JP5819693B2 - Colored photosensitive resin composition, color filter and display device - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition, a color filter, and a display device.

  Generally, the color filter is manufactured by a lithography method. In this lithography method, first, a black colored photosensitive resin composition is coated on a substrate, and then exposed and developed to form a black matrix. Next, for each of the colored photosensitive resin compositions of red, green, and blue, application, drying, exposure, and development are repeated, and a color filter is manufactured by forming pixel areas of each color at predetermined positions.

  The colored photosensitive resin composition used for the color filter is prepared by first dispersing a pigment and a pigment dispersant in a solvent to obtain a pigment dispersion, and then adding other components such as a resin to the pigment dispersion and mixing them. It is common to prepare by.

  Conventionally, the solvent has high solubility with respect to each component contained in the colored photosensitive resin composition, or when the colored photosensitive resin composition is applied to a substrate or the like, it has excellent coatability and evaporability. In many cases, ester-based and ketone-based solvents were used. However, in the case of a colored photosensitive resin composition containing an organic pigment and a pigment dispersant, the pigment dispersant is difficult to dissolve in an ester-based or ketone-based solvent, and the particle size of the pigment cannot be made fine. When the colored photosensitive resin composition is used, there is a problem that a color filter having high contrast cannot be produced. In contrast, when a solvent having an amide structure is used as the solvent, the solubility of the pigment dispersant can be increased, the pigment particle size can be reduced, and a colored photosensitive resin composition having a high transmittance can be prepared. It has been reported that when used, a color filter having a high contrast could be produced (see Patent Document 1).

JP 2003-330165 A

  On the other hand, in the colored photosensitive resin composition using an inorganic pigment as a pigment, when an ester solvent or a ketone solvent is used as a solvent, there is a problem that a large viscosity change occurs due to long-term storage, and patterning characteristics deteriorate. . For this reason, the coloring photosensitive resin composition excellent in storage stability was desired.

  The present invention provides a colored photosensitive resin composition excellent in stability over time of viscosity and patterning characteristics, a color filter formed using the colored photosensitive resin composition, and a display device including the color filter. Objective.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by containing a specific solvent, and have completed the present invention.

  A first aspect of the present invention is a colored photosensitive resin composition containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an inorganic pigment, and a solvent, wherein the solvent has a amide structure. It is a coloring photosensitive resin composition characterized by including.

  The second aspect of the present invention is a color filter formed using the colored photosensitive resin composition according to the present invention, and the third aspect of the present invention is a display device comprising the color filter according to the present invention. is there.

  According to the present invention, it is possible to obtain a colored photosensitive resin composition having excellent stability over time of viscosity and patterning characteristics. For this reason, the colored photosensitive resin composition which concerns on this invention can be used suitably for preparation of various color filters, and a display apparatus provided with the same.

  The colored photosensitive resin composition according to the present invention contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an inorganic pigment, and a solvent. First, these constituent components will be described.

<Alkali-soluble resin>
It does not specifically limit as alkali-soluble resin used by this invention, A conventionally well-known alkali-soluble resin can be used. In this specification, the alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a resin film having a thickness of 1 μm is formed on the substrate, and 2.38% by mass at 23 ° C. When dissolved in an aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute, it is dissolved in a film thickness of 0.01 μm or more.

  As the alkali-soluble resin, for example, a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used.

  Among these, the resin represented by the following formula (a-1) is preferable. The resin represented by the formula (a-1) itself is preferable in terms of high photocurability.

In the formula ^{(a-1), X} a represents a group represented by the following formula (a-2).

In the above formula (a-2), each R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, each R ^a2 independently represents a hydrogen atom or a methyl group, W ^a represents a single bond or a group represented by the following formula (a-3).

In the formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, in said formula (a-1), m shows the integer of 0-20.

Moreover, as an alkali-soluble resin having an ethylenically unsaturated group, a polyester obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol and a monobasic acid or a polybasic acid. (Meth) acrylate; Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; Bisphenol A type epoxy resin, Bisphenol F type epoxy resin Bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine Epoxy resins, and epoxy resins such as dihydroxybenzene type epoxy resin, can also be used (meth) epoxy obtained by reacting acrylic acid (meth) acrylate resin.
In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid. Similarly, “(meth) acrylate” means both acrylate and methacrylate.

  The mass average molecular weight of the alkali-soluble resin is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

  The content of the alkali-soluble resin is preferably 5 to 80% by mass and more preferably 15 to 50% by mass with respect to the solid content of the colored photosensitive resin composition. Solid content here is components other than a solvent. By making it in the above-mentioned range, there is a tendency that a balance of developability is easily obtained.

<Photopolymerizable monomer>
The colored photosensitive resin composition according to the present invention contains a photopolymerizable monomer. Photopolymerizable monomers include monofunctional monomers and polyfunctional monomers.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

  The content of the photopolymerizable monomer is preferably 1 to 30% by mass and more preferably 5 to 20% by mass with respect to the solid content of the colored photosensitive resin composition. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

<Photopolymerization initiator>
The colored photosensitive resin composition according to the present invention contains a photopolymerization initiator. It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl- 4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4 -Dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone , 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, 2-mercapto Benzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophe ) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4′-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4′-bisdiethylaminobenzophenone (ie, ethyl Michler's) Ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether , Benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert- Butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenyl Acridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9- Cridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5 -Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Toxistyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl -6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- Trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, “IRGACURE OXE02, IRGACURE OXE01, IRGACURE 369, IRGACURE 651, IRGAC RE 907 "(trade name: manufactured by BASF)," NCI-831 "(trade name: ADEKA Co., Ltd.), and the like. Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator, and it is particularly preferable to use an oxime-based photopolymerization initiator having a carbazole skeleton. These photopolymerization initiators can be used alone or in combination of two or more.

  It is preferable that content of a photoinitiator is 0.5-20 mass% with respect to solid content of a coloring photosensitive resin composition. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.

<Inorganic pigment>
The colored photosensitive resin composition according to the present invention contains an inorganic pigment. It does not specifically limit as an inorganic pigment, A conventionally well-known inorganic pigment can be used.

Specific examples of inorganic pigments include carbon black, titanium black, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Examples include various metal oxides such as Sb, Hg, Pb, Bi, Si, and Al, composite oxides, metal sulfides, metal sulfates, and metal carbonates.
When forming the black matrix, it is preferable to use carbon black having a high light shielding property. As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, lamp black and the like can be used, but it is particularly preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

  Resin-coated carbon black has low conductivity compared to carbon black without resin coating, so there is less current leakage when used as a black matrix for liquid crystal display elements such as liquid crystal displays, and high reliability and low consumption Can produce power displays.

  Further, a dispersant may be further used in order to uniformly disperse the inorganic pigment. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the inorganic pigment, it is preferable to use an acrylic resin-based dispersant.

  The content of the inorganic pigment is preferably 5 to 70% by mass and more preferably 25 to 55% by mass with respect to the solid content of the colored photosensitive resin composition. By setting it as said range, a black matrix and each colored layer can be formed with the target pattern, and it is preferable. Particularly when a black matrix is formed, it is preferable to adjust the amount of the inorganic pigment in the colored photosensitive resin composition so that the OD value per 1 μm of film thickness is 4 or more. If the OD value per film thickness of 1 μm in the black matrix is 4 or more, a sufficient display contrast can be obtained when used in a black matrix of a liquid crystal display.

<Solvent>
The colored photosensitive resin composition according to the present invention contains a solvent, and the solvent contains a solvent having an amide structure. Here, the solvent having an amide structure is a solvent having a bond between a carbonyl group and nitrogen, and means carboxylic acid amide, imide, urea, derivatives thereof, and the like. By including the solvent having an amide structure, the stability with time of viscosity and the stability with time of patterning characteristics are improved.

  As the solvent having the amide structure, a solvent represented by the following formula (1) or (2) is preferably used.

In said formula (1), R < ¹ > shows a hydrogen atom or an alkyl group each independently, X shows a hydrogen atom, an alkyl group, or an amino group.

In the above formula ^{(2), R 2, R} 3 each represent a hydrogen atom or an alkyl radical, n is an integer of 1-3.

R ¹ , R ² , and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. N is preferably 1 or 2.

  The solvent having the amide structure preferably has a boiling point of 150 to 250 ° C. By setting it as the above range, the coating film is sufficiently volatilized without causing bumping at the time of drying after the colored photosensitive resin composition is applied on the substrate, so that surface defects and surface roughness are hardly caused.

  As the solvent having an amide structure represented by the above formula (1) or (2) and having a boiling point of 150 to 250 ° C., 1,1,3,3-tetramethylurea, 1,1,3,3-tetraethyl Urea, dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, N, N-dimethylpropion Examples include amide, N-methylacetamide, N-methylformamide and the like.

  The solvent having an amide structure is preferably used in combination with other solvents generally used for colored photosensitive resin compositions. Other commonly used solvents are those that disperse or dissolve alkali-soluble resins, photopolymerizable monomers, photopolymerization initiators, inorganic pigments, and that do not react with these components and have appropriate volatility. Often, examples include polyalkylene glycol monoalkyl ethers, polyalkylene glycol monoalkyl ether acetates, ketones, esters, and aromatic hydrocarbons.

  Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol Mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol Monomethyl ether, dipropylene glyco (Poly) alkylene glycol monoalkyl ethers such as dimethyl monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl (Poly) alkylene glycol monoalkyl ether acetates such as ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, die Other ethers such as lenglycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; lactic acid such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate Alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate 2-methyl-3-hydroxybutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, vinegar Isopropyl acid, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvin Other esters such as acid n-propyl, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in combination of two or more.

  Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3-methoxybutyl acetate, ethyl lactate, ethylene glycol Monoethyl ether is preferable because the dispersibility of the inorganic pigment can be improved, and it is particularly preferable to use propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate.

  It is preferable to combine these solvents and the solvent having the amide structure to form a solvent for the colored photosensitive resin composition, and the solvent having the amide structure is included in 1 to 90% by mass in the total solvent. Is preferable, and it is more preferable to contain 1-50 mass%.

  The content of the solvent is preferably such that the total concentration of the total solid content of the colored photosensitive resin composition is 1 to 50% by mass from the viewpoint of the coating property and stability of the colored photosensitive resin composition to be obtained. The amount of 5 to 30% by mass is more preferable.

  The colored photosensitive resin composition according to the present invention may contain various additives as necessary.

  Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio It can be mentioned the residue improving agents such as Le.

  In the present invention, the colored photosensitive resin composition can be prepared by an appropriate method. A preferable method for preparing a colored photosensitive resin composition is, for example, a bead mill, a roll mill, etc. And then mixing and dispersing while pulverizing to obtain a dispersion, and then adding an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and, if necessary, additional solvents and additives to the dispersion. The method of preparing by adding and mixing can be mentioned.

  The colored photosensitive resin composition prepared in this way is excellent in stability over time of viscosity and patterning characteristics.

≪Color filter, display device≫
The color filter according to the present invention comprises a colored layer formed using the colored photosensitive resin composition according to the present invention. A coating film is formed using a colored photosensitive resin composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance, and the coating film is irradiated with radiation in a predetermined pattern and developed. Thus, for example, a color filter pixel or a black matrix of a liquid crystal display can be formed.

  The display device according to the present invention includes such a color filter, and examples of the display device include a liquid crystal display and an organic EL display.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not restrict | limited at all by these Examples.

<Preparation of colored photosensitive resin composition>
[Example 1]
The following components were mixed, and the mixture was stirred for 1 hour, and then filtered through a 5 μm membrane filter to prepare a colored photosensitive resin composition.
Alkali-soluble resin Resin A (solid content 55%, solvent: 3-methoxybutyl acetate) ... 60 parts by massPhotopolymerizable monomer Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) ... 25 parts by mass Photoinitiator Etanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) “IRGACURE OXE-02” (trade name: 15 parts by mass, inorganic pigment, carbon dispersion “CF black” (trade name: 25% solids by Mikuni Dye Co., Ltd.) Solvent: 3-methoxybutyl acetate, 400 parts by mass, solvent 3-methoxy Butyl acetate / 1,1,3,3-tetramethylurea / propylene glycol monomethyl acetate = 55/10/35 (mass ratio) 300 parts by weight

The synthesis method of the resin A is as follows.
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following transparent formula (a-4) colorless and transparent.

Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Resin A. The disappearance of the acid anhydride group was confirmed by IR spectrum.
In addition, this resin A corresponds to the compound represented by the said Formula (a-1).

[Examples 2 to 10 and Comparative Examples 1 to 9]
A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the mixing ratio (mass ratio) of the solvent was changed as shown in Table 1.

ＭＢＡ：３−メトキシブチルアセテート
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＥＬ：エチルラクテート
エチルセロソルブ：エチレングリコールモノエチルエーテル
ＡＮ：シクロヘキサノン
γ−ＢＬ：γ−ブチロラクトン
δ−ＶＬ：δ−バレロラクトン
ε−ＣＬ：ε−カプロラクトン
ＴＭＵ：１，１，３，３−テトラメチルウレア
ＤＭＦ：ジメチルホルムアミド
ＤＭＡＣ：ジメチルアセトアミド
ＤＭＩ：１，３−ジメチル−２−イミダゾリジノン

MBA: 3-methoxybutyl acetate PGMEA: propylene glycol monomethyl ether acetate EL: ethyl lactate ethyl cellosolve: ethylene glycol monoethyl ether AN: cyclohexanone γ-BL: γ-butyrolactone δ-VL: δ-valerolactone ε-CL: ε- Caprolactone TMU: 1,1,3,3-tetramethylurea DMF: dimethylformamide DMAC: dimethylacetamide DMI: 1,3-dimethyl-2-imidazolidinone

<Evaluation of colored photosensitive resin composition>
[Viscosity stability evaluation]
After the colored photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were stored at the initial stage of preparation and 25 ° C. for 7 days, the viscosity was measured using an E-type viscometer, and the initial and after storage The viscosity difference was determined. The evaluation index was evaluated as ○ when the viscosity difference was less than 0.1 and × when 0.1 or more. The results are shown in Table 2.

As can be seen from Table 2, when the solvent contains 1,1,3,3-tetramethylurea, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, which are solvents having an amide structure Even after storage for 7 days, the difference from the initial viscosity was 0.03 to 0.04, and the viscosity was stable over time.
Even when δ-valerolactone and ε-caprolactone were contained in the solvent, the viscosity was excellent in stability over time.

[Patterning characteristic stability evaluation]
After the colored photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were stored at the initial stage of preparation and 25 ° C. for 7 days, spin coaters (Corning Co., Ltd.) were prepared on different glass substrates (10 mm × 10 mm). Manufactured by Eagle-XG) and pre-baked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of 1.0 μm. Subsequently, this coating film was exposed at 50 mJ / cm ² (exposure gap 50 μm) using a mirror projection aligner (Topcon Corporation, TME-150 RTO). During exposure, exposure was performed through masks having line widths of 4, 6, 8, 10, 12, 14, 16, 18, and 20 μm. After exposure, the film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C. for 60 seconds, and then the presence or absence of resolution of each line width was confirmed with an optical microscope, and the thinnest line patterned was confirmed. The difference between the thinnest line widths that could be patterned between the initial stage and after storage was evaluated. The difference was evaluated as ◎ when the difference was 0 μm, ○ when 2 to 4 μm, and × when it was 6 μm or more. The results are shown in Table 3.

  As can be seen from Table 3, any colored photosensitive resin composition exhibited good micropatterning characteristics at the initial stage of preparation. If the solvent contains 1,1,3,3-tetramethylurea, dimethylformamide, dimethylacetamide, or 1,3-dimethyl-2-imidazolidinone, which are solvents having an amide structure, after storage for 7 days The fine patterning characteristics remained the same as in the initial stage, and the temporal stability of the patterning characteristics was excellent. On the other hand, in other cases, the patterning characteristics were deteriorated. In particular, in Comparative Examples 8 and 9, which had excellent viscosity stability over time, the patterning characteristics deteriorated significantly.

  Thus, in a colored photosensitive resin composition containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an inorganic pigment, and a solvent, if the solvent contains a solvent having an amide structure, the viscosity and patterning characteristics over time. A product having excellent stability was obtained.

Claims (7)

Alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, inorganic pigments, and a colored photosensitive resin composition containing a solvent, viewed contains a solvent wherein the solvent is an amide structure,
The solvent solvent having an amide structure represented by the following formula (1) or (2) (excluding dimethylacetamide and diethylacetamide.) Containing, colored photosensitive resin composition.

(In the formula, each R ¹ independently represents a hydrogen atom or an alkyl group, and X represents a hydrogen atom, an alkyl group, or an amino group.)

^(Wherein, R 2, ^{R 3} each independently represent a hydrogen atom or an alkyl radical, n is an integer of 1-3.) The colored photosensitive resin composition according to claim 1 , wherein the solvent having the amide structure has a boiling point of 150 to 250 ° C. The solvent having the amide structure is 1,1,3,3-tetramethylurea, 1,1,3,3-tetraethylurea, dimethylformamide, diethylformamide, 1,3-dimethyl-2-imidazolidone, 1,3- It is at least one selected from the group consisting of dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, N, N-dimethylpropionamide, N-methylacetamide and N-methylformamide. Item 3. The colored photosensitive resin composition according to Item 1 or 2. The solvent includes the solvent having the amide structure, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3-methoxybutyl. The colored photosensitive resin composition according to any one of claims 1 to 3, which is combined with at least one solvent selected from the group consisting of acetate, ethyl lactate and ethylene glycol monoethyl ether. The colored photosensitive resin composition according to any one of claims 1 to 4 , wherein a ratio of the solvent having an amide structure is 1 to 90% by mass in all the solvents. The color filter formed using the colored photosensitive resin composition of any one of Claim 1 to 5 . A display device comprising the color filter according to claim 6 .