滤色器的显示装置。
【解决技术问题的手段】
为了实现上述目的,本发明提供一种着色感光性树脂组合物,其特征在于,该着色感光性树脂组合物包括(A)色料;(B)碱溶性树脂;(C)光聚合性化合物;(D)光聚合引发剂和(E)溶剂,
上述(A)色料包括选自由红色、蓝色和紫色组成的组中的至少一种色料和黑色颜料,
以0.5至3μm的厚度形成膜时,在380nm至780nm的光谱波长下的透射率为80%以上。
此外,本发明提供一种使用该着色感光性树脂组合物制造的滤色器以及包括该滤色器的显示装置。
【发明效果】
本发明的着色感光性树脂组合物、使用其制造的滤色器以及包括该滤色器的显示装置可以提供优异的对比度、色纯度和反射率效果,低温固化性和防外部光反射效果也优异,因此可以替代显示装置中的偏光板,适合实现屏下摄像头(UDC),从而解决以往的固色、即灰色的再现性和工艺性不足的问题。
此外,当根据本发明的着色感光性树脂组合物、使用其制造的滤色器以及包括该滤色器的显示装置以0.5至3μm的厚度形成膜时,在380nm至780nm的光谱波长下的透射率为80%以上,可以防止OLED光源的寿命过度缩短,提高光源的效率。
具体实施方式
本发明涉及能够提供优异的对比度、色纯度和反射率效果,并且具有优异的低温固化性和防止外部光反射效果,可以替代显示装置中的偏光板,解决以往的着色感光性树脂组合物的固色、即灰色的再现性和工艺性不足的问题,适合实现屏下摄像头(UDC)的着色感光性树脂组合物、使用该树脂组合物制造的滤色器以及包括该滤色器的显示装置。
另外,本发明涉及在380至780nm的光谱波长处具有80%以上的(光)透射率,从而防止OLED光源的寿命过度缩短,提高光源的效率的着色感光性树脂组合物、、使用其制造的滤色器以及包括上述滤色器的显示装置。
以下详细说明本发明。
<着色感光性树脂组合物>
本发明的着色感光性树脂组合物包括(A)色料;(B)碱溶性树脂;(C)光聚合性化合物;和(D)光聚合引发剂,并且可以进一步包括(E)溶剂。
(A)色料
本发明的着色感光性树脂组合物作为(A)色料必须含有选自由红色色料、蓝色色料和紫色色料组成的组中的至少色料和黑色颜料。
具体而言,本发明的着色感光性树脂组合物混合使用上述色料和黑色颜料,形成厚度为0.5至3μm的膜时,在上述膜的厚度方向上,在380至780nm波段的(光)透射率可以为80%以上,反射率可以为10%以下。
此外,优选本发明的着色感光性树脂组合物在形成厚度为0.5至3μm的薄膜时,在光谱波长为550至590nm处的透射率可以为80%以上。
在以往的着色感光性树脂组合物的情况下,由于无法降低透射率,外部光反射率过高,或者为了赋予防止外部光反射效果使380~780nm的可见光波段区域的透射率过低,OLED光源的效率反而降低,存在光源寿命过度消耗的问题。
然而,本发明的着色感光性树脂组合物通过提供足以取代偏光板的防止外部光反射效果的同时提供80%以上的透射率,从而可以保持显示器的亮度,因此具有最大限度地提高了光源的寿命和效率的优点。
红色色料、蓝色色料和/或紫色色料
上述色料可以包含颜料和染料中的一种以上。
上述颜料具体可以举出在显色指数(The society of Dyers and Colourists出版)中被分类为颜料的化合物,更具体地说,优选具有以下的显色指数(C.I.)编号的颜料,但不限于这些。
但是,在绿色和黄色色料的情况下,通过实验确认了与本发明的红色色料、蓝色色料或紫色色料相比,反射率降低,并且会出现波长不平坦(flat)的问题。
本发明所包含的红色色料可以包含红色颜料和红色染料中的一种以上。
作为本发明的红色颜料,例如可以为选自由C.I.颜料红9、97、105、122、123、144、149、166、168、176、177、180、192、215、216、224、242、254、255和264组成的组中的一种以上,优选C.I.颜料红179、C.I.颜料红177、C.I.颜料红209、C.I.颜料红242和C.I.颜料红254。
本发明的红色染料例如可以举出如C.I.溶剂红8、45、49、89、111、122、125、130、132、146和179等的C.I.溶剂染料;
如C.I.酸性红1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,158,176,182,183,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349,382,383,394,401,412,417,418,422和426等的C.I.酸性染料;
如C.I.直接红79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246和250等的C.I.直接染料;
如C.I.媒染剂红1,2,3,4,9,11,12,14,17,18,19,22,23 24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94和95等的C.I.媒染剂染料。
作为本发明的红色色料,优选可以包含选自由C.I.颜料红177、C.I.颜料红179、C.I.颜料红209、C.I.颜料红242和C.I.颜料红254组成的组中的一种以上。
本发明中包含的蓝色色料可以包含蓝色颜料和蓝色染料中的一种以上。
本发明的蓝色颜料例如可以为选自由蓝色C.I.颜料15(15:3,15:4,15:6等),21,28,60,64和76组成的组中的一种以上,其中优选C.I.颜料蓝15:3,C.I.颜料蓝15:4,C.I.颜料蓝15:6,C.I.颜料蓝16,C.I.颜料蓝21,C.I.颜料蓝28,C.I.颜料蓝60,C.I.颜料蓝64和C.I.颜料蓝76。
本发明的蓝色染料例如可以举出如C.I.溶剂蓝35、37、59和67等的C.I.溶剂染料;
如C.I.酸性蓝1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103,112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324:1,335和340等的C.I.酸性染料;
如C.I.直接蓝38,44,57,70,77,80,81,84,85,86,90,93,94,95,97,98,99,100,101,106,107,108,109,113,114,115,117,119,137,149,150,153,155,156,158,159,160,161,162,163,164,166,167,170,171,172,173,173,172,173,172,172,188,189,190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252,256,257,259,260,268,274,275和293等的C.I.直接染料;
如C.I.媒染剂蓝1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83和84等的C.I.媒染剂染料。
作为本发明的蓝色色料优选选自由C.I.颜料蓝15:3,C.I.颜料蓝15:4,C.I.颜料蓝15:6,C.I.颜料蓝16,C.I.颜料蓝21,C.I.颜料蓝28,C.I.颜料蓝60,C.I.颜料蓝64和C.I.颜料蓝76组成的组中的一种以上。
本发明所包含的紫色色料可以包含紫色颜料和紫色染料中的一种以上。
作为本发明的紫色颜料例如可以为选自由C.I.颜料紫14、19、23、32、33、36和38组成的组中的一种以上,优选C.I.颜料紫14、C.I.颜料紫19、C.I.颜料紫23、C.I.颜料紫29、C.I.颜料紫32、C.I.颜料紫33、C.I.颜料紫36、颜料紫37和C.I.颜料紫38。
本发明的紫色染料例如可以举出如C.I.酸紫6B、7、9、17和19等的C.I.酸性染料,;
如C.I.直接紫47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103和104等的C.I.直接染料;
如C.I.媒染剂紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53和58的C.I.媒染剂染料。
作为本发明的紫色色料优选包括选自由C.I.颜料紫14、C.I.颜料紫19、C.I.颜料紫23、C.I.颜料紫29、C.I.颜料紫32、C.I.颜料紫33、C.I.颜料紫36、C.I.颜料紫37和C.I.38颜料紫组成的组中的一种以上。
相对于着色感光性树脂组合物的总重量,上述红色色料、蓝色色料和/或紫色色料可以包括0.1至3重量%,优选0.3至1.2重量%。当包含在上述范围内时,在防止外部光反射效果和可视性方面具有优势,可以保持80%以上的透射率和10%以下的反射率。但是,当超出上述范围来包含时,反射率会降低,短波长透射率会增加,可能会导致难以形成平坦(flat)的透射光谱的问题。
黑色颜料
本发明的色料中所包含的黑色颜料可用于吸收可见光波长段的光。
上述黑色颜料可以单独使用黑色有机颜料,或者可以混合使用黑色有机颜料和黑色无机颜料。当包含黑色有机颜料时,因为具有比着色感光性树脂组合物更低的介电常数而优选。另外,当仅单独包含黑色无机颜料时,与黑色有机颜料相比,介电常数高,因此绝缘膜的生成中可能会出现问题而不优选。
上述黑色有机颜料是与红色、蓝色和绿色颜料混合的颜料,可以使用选自由C.I.颜料黑1、C.I.颜料黑7等的有机炭黑、内酰胺黑、苝黑、菁黑和苯胺黑组成的组中的一种以上,但不限于此。
上述选自由红色色料、蓝色色料和紫色色料组成的组中的一种以上的色料和黑色颜料的重量比可为0.4:0.6至0.1:0.9。当黑色颜料的含量增加时,在反射率方面是有利的,但可能出现透射率降低的问题,因此当将色料和黑色颜料的重量比以上述重量比范围的方式包括色料和黑色颜料时,由于会增加所降低的透射率的同时生成在全波长区域具有没有起伏的平坦的透射率而优选。
相对于本发明的着色感光性树脂组合物的总重量,可以包括0.1至3重量%的上述(A)色料。当包含在上述范围时,在防止外部光反射效果和可见性方面具有优势,并且透射率可以保持80%以上。如果色料超过3重量%,出现透光率降低的问题,从而降低屏幕的亮度。
其他颜料或染料
本发明的(A)色料在不损害本发明目的的范围内还可以包括在本领域通常使用的有机颜料、无机颜料、染料等。
作为有机颜料,可使用用于印刷油墨,喷墨油墨等的各种颜料,具体可以举出水溶性偶氮颜料,不溶性偶氮颜料,酞菁素颜料,喹吖啶酮颜料,异吲哚啉颜料,佩里伦颜料,铁酮颜料,二恶嗪颜料,蒽醌颜料、二蒽醌颜料、邻氨基甲嘧啶颜料、蒽嵌蒽醌颜料、靛蒽醌颜料、皮蒽酮颜料或吡咯并吡咯二酮颜料等。
上述无机颜料可包括金属化合物如金属氧化物或金属络合物,具体地,铁、钴、铝、镉、铅、铜、钛、镁、铬、锌或锑等金属的氧化物或复合金属氧化物等。
上述有机颜料和无机颜料可以为显色指数(The society of Dyers andColourists出版)中被分类为颜料的化合物,更具体地说,可以为如下所述的显色指数(C.I.)编号的颜料,但不限于此。
上述染料如果对有机溶剂具有溶解性或可分散性,则可以无限制地使用。优选使用对有机溶剂具有溶解性并且能够保证对碱性显影液的溶解度和耐热性、耐溶剂性等的可靠性的染料。
作为上述染料,可以使用具有磺酸或羧酸等酸性基团的酸性染料、酸性染料与含氮化合物的盐、酸性染料的磺酰胺物等它们的衍生物,除此之外,也可以选择偶氮类、氧杂蒽类、酞菁类的酸性染料及其衍生物。
颜料分散剂
添加上述颜料分散剂是为了颜料的解聚和保持稳定性,可以无限制地使用本领域常用的颜料分散剂。例如,可举出阳离子系、阴离子系、非离子系、两性、聚酯系、聚胺系等表面活性剂,它们可以分别单独使用或组合两种以上使用。
上述阳离子系表面活性剂的具体例可以举出硬脂胺盐酸盐和月桂基三甲基氯化铵等胺盐或季铵盐等。
作为上述阴离子系表面活性剂的具体例可以举出月桂醇硫酸钠、油醇硫酸钠等高级醇硫酸盐类,月桂基硫酸钠、月桂基硫酸铵等烷基硫酸盐类,十二烷基苯磺酸钠、十二烷基萘磺酸钠等烷基芳基磺酸盐类等。
作为上述非离子系表面活性剂的具体例可以举出聚氧乙烯烷基醚、聚氧乙烯芳基醚、聚氧乙烯烷基芳基醚、其他聚氧乙烯衍生物、氧乙烯/氧丙烯嵌段共聚物、脱水山梨糖醇脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、甘油脂肪酸酯、聚氧乙烯脂肪酸酯、聚氧乙烯烷基胺等。
此外,可举出聚氧乙烯烷基醚类、聚氧乙烯烷基苯基醚类、聚乙二醇二酯类、脱水山梨糖醇酐脂肪酸酯类、脂肪酸改性聚酯类、叔胺改性聚氨酯类、聚乙烯亚胺类等。
另外,作为上述颜料分散剂,优选含有甲基丙烯酸丁酯(BMA)或甲基丙烯酸N,N-二甲基氨基乙酯(DMAEMA)等丙烯酸酯系分散剂(以下称为丙烯酸酯系分散剂)。上述丙烯酸酯系分散剂优选使用通过活性控制方法制备的丙烯酸酯系分散剂,市售产品可以举出DISPERBYK-2000、DISPER BYK-2001、DISPER BYK-2070或DISPER BYK-2150,上述丙烯酸酯系分散剂可以单独使用一种,也可以两种以上组合使用。
作为上述颜料分散剂,除了丙烯酸酯系分散剂之外,还可以使用其他树脂类型的颜料分散剂。上述其他树脂类型的颜料分散剂可以举出已知的树脂类型颜料分散剂,特别是以聚氨酯和聚丙烯酸酯为代表的聚羧酸酯;不饱和聚酰胺、多羧酸、多羧酸的(部分)胺盐、多羧酸的铵盐、多羧酸的烷基胺盐、聚硅氧烷、长链聚氨基酰胺磷酸盐、含羟基的多羧酸的酯及其改性产物;或由具有游离羧基的聚酯与聚(低级亚烷基亚胺)反应形成的酰胺或其盐等油性分散剂;(甲基)丙烯酸-苯乙烯共聚物、(甲基)丙烯酸-(甲基)丙烯酸酯共聚物、苯乙烯-马来酸共聚物、聚乙烯醇或聚乙烯吡咯烷酮等水溶性树脂或水溶性高分子化合物;聚酯;改性聚丙烯酸酯;环氧乙烷/环氧丙烷的加成物;以及磷酸酯。
作为上述其他树脂类型的颜料分散剂的市售品,作为阳离子系树脂分散剂例如可以举出BYK(Big)Chemi Corporation的商品名:DISPER BYK-160、DISPER BYK-161、DISPERBYK-162、DISPER BYK-163、分散剂BYK-164、分散剂BYK-166、分散剂BYK-171、分散剂BYK-182、分散剂BYK-184;巴斯夫公司的商品名:EFKA-44、EFKA-46、EFKA-47、EFKA-48、EFKA-4010、EFKA-4050、EFKA-4055、EFKA-4020、EFKA-4015、EFKA-4060、EFKA-4300、EFKA-4330、EFKA-4400、EFKA-4406、EFKA-4510、EFKA-4800;Lubrizol公司的商品名:SOLSPERS-24000、SOLSPERS-32550、NBZ-4204\/10;Kawaken Fine Chemicals公司的商品名:HINOACT T-6000、HINOACT T-7000、HINOACT T-8000;Ajinomoto Corporation的商品名:AJISPUR PB-821、AJISPUR PB-822、AJISPUR PB-823;共荣社化学株式会社的商品名:FLORENE DOPA-17HF、FLORENE DOPA-15BHF、FLORENE DOPA-33、FLORENE DOPA-44等。
除了上述丙烯酸酯系分散剂之外的上述其他树脂系颜料分散剂可以单独使用或两种以上组合使用,或者可以与丙烯酸酯系分散剂组合使用。
基于100重量份的上述色料固体含量,上述颜料分散剂的含量可以为1至50重量份,优选5至30重量份。如果颜料分散剂的含量在上述范围内,则可以得到粒径均一的分散颜料,因此优选。如果分散剂的含量超过50重量份,则粘度可能会增加,如果分散剂的含量小于1重量份,则可能难以使颜料微粒化,或者会引起分散后的凝胶化等问题。
(B)碱溶性树脂
碱溶性树脂是给显影工序中使用的碱性显影液赋予溶解性的成分,只要能够溶解于碱性显影液即可,可以没有限制地使用。上述碱溶性树脂对在形成图案时的显影处理工序中使用的碱性显影液具有溶解性,为了提高低温固化性,优选共聚(b1)具有羧基的烯属不饱和单体来制备。
上述碱溶性树脂的酸值优选为30至200mgKOH/g。当碱溶性树脂的酸值小于30mgKOH/g时,感光性树脂组合物难以确保充分的显影速度,如果超过200mgKOH/g,则与基板的密合性降低,图案容易短路,与色料的相容性出现问题,感光性树脂组合物内的色料析出,或者感光性树脂组合物的储存稳定性降低,从而粘度容易上升。
上述碱溶性树脂的重均分子量(例如,通过使用聚苯乙烯作为标准材料的凝胶渗透色谱法(GPC)测量)可以为约3,000至50,000,优选5,000至30,000。在上述分子量范围内,可以抑制显影工序中的膜损失并且可以提高图案稳定性。
(b1)具有羧基的烯属不饱和单体
作为具有羧基的烯属不饱和单体的具体例可以举出丙烯酸、甲基丙烯酸、巴豆酸等一元羧酸;富马酸、中康酸、衣康酸等二羧酸以及上述二羧酸的酸酐;在两末端具有羧基和羟基的聚合物的单(甲基)丙烯酸酯,例如ω-羧基聚己内酯单(甲基)丙烯酸酯等,优选丙烯酸和甲基丙烯酸。
此外,上述碱溶性树脂可以通过与具有羧基的烯属不饱和单体(b2)可共聚的不饱和单体进行聚合来制备。
(b2)可共聚的不饱和单体
上述可共聚的不饱和聚合单体的具体例可以举出作为具有缩水甘油基的不饱和单体的甲基丙烯酸缩水甘油酯;(甲基)丙烯酸羟乙酯类等的具有羟基的烯属不饱和单体,例如(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸4-羟丁酯、(甲基)丙烯酸2-羟基-3-苯氧基丙酯、N-羟乙基丙烯酰胺等;苯乙烯、乙烯基甲苯、α-甲基苯乙烯、对氯苯乙烯、邻甲氧基苯乙烯、间甲氧基苯乙烯、对甲氧基苯乙烯、邻乙烯基苄基甲基醚、间乙烯基苄基甲基醚、对乙烯基苄基甲基醚、邻乙烯基苄基缩水甘油醚、间乙烯基苄基缩水甘油醚、对乙烯基苄基缩水甘油醚等的芳香族乙烯基化合物;N-环己基马来酰亚胺、N-苄基马来酰亚胺、N-苯基马来酰亚胺、N-邻羟基苯基马来酰亚胺、N-间羟基苯基马来酰亚胺、N-对羟基苯基马来酰亚胺、N-邻甲基苯基马来酰亚胺、N-间甲基苯基马来酰亚胺、N-对甲基苯基马来酰亚胺、N-邻甲氧基苯基马来酰亚胺、N-间-甲氧基苯基马来酰亚胺、N-对-甲氧基苯基马来酰亚胺等的N-取代马来酰亚胺化合物;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯和(甲基)丙烯酸叔丁酯等的(甲基)丙烯酸烷基酯;(甲基)丙烯酸环戊酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸2-甲基环己酯、(甲基)丙烯酸三环[5.2.1.0 2,6]癸-8-酯、二环戊氧基乙基(甲基)丙烯酸酯、(甲基)丙烯酸异冰片酯等的脂环族(甲基)丙烯酸酯类;(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等的(甲基)丙烯酸芳酯类;3-(甲基丙烯酰氧甲基)氧杂环丁烷、3-(甲基丙烯酰氧甲基)-3-乙基氧杂环丁烷、3-(甲基丙烯酰氧甲基)-2-三氟甲基氧杂环丁烷;3-(甲基丙烯酰氧甲基)-2-苯基氧杂环丁烷、2-(甲基丙烯酰氧甲基)氧杂环丁烷;2-(甲基丙烯酰氧基甲基)-4-三氟甲基氧杂环丁烷等的不饱和氧杂环丁烷化合物;等等,但不限于此。
上述可共聚的不饱和单体中的每一种可以单独使用或两种以上组合使用。
相对于着色感光性树脂组合物的总重量,上述碱溶性树脂的含量可以为10至80重量%,优选15至50重量%,更优选20至30重量%。当上述碱溶性树脂包含在上述范围内时,在显影液中的溶解度充分而容易形成图案,并且在显影时防止曝光部的像素部分的膜减少,改善非像素部分的遗漏性,因此优选。
(C)光聚合性化合物
上述光聚合性化合物是能够通过以下(D)光聚合引发剂的作用来发生聚合的化合物,可以使用单官能单体、双官能单体或多官能单体,优选可以使用双官能以上的多官能单体。
上述单官能单体的具体例可以为壬基苯基卡必醇丙烯酸酯、2-羟基-3-苯氧基丙基丙烯酸酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羟乙酯或N-乙烯基吡咯烷酮等,但不限于此。
上述双官能单体的具体例可以为1,6-己二醇(甲基)丙烯酸酯、乙二醇(甲基)丙烯酸酯、新戊基乙醇基(甲基)丙烯酸酯、(甲基)丙烯酸三乙二醇酯、双酚A的双(丙烯酰氧乙基)醚或3-甲基戊烷二醇(甲基)丙烯酸酯等,但不限于此。
上述多官能单体的具体例可以举出三羟甲基丙烷三(甲基)丙烯酸酯、乙氧基化的三羟甲基丙烷三(甲基)丙烯酸酯、丙氧基化的三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇(甲基)丙烯酸酯、乙氧基化的二季戊四醇六(甲基)丙烯酸酯,丙氧基化的二季戊四醇六(甲基)丙烯酸酯或二季戊四醇六(甲基)丙烯酸酯等,但不限于此。
此外,相对于着色感光性树脂组合物的总重量,上述光聚合性化合物可以包括5至50重量%,优选7至45重量%,更优选10至20重量%。当上述光合化合物包括在上述范围内时,像素部的强度和平滑度良好,因此优选。
(D)光聚合引发剂
本发明中的上述光聚合引发剂通过如可见光、紫外线、远紫外线、电子射线、X射线等放射线的曝光而产生能够引发上述光聚合性化合物聚合的自由基的化合物。
上述光聚合引发剂可以举出例如苯乙酮系化合物、二苯甲酮系化合物、双咪唑系化合物、三嗪系化合物、肟酯系化合物和噻吨酮系化合物等。
在本发明中,光聚合引发剂可以单独使用或两种以上组合使用,优选使用一种以上的肟酯类化合物。
上述苯乙酮系化合物的具体例可以举出二氧苯乙酮、2-羟基-2-甲基-1-苯基丙烷-1-酮、苄基二甲基酮、2-羟基-1-[4-(2-羟基乙氧基)苯基]-2-甲基丙烷-1-酮、1-羟基环酰基苯基酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉基丙烷-1-酮,2-苄基-2-二甲氨基-1-(4-吗啉基苯基)丁烷-1-酮、2-羟基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷-1-酮、2-(4-甲基苄基)-2-(二甲基氨基)-1-(4-吗啉基苯基)丁烷-1-酮等。
上述二苯甲酮系化合物可以举出例如二苯甲酮、邻(甲氧基羰基)二苯甲酮、4-苯基二苯甲酮、4-(4-甲基苯硫基)二苯甲酮、3,3',4,4'-四(叔丁基过氧羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等。
上述双咪唑化合物的具体例可以举出2,2'-双(2-氯苯基)-4,4',5,5'-四苯基-1,2'-双咪唑、2,2'-双(2,3-二氯苯基)-4,4',5,5'-四苯基-1,2'-双咪唑、2,2'-双(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)-1,2'-双咪唑、2,2'-二(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)-1,2'-双咪唑、2,2-双(2,6-二氯苯基)-4,4',5,5'-四苯基-1,2'-双咪唑或位于4,4',5,5'位置的苯基被烷氧羰基取代的咪唑化合物等。其中,优选使用2,2'-双(2-氯苯基)-4,4',5,5'-四苯基-1,2'-双咪唑、2,2'-双(2,3-二氯苯基)-4,4',5,5'-四苯基-1,2'-双咪唑、2,2-双(2,6-二氯苯基)-4,4',5,5'-四苯基-1,2'-双咪唑。
上述三嗪化合物的具体例可举出2,4-双(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-双(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-双(三氯甲基)-6-苯并芘-1,3,5-三嗪、2,4-双(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-双(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-双(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-双(三氯甲基)-6-[2-(4-二乙氨基-2-甲基苯基)乙烯基]-1,3,5-三嗪、2,4-双(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪等。
上述肟酯系化合物包括邻乙氧基羰基-α-氧基亚胺基-1-苯基丙烷-1-酮、1,2-辛二酮、-1-(4-苯硫基)苯基、-2-(邻苯甲酰氧基)、乙酮、-1-(9-乙基)-6-(2-甲基苯甲酰基-3-基)-、1-(邻乙酰氧基)等,常用的产品有CGI-124(汽巴嘉基公司)、CGI-224(汽巴嘉基公司)、Irgacure OXE-01(巴斯夫公司)、Irgacure OXE-02(巴斯夫公司)等产品、N-1919(ADEKA公司)、NCI-831(ADEKA公司)等。
上述噻吨酮系化合物可以为例如2-异丙基噻吨酮、2,4-二乙基噻吨酮、2,4-二氯噻吨酮、1-氯-4-丙氧基噻吨酮等。
此外,上述光聚合引发剂还可以包括光聚合引发助剂,以提高本发明的红外透射感光性树脂组合物的灵敏度。本发明的红外透射感光性树脂组合物含有光聚合引发助剂,进一步提高灵敏度,从而提高生产率。
作为上述光聚合引发助剂,可以优选使用例如选自胺化合物、羧酸化合物和具有巯基的多官能硫醇化合物组成的组中的一种以上的化合物。
作为上述胺化合物,优选使用芳香族胺化合物,特别是可以使用三乙醇胺、甲基二乙醇胺、三异丙醇胺等脂肪族胺化合物、4-甲氨基苯甲酸酯、4-二甲氨基苯甲酸乙酯、4-二甲氨基苯甲酸异戊酯、4-二甲氨基苯甲酸2-乙基己酯、苯甲酸2-二甲氨基乙酯、N,N-二甲基对甲苯甲醛、4,4'-双(二甲氨基)二苯甲酮(统称为:米希勒酮)、4,4'-双(二乙氨基)二苯甲酮等。
上述羧酸化合物优选为芳香族异质乙酸,具体为苯硫代乙酸、甲基苯硫代乙酸、乙基苯硫代乙酸、甲基乙基苯硫代乙酸、二甲基苯硫代乙酸、甲氧基苯硫代乙酸、甲氧基苯基苯硫代乙酸、二甲氧基苯硫代乙酸、氯苯硫代乙酸、二氯苯硫代乙酸、N-苯基甘氨酸、苯氧基乙酸、萘硫代乙酸、N-萘基甘氨酸、萘氧乙酸等。
上述具有巯基的多官能硫醇化合物可以举出例如2-巯基苯并噻唑、1,4-双(3-巯基丁酰氧基)丁烷、1,3,5-三(3-巯基丁烯基氧乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮,三羟甲基丙三(3-巯基丙酸酯),季戊四醇四(3-巯基丁酸酯)、季戊四醇四(3-巯基丙酸酯)、二季戊四醇六(3-巯基丙酸酯)、四乙二醇双(3-巯基丙酸酯)等。
相对于本发明的着色感光性树脂组合物的总重量,上述光聚合引发剂可包括0.1至40重量%,优选0.1至10重量%。当光聚合引发剂包括在上述范围内时,着色感光性树脂组合物具有高灵敏度,缩短曝光时间,提高生产率,可以保持高分辨率,像素部的强度和像素部表面的平滑度良好。
此外,当包含光聚合引发助剂时,可以包括总光聚合引发剂的10至100重量%,优选20至100重量%。当上述光聚合引发助剂包括在上述范围内时,着色感光性树脂组合物的灵敏度更高,提供使用上述组合物形成的滤色器的生产率的提高效果。
(E)溶剂
本发明的溶剂优选丙二醇单甲醚乙酸酯,但如果可溶解着色感光性树脂组合物,则可以无特别限制地追加使用。
上述可追加使用的溶剂特别优选醚类、芳香烃类、酮类、醇类、酯类或酰胺类等。具体为乙二醇单甲醚、乙二醇单乙醚、乙二醇单丙基醚、乙二醇单丁醚、二甘醇二甲醚、二甘醇乙醚、二甘醇二丙醚、二甘醇二丁醚、丙二醇单甲醚、丙二醇单乙醚、醚类如丙二醇单丙醚、丙二醇单丁醚、二丙二醇二甲醚、二丙二醇二乙醚、二丙二醇二丙醚和二丙二醇二丁醚;苯甲苯、二甲苯、均三甲苯等芳烃;甲乙酮、丙酮、甲基戊基酮、甲基异丁基酮、环己酮等酮类;乙醇、丙醇、丁醇、己醇、环己醇、乙二醇、甘油等醇类;3-乙氧基丙酸乙酯;3-甲氧基丙酸甲酯、甲氧基乙基乙酸酯、乙氧基乙基乙酸酯、乙酸乙酯、乙酸丁酯、乙酸戊酯、乳酸甲酯、乳酸乙酯、乳酸丁酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基-1-丁酯、乙酸甲氧基戊酯、乙二醇单乙酸酯、乙二醇二乙酸酯、乙二醇单甲醚乙酸酯、乙二醇单乙醚乙酸酯、二甘醇单乙酸酯、二甘醇二乙酸酯、二甘醇单丁醚乙酸酯、丙二醇单乙酸酯、丙二醇二乙酸酯、丙二醇单乙醚乙酸酯、碳酸亚乙酯、碳酸亚丙酯、γ-丁内酯等酯类。上述溶剂可以使用选自由示例性溶剂组成的组中的一种或混合两种以上使用。
在上述溶剂中,从涂布性和干燥性的角度考虑,优选可以使用沸点为100至200℃的有机溶剂,更优选亚烷基二醇烷基醚乙酸酯类、酮类、3-乙氧基丙酸乙酯或3-甲氧基丙酸甲酯等酯类,进一步优选使用丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、环己酮、3-乙氧基丙烯酸乙酯、3-甲氧基丙烯酸甲酯等。这些溶剂可以分别单独使用或混合两种以上使用。
上述溶剂的含量可以以使着色感光性树脂组合物的总重量成为100重量%的剩余量包含。具体地,本发明中的“剩余量”是指使得进一步包括本发明的必须成分和其他附加成分的组合物的总重量成为100重量%的剩余量,并不因为上述“残留量”的含义而限定本发明的着色感光性树脂组合物不包含追加成分。例如,相对于着色感光性树脂组合物的总重量,上述溶剂的含量可以为50至95重量%,优选50至60重量%,但不限于此。
(F)氧杂蒽系化合物
本发明的着色感光性树脂组合物还可以含有氧杂蒽系化合物。
上述氧杂蒽系化合物是分子中具有氧杂蒽骨架的化合物,可以进一步提高着色感光性树脂组合物的保存稳定性。
上述氧杂蒽系化合物可以举出例如C.I.酸性红51、52、87、91、92、94、289、388、C.I.酸性紫9、30、C.I.碱性红1(Rhodamine 6G)、2、3、4,8,C.I.碱性红10(Rhodamine B),11,C.I.碱性紫10,11,25,C.I.溶剂红218,C.I.现代红27,C.I.活性红36(Rose Bengal B),Sulforodamine B,Sulforodamine G等,但不限于此,这些染料可以单独使用或两种以上组合使用。
更优选包括选自由C.I.酸性红52、C.I.酸性红289、C.I.酸性红91、C.I.酸性红92、C.I.酸性红94和Rhodamine B组成的组中的一种以上。
相对于上述(A)色料的总重量,上述氧杂蒽系化合物的含量优选为1至20重量%。氧杂蒽系化合物具有优异的透射率和耐热性,但由于缺乏对溶剂的溶解性和相容性,难以在着色感光性树脂组合物中使用足够的量。当包含低于上述范围的上述氧杂蒽系化合物时,难以期待透射率和储存稳定性的改善效果。当超过上述范围时,氧杂蒽系化合物的溶解度降低,涂膜内容易发生析出等异物,对比度降低,着色感光性树脂组合物的储存稳定性可能会劣化。
(G)添加剂
本发明的着色感光性树脂组合物除上述成分外,在不损害本发明的目的的范围内根据本领域技术人员的需要还可以含有流平剂、填料、其他高分子化合物、密合促进剂、紫外线吸收剂、抗凝剂等公知的添加剂。
上述流平剂可以包括硅氧烷系表面活性剂、氟系表面活性剂和具有氟原子的硅氧烷系表面活性剂。它们可以在侧链中具有聚合性基团。
上述硅氧烷系表面活性剂可以举出在分子中具有硅氧烷键的表面活性剂。具体来说,可以举出东丽有机硅DC3PA、SH7PA、DC11PA、SH21PA、SH28PA、SH29PA、SH30PA、SH8400(Dow Corning Toray Co.,Ltd.)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(Shin-Etsu Silicone公司)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452和TSF4460(Momentive Performance Materials Japan LLC)。
上述氟系表面活性剂可以举出在分子中具有碳氟链的表面活性剂。具体而言,可以举出Fluorad FC4430、FC431(住友3M Ltd.)、Megaface F142D、Megaface F171、MegafaceF172、Megaface F173、Megaface F177、Megaface F183、Megaface F554、Megaface R30、Megaface RS-718-K(DIC Corporation)、EFTOP EF301、EFTOP EF303、EFTOP EF351、EFTOPEF352(三菱材料电子化学株式会社)、SURFLON S381、SURFLON S382、SURFLON SC101、SURFLON SC105(旭硝子株式会社制)、E5844(大金精细化学研究所)等。
具有氟原子的有机硅系表面活性剂可以举出在分子中具有硅氧烷键和碳氟链的表面活性剂。具体而言,可以举出Megaface R08、Megaface BL20、Megaface F475、MegafaceF477和F443(DIC Corporation)等。
上述填料具体可以使用玻璃、二氧化硅、氧化铝等,但不限于此。
上述其他高分子化合物具体可以举出环氧树脂和马来酰亚胺树脂等可固化树脂,聚乙烯醇、聚丙烯酸、聚乙二醇单烷基醚、多氟烷基丙烯酸酯、聚酯和聚氨酯等热塑性树脂,但不限于此。
上述密合促进剂具体可以使用选自由乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、N-(2-氨乙基)-3-氨丙基甲基二甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、3-缩水甘油氧基丙基三甲氧基硅烷、3-缩水甘油氧基丙基甲基二甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-氯丙基甲基二甲氧基硅烷、3-氯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-巯基丙基三甲氧基硅烷、3-异氰酸酯丙基三甲氧基硅烷和3-异氰酸酯丙基三乙氧基硅烷组成的组中的一种或它们的混合物。
上述紫外线吸收剂具体可以使用2-(3-叔丁基-2-羟基-5-甲基苯基)-5-氯苯并噻唑、烷氧基二苯甲酮等,但不限于此。
上述抗凝剂具体可以使用聚丙烯酸钠,但不限于此。
<滤色器和显示装置>
本发明提供由上述着色感光性树脂组合物制造的滤色器和显示装置。
上述滤色器的厚度可根据目的或用途适当调整,通常为0.1至30μm,优选为1至8μm。
可以将上述着色感光性树脂组合物涂布在基板上并干燥以形成着色膜。涂布后加热干燥(预烘烤)或减压干燥后进行加热使溶剂等挥发成分挥发,上述加热温度为70至200℃,优选80至130℃。
基板也可以是滤色器本身的基板、固态成像装置或显示装置等中的设置滤色器的区域,并没有特别限制。上述基板可以是玻璃、硅(Si)、氧化硅(SiOx)或高分子基板,高分子基板为聚醚砜(polyethersulfone,PES)或聚碳酸酯(polycarbonate,PC)等。
上述涂布法可以通过辊涂法、旋涂法、狭缝涂布法、喷墨印刷法等涂布法或印刷工序等来进行。
之后,可以对上述着色膜进行曝光和显影,形成对应于每个像素的着色图案。
上述曝光工序可以包括使用掩模选择性地曝光上述像素区域的UV曝光(例如,使用g线、h线、i线或KrF光源)。之后,通过使用显影液选择性地去除未曝光区域,可以形成具有所需图案形状的着色图案。
上述显影液可以包括例如无机或有机碱性化合物。上述无机碱性化合物的实例可以举出氢氧化钠、氢氧化钾、磷酸氢二钠、磷酸二氢钠、磷酸氢二铵、磷酸二氢铵、磷酸二氢钾、硅酸钠、硅酸钾、可以举出碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、硼酸钠、硼酸钾、氨等。有机碱性化合物的实例可以举出氢氧化四甲铵、氢氧化2-羟乙基三甲铵、一甲胺、二甲胺、三甲胺、可以举出单乙胺、二乙胺、三乙胺、单异丙胺、二异丙胺、乙醇胺等。它们可以单独使用或两种以上组合使用。
在上述显影工序之后,可以通过额外的热固化工序(后烘烤、后烧成)使着色图案更加硬化,此时加热温度可以为90至180℃,加热时间为5至180分钟,优选15至90分钟,但不限于此。
通过上述工序制造的着色图案的滤色器通过包括作为色料的选自由红色、蓝色和紫色组成的组中的至少一种色料和黑色颜料(优选黑色有机颜料),从而具有能够代替偏光板的低反射率、优异的外部光反射效果和提高显示器的可见性的优点。
此外,本发明提供一种包含上述滤色器的显示装置。
上述显示装置可以包括如固体成像元件如CCD图像传感器、CMOS图像传感器等固体成像装置,如光源等发光装置,图像显示装置等通常可以包括在显示装置中的其余的部件。
本发明的上述显示装置可以是柔性显示装置,特别是可以是在其中实现屏下摄像头(UDC)的显示装置。
在下文中,为了具体说明本发明,将通过实施例进行详细说明。然而,根据本发明的实施例可以变形为各种其它形式,并且本发明的范围不应被解释为仅限于下面描述的实施例。本发明的实施例是为了给本领域的具有一般知识的人员更全面地说明本发明而提供。
<颜料分散组合物的制备>
制备例1.颜料分散组合物M1
将有机炭黑15重量份、作为分散剂的Azispa PB821(Ajinomoto fine techno公司)6重量份、作为溶剂的丙二醇单甲醚乙酸酯79重量份利用珠磨机混合/分散12小时,制得颜料分散组合物M1。
制备例2.颜料分散组合物M2
将作为颜料的12.0重量份的C.I.颜料红177、作为颜料分散剂的DISPERBYK-2001(由BYK公司制备)5.0重量份、作为溶剂的4-羟基-4-甲基-2-戊酮13.0重量份、丙二醇甲醚乙酸酯70.0重量份通过珠磨机混合/分散12小时,制得颜料分散组合物M2。
制备例3.颜料分散组合物M3
将作为颜料的12.0重量份的C.I.颜料红254、作为颜料分散剂的DISPERBYK-2001(由BYK公司制备)5.0重量份、作为溶剂的4-羟基-4-甲基-2-戊酮13.0重量份、丙二醇甲醚乙酸酯70.0重量份通过珠磨机混合/分散12小时,制备颜料分散组合物M3。
制备例4.颜料分散组合物M4
将作为颜料的12.0重量份的颜料蓝15:6、作为颜料分散剂的DISPERBYK-2001(由BYK公司制备)4.0重量份、作为溶剂的丙二醇甲醚乙酸酯44重量份、丙二醇甲醚40重量份通过珠磨机混合/分散12小时,制备颜料分散组合物M4。
制备例5.颜料分散组合物M5
将作为颜料的13重量份的C.I.颜料紫23、作为颜料分散剂的D ISPERBYK-2001(由BYK公司制备)7重量份、作为溶剂的丙二醇甲醚乙酸酯76重量份、丙二醇甲醚4重量份通过珠磨机混合/分散12小时,制得颜料分散组合物M5。
制备例6.颜料分散组合物M6
将作为颜料的12.0重量份的C.I.颜料绿58、作为颜料分散剂的DISPERBYK-2001(由BYK公司制备)5.0重量份、作为溶剂的4-羟基-4-甲基-2-戊酮为13.0重量份、丙二醇甲醚乙酸酯70.0重量份通过珠磨机混合/分散12小时,制得颜料分散组合物M6。
制备例7.颜料分散组合物M7
将作为颜料的12.0重量份的C.I.颜料黄150、DISPERBYK-2001的(由BYK公司制备)5.0重量份、作为溶剂的4-羟基-4-甲基-2-戊酮13.0重量份、丙二醇甲醚乙酸酯70.0重量份通过珠磨机混合/分散12小时,制得颜料分散组合物M7。
制备例8.颜料分散组合物M8
将作为颜料的12.0重量份的C.I.颜料蓝16、作为颜料分散剂的DISPERBYK-2001(由BYK公司制备)4.0重量份、作为溶剂的丙二醇甲醚乙酸酯44重量份、丙二醇甲醚40重量份通过珠磨机混合/分散12小时,制得颜料分散组合物M8。
制备例9.颜料分散组合物M9
将作为颜料的13重量份的C.I.颜料紫37、作为颜料分散剂的DISPERBYK-2001(由BYK公司制备)7重量份、作为溶剂的丙二醇甲醚乙酸酯76重量份、丙二醇甲醚4重量份通过珠磨机混合/分散12小时,制得颜料分散组合物M9。
合成例1.碱性可溶性树脂的合成
将丙二醇单甲醚乙酸酯120重量份、丙二醇单甲醚80重量份、AIBN 2重量份、丙烯酸13.0重量份、甲基丙烯酸苄酯10重量份、苯乙烯57.0重量份、甲基丙烯酸甲酯20重量份和巯基正十二烷3重量份加入到具有搅拌器、温度计回流冷却管、分装滴管和氮气引入管的烧瓶中,进行氮气置换。之后,进行搅拌并将反应液的温度升至110℃,反应6小时。由此合成的碱溶性树脂的固体的酸值为100.2mgKOH/g,GPC测得的重均分子量Mw约为6,000。
<着色感光性树脂组合物的制备>
根据以下的表1和表2的组成制备实施例和比较例的着色感光性树脂组合物。
【表1】
【表2】
(A):颜料分散组合物
A1:制备例1的颜料分散组合物M1、有机炭黑
A2:制备例2的颜料分散组合物M2、颜料红177
A3:制备例3的颜料分散组合物M3、颜料红254
A4:制备例4的颜料分散组合物M4、颜料蓝15:6
A5:制备例5的颜料分散组合物M5、C.I.颜料紫23
A6:制备例6的颜料分散组合物M6,C.I.颜料绿58
A7:制备例7的颜料分散组合物M7、C.I.颜料黄150
A8:制备例8的颜料分散组合物M8、C.I.颜料蓝16
A9:制备例9的颜料分散组合物M9,C.I.颜料紫37
(B)碱溶性树脂:合成例1的碱溶性树脂
(C)光聚合性化合物:二季戊四醇六丙烯酸酯(KAYARD DPHA;由日本化药株式会社制造)
(D)光聚合引发剂:2-O-苯甲酰肟-1-[4-(苯硫基)苯基]-1,2-辛二酮(OXE-01;巴斯夫制造)
(E)溶剂(丙二醇单甲醚乙酸酯)
<实验例>
使用上述实施例和比较例制备的着色感光性树脂组合物制备滤色器。
实验例1.膜厚测量
具体地,将上述的每种着色感光性树脂组合物通过旋涂法施加在2英寸见方的玻璃基板(由康宁公司制备的“EAGLE XG”)上,然后置于加热板上并在100℃的温度下保持3分钟以形成薄膜。接着,在上述薄膜上放置具有在1至100%范围内阶段性地改变透射率的图案和3×3cm的曝光部图案的测试光掩膜,并以与测试光掩模的间距为100μm的方式照射紫外线。此时,紫外线光源使用含有所有g,h,i线的1KW高压汞灯以100mJ/cm2的照度进行照射,并且没有使用特殊的滤光片。将上述紫外线照射后的薄膜浸泡在THMA 2.38%水溶液中2分钟而显影。使用蒸馏水清洗涂布上述薄膜的玻璃板,吹氮气进行干燥,并在100℃的加热炉中加热60分钟而制造滤色器。膜厚由膜厚测量装置(DEKTAK6M;Veeco公司制造)测量,测得的薄膜厚度为1.5μm。
实验例2.特性评价
2.1透射率测量
关于光谱,除了未使用测试光掩模以外,与上述实验例1同样地制造滤色器之后,使用色度计(奥林巴斯生产,OSP-200)测量透射率,结果如下表2所示。此外,使用色度计(由奥林巴斯制造,OSP-200)测量380nm至780nm范围内可见光区域的光谱透射率,结果示于表3。
2.2反射率测量
除了未使用测试光掩模以外,与上述实施例1同样地制造滤色器之后,通过积分球反射率测量仪(柯尼卡美能达,光谱光度计CM-3700d)在涂层表面测量2度正反射率,结果示于下表3。
2.3耐光性评价
将获得的涂膜用耐光性测试仪(阳光测试CPS+,东洋精机公司制造)照射氙灯光48小时。测量照射前后x-y色度坐标(x,y)和Y,用JIS Z 8730:2009中描述的方法由上述测量值计算出色差△Eab*,结果示于表3。△Eab*越小表示颜色变化越小,当△Eab*为3以下时,其涂膜作为滤色器在实用上没有问题。此外,如果涂膜的感光性良好,则可以说由相同的着色固化性树脂组合物制造的图案也具有良好的耐光性。
【表3】
参见上述表3,可以确认到在包含本发明的黑色颜料和色料的实施例的情况下,耐光性优异,并且满足每个波长区域和整个波长中的透射率和反射率范围。
但是,当仅包括黑色颜料时,当包括黑色颜料和绿色或黄色色料时,以及当红色色料的含量过多时,可以确认到不满足本发明的透射率和反射率的范围。
Claims (15)
1.一种着色感光性树脂组合物,其特征在于,
包括(A)色料;(B)碱溶性树脂;(C)光聚合性化合物;(D)光聚合引发剂和(E)溶剂,
所述(A)色料包括选自由红色色料、蓝色色料和紫色色料组成的组中的一种以上的色料和黑色颜料,
形成厚度0.5至3μm的膜时,在光谱波长380至780nm的总透射率为80%以上。
2.根据权利要求1所述的着色感光性树脂组合物,其特征在于,由所述着色感光性树脂组合物形成的着色图案的反射率为10%以下。
3.根据权利要求1所述的着色感光性树脂组合物,其特征在于,形成厚度0.5至3μm的膜时,在光谱波长550nm至590nm的透射率为80%以上。
4.根据权利要求1所述的着色感光性树脂组合物,其特征在于,
相对于本发明的着色感光性树脂组合物的总重量,所述红色色料、蓝色色料和/或紫色色料含有0.3至1.2重量%。
5.根据权利要求1所述的着色感光性树脂组合物,其特征在于,相对于着色感光性树脂组合物的总重量,所述(A)色料含有0.1至3重量%。
6.根据权利要求1所述的着色感光性树脂组合物,其特征在于,所述红色色料包含选自由C.I.颜料红177、C.I.颜料红179、C.I.颜料红209、C.I.颜料红242和C.I.颜料红254组成的组中的一种以上。
7.根据权利要求1所述的着色感光性树脂组合物,其特征在于,所述蓝色色料包含选自由C.I.颜料蓝15:3、C.I.颜料蓝15:4、C.I.颜料蓝15:6、C.I.颜料蓝16、C.I.颜料蓝21、C.I.颜料蓝28、C.I.颜料蓝60、C.I.颜料蓝64和C.I.颜料蓝76组成的组中的一种以上。
8.根据权利要求1所述的着色感光性树脂组合物,其特征在于,所述紫色色料包含选自由C.I.颜料紫14、C.I.颜料紫19、C.I.颜料紫23、C.I.颜料紫29、C.I.颜料紫32、C.I.颜料紫33、C.I.颜料紫36、C.I.颜料紫37和C.I.颜料紫38组成的组中的一种以上。
9.根据权利要求1所述的着色感光性树脂组合物,其特征在于,所述黑色颜料为黑色有机颜料。
10.根据权利要求9所述的着色感光性树脂组合物,其特征在于,所述黑色有机颜料包含选自由混合红色、蓝色和绿色颜料的颜料、C.I.颜料黑1、C.I.颜料黑7、有机炭黑、内酰胺黑、苝黑、菁黑和苯胺黑组成的组中的一种以上。
11.根据权利要求1所述的着色感光性树脂组合物,其特征在于,选自由红色色料、蓝色色料和紫色色料组成的组中的一种以上的色料与黑色颜料的重量比为0.4:0.6至0.1:0.9。
12.根据权利要求1所述的着色感光性树脂组合物,其特征在于,进一步含有氧杂蒽系化合物。
13.一种滤色器,其使用权利要求1至12中任一项所述的着色感光性树脂组合物制造。
14.一种显示装置,包括权利要求13所述的滤色器。
15.根据权利要求14所述的显示装置,其特征在于,所述显示装置为柔性显示装置。
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