JP2008249987A - Photosensitive resist composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resist composition for color filter with which a thin film pattern having high light shielding property can be easily formed by a photolithographic process, the residue in an unexposed part after alkali development can be suppressed and a favorable pattern profile and sensitivity are obtained, and to improve reliability and manufacturing yield of a color filter and a liquid crystal display device. <P>SOLUTION: The photosensitive resist composition comprises at least a pigment (A), an acrylic polymer (B), a monomer (C), a photopolymerization initiator (D) and a solvent (E), wherein the monomer (C) comprises a bisphenolfluorene type acrylate and/or a diacrylate of bisphenol-A epoxy resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a black photosensitive resin composition and a colored pattern formed using the same, and more particularly to a photosensitive color resist composition for a color filter and a color filter for a liquid crystal display device.

  A color filter is usually manufactured by a method in which different hues of red, green, and blue are sequentially formed in a striped or mosaic color pattern on the surface of a transparent substrate such as glass or plastic sheet on which a black matrix is formed. Yes. The black matrix used as the light-shielding film plays a role of preventing a decrease in contrast and color purity due to light leakage between pixels.

  Conventionally, vapor deposition films of metals or metal compounds such as chromium, nickel, and aluminum have been used as the black matrix, but the process is complicated and expensive, and the surface of the metal thin film is highly reflective. There is a problem. Therefore, as a solution to this problem, a pigment dispersion method using a resin composition in which a pigment is dispersed is currently mainstream.

  There are negative and positive pigment dispersion methods, but negative photosensitive compositions mainly composed of acrylic polymers, acrylic polyfunctional monomers or oligomers, photoinitiators, solvents and pigments are widely used. Yes. When forming a negative color filter, a pixel pattern is usually obtained by applying a color resist on a substrate, drying it, irradiating it with ultraviolet rays through a photomask, developing it, and dissolving the unexposed area with a developer. Form. By repeating this cycle for the required number of colors, a colored coating pattern can be obtained.

  In a color filter having a black matrix formed by this pigment dispersion method, it is sensitive to an epoxy compound having a fluorene skeleton or a bisphenol type structure as in Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5. A photosensitive resin composition containing a compound to which a functional group is added or a compound obtained by further acid-modifying these is described. It has extremely excellent heat resistance and high adhesion due to its fluorene structure, but on the other hand, the adhesion of the unexposed part is also improved, so it is not sufficiently dissolved, and the pigment on the substrate It will cause the residue to remain. In particular, in order to stably disperse titanium black, it is necessary to use a polymer dispersant having both an acid value and an amine value. When combined with a photosensitive resin composition having a fluorene skeleton, There is a problem that a residue occurs in an unexposed portion.

In addition, the photosensitive resin composition for black matrix using the alkali-soluble resin containing the fluorene skeleton as a binder still has a problem that the sensitivity at the time of exposure is still low and the pattern edge shape after development is not good.
Japanese Patent Laid-Open No. 05-070528 Japanese Patent Laid-Open No. 08-278629 Japanese Patent Application Laid-Open No. 08-327813 JP 09-241339 A Japanese Patent Laid-Open No. 10-158374

  The present invention was devised in view of the circumstances as described above, and the object of the present invention is to easily form a pattern having a thin film and high light-shielding property by a photolithography method, and to leave a remaining unexposed portion after alkali development. It is intended to provide a photosensitive resist composition for a color filter having a good pattern shape and sensitivity, and to improve the reliability of the color filter and the liquid crystal display device and to improve the yield.

  In order to solve the above problems, the present invention has the following configuration.

  (1) In the photosensitive resist composition containing at least the pigment (A), the acrylic polymer (B), the monomer (C), the photoinitiator (D), and the solvent (E), the monomer (C) is: A photosensitive resist composition, which is a compound represented by the following general formula (1) and / or general formula (2).

(In the formula, R ¹ , R ⁴ and R ⁵ represent a hydrogen atom or a methyl group, R ² represents an arbitrary organic group. R ³ may have a substituent and has 1 to 10 carbon atoms. An alkyl group, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group, a cycloalkyl having 5 to 12 carbon atoms, an aryl group or arylene group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, m represents 0. An integer of -10, n is an integer of 1-20.)
(2) The photosensitive resist composition according to (1), wherein R ² is a substituent represented by the following general formula (3).

(In the formula, R ⁶ is represented by any one of an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group, and these may have a substituent.)
(3) The photosensitive resist composition according to any one of (1) and (2), wherein the photoinitiator (D) comprises a compound represented by the following general formula (4) as an essential component: object.

(In the formula, R ⁷ represents a hydrogen atom or a monovalent organic group, and R ⁸ is represented by a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.)
(4) The photosensitive resist composition according to claim 3, wherein the monovalent organic group is a substituent represented by the following general formula (5) or (6).

  (5) The photosensitive resist composition according to any one of (1) to (4), wherein the acrylic polymer (B) has a carboxyl group.

(6) The photosensitive resist composition according to any one of (1) to (5), wherein the acrylic polymer (B) has an ethylenically unsaturated group in a side chain.
(7) The photosensitive resist composition according to any one of (1) to (6), wherein the pigment (A) is titanium black and / or carbon black.
(8) A color filter using the photosensitive resist composition according to any one of (1) to (7).

  When the photosensitive resist composition for a color filter according to the present invention is used, a color filter having good pattern shape and sensitivity can be produced without generating a pigment residue on the substrate during development, and a liquid crystal display device. Reliability can be increased and yield can be improved.

Hereinafter, the components of the present invention will be described.
In the present invention, an organic pigment or an inorganic pigment is used as the pigment (A).
Examples of such pigments include compounds classified as pigments in Color Index CI (published by The Society of Dyers and Colorists). As a specific example, as a red pigment, Color Index No. Pigment Red (hereinafter abbreviated as PR) 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 254, and the like, and Color Index No. Pigment Green (hereinafter abbreviated as PG) 7, 36, and the like, as a blue pigment, Color Index No. Pigment Blue (hereinafter abbreviated as PB) 15: 3, 15: 4, 15: 6, 21, 22, 60, 64, and the like, and Color Index No. Pigment Yellow (hereinafter abbreviated as PY) 20, 24, 86, 93, 109, 110, 117, 129, 138, 139, 150, 153, and the like, and Color Index No. Pigment Violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 37, 40, 50, and the like are Color Index No. Pigment Orange (hereinafter abbreviated as PO) 36, 43, 51, 55, 59, 61 and the like are Color Index No. Pigment black 7 or the like, carbon black, titanium black, metal oxide, or the like can be used. These pigments may be used alone or in combination of two or more. In addition, pigment derivatives such as sulfonic acids of pigments obtained by sulfonated organic pigments, specifically sulfonic acids of copper phthalocyanine, sulfonic acids of diketopyrrolopyrrole (PR254), sulfonic acids of quinophthalone (PY138), etc. When added in an amount of 0.5 to 10% by mass, preferably 2 to 7% by mass, there is an effect of stabilizing the dispersion of the pigment, which is preferable. Furthermore, it is preferable to use a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, or a polyallylamine polymer dispersant in combination at the time of dispersion because of the effect of stabilizing the dispersion. Since these polymer dispersants do not have photosensitivity, there is a concern that the photosensitivity of the target color resist may be deteriorated if added in a large amount. Therefore, an appropriate addition amount considering dispersion stability and photosensitivity is required. Is desirable. In particular, when the polyethyleneimine polymer dispersant or polyallylamine polymer dispersant is added to the pigment in an amount of 5 to 50 (mass%), more preferably 7 to 40 (mass%), the photosensitive performance is not deteriorated. Furthermore, there is an effect of highly stabilizing dispersion, which is even more preferable. These polymer dispersants include “Solspers (registered trademark)” 24000 (or 24000SC, 32500, 33500) manufactured by Abyssia Co., Ltd., “EFKA (registered trademark)” 4047 (or 4046) manufactured by Efka, and Ajinomoto Fine Techno. It is commercially available under trade names such as “Azisper (registered trademark)” PB821 (or PB822 etc.) manufactured by KK

The composition of the present invention is particularly effective when a green pixel or a resin black matrix (hereinafter referred to as resin BM) having a high pigment ratio in the coating film is formed. As the pigment for the resin BM, a mixture of a red pigment and a blue and / or violet pigment, titanium black, and carbon black are preferable. In particular, when forming the resin BM, when titanium black is used, a material excellent in photosensitive characteristics such as sensitivity during exposure can be obtained. Among titanium blacks, those having a high titanium nitride content are more preferable because high optical density (OD) can be obtained with the same film thickness. In addition, when titanium black and carbon black are mixed in a mass ratio of 50 ± 10% by mass, the transmitted color of the coating film is not bluish (titanium black color) or yellow (carbon black color) and close to neutral (neutral). Therefore, it is particularly suitable as a resin BM. Carbon black preferably has a primary particle diameter of 10 to 80 nm and its surface is oxidized with hypochlorous acid, nitric acid, hydrogen peroxide, or the like. In particular, those having an acid value of 1 to 30 (mgKOH / g), more preferably 5 to 25 (mgKOH / g) are preferable in terms of adhesion and solubility during development.
In the present invention, the acrylic polymer (B) is an essential component, but an acrylic polymer having a carboxyl group is preferably used as the acrylic polymer (B). As the acrylic polymer having a carboxyl group, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid and the like.

  These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, methacryl Isopropyl acrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, polystyrene having a methacryloyl group, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and the like can be mentioned. Not shall. In particular, a quaternary copolymer selected from methacrylic acid and / or acrylic acid and methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene has an average molecular weight Mw of 2,000 to 100,000, an acid value of 50 to 150 (mgKOH / The polymer g) is preferred from the viewpoint of solubility in an alkali developer. Outside this range, the dissolution rate in the alkaline developer is undesirably lowered or increased too much.

  Further, when an acrylic polymer having an ethylenically unsaturated group in the side chain is used, the sensitivity at the time of exposure and development is improved, so that it can be preferably used. As an ethylenically unsaturated group, an acryl group and a methacryl group are preferable. Such an acrylic polymer can be subjected to an addition reaction of an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to a carboxyl group of an acrylic (co) polymer having a carboxyl group.

  Specific examples of the acrylic polymer having an ethylenically unsaturated group in the side chain include a copolymer described in Japanese Patent No. 3120476, JP-A-8-262221, or a commercially available acrylic polymer. Examples thereof include curable resin “Cyclomer (registered trademark) P” (Daicel Chemical Industries, Ltd.), alkali-soluble cardo resin, and the like. In particular, an acrylic polymer having an ethylenically unsaturated group in the side chain has an average molecular weight (Mw) of 2,000 to 100,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier, and using a standard polystyrene calibration curve) The polymer having an acid value of 70 to 150 (mg KOH / g) is most preferable from the viewpoints of photosensitive characteristics, solubility in an ester solvent, and solubility in an alkali developer.

  In the present invention, the monomer (C) is obtained by reacting a bisphenolfluorene type epoxy compound or a bisphenol type epoxy compound with an ethylenically unsaturated group-containing compound having a functional group capable of reacting with an epoxy group, and a hydroxyl group of the resulting product. It is synthesized by further reacting a reactive compound.

  The monomer (C) is particularly represented by the following general formula (1) and / or general formula (2).

(In the formula, R ¹ , R ⁴ and R ⁵ represent a hydrogen atom or a methyl group, R ² represents an arbitrary organic group. R ³ may have a substituent and has 1 to 10 carbon atoms. An alkyl group, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group, a cycloalkyl having 5 to 12 carbon atoms, an aryl group or arylene group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms are represented. It is an integer of -10.)
Here, the alkyl group for R ³ preferably has 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, or a propylene group. N is an integer of 0 to 10, preferably 0 to 5, and more preferably 0 to 2.

R ² represents a substituent represented by the following general formula (3).

(In the formula, R ⁶ is represented by any one of an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group, and these may have a substituent.)
Here, the alkyl group of R ⁶ preferably has 1 to 10 carbon atoms, the alkenyl group preferably has 2 to 10 carbon atoms, and the cycloalkenyl group has 3 to 10 carbon atoms. preferable. Further, the aryl group preferably has 6 to 15 carbon atoms, and among them, the aryl group is preferable in the present invention. Preferred examples include methyl group, ethyl group, methoxy group, ethoxy group, ethynyl group, propynyl group, phenol group, benzoyl group, toluyl group and the like.

  As other components, polyfunctional and monofunctional acrylic monomers or oligomers can be used. Examples of the polyfunctional monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylate, anhydrous Phthalic acid propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, alkyd modified (meth) acrylate, or tripropylene glycol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythri Tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2-bis [4- (3-acryloxy-2 -Hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3 -Acryloxy-2-hydroxypropoxy) phenyl] ether, 4,4'-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2- Hydroxypropoxy ) Phenyl] fluorene, 9,9-bis [3-methyl-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- (3-acryloxy-2- Hydroxypropoxy) phenyl] fluorene, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol full orange acrylate, biscresol full orange methacrylate and the like.

  Further, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, tris-[(mercaptopropionyloxy) -ethyl] -isocyanate Examples thereof include nurate or polyfunctional thiol compounds such as bisfluorene-based thiol compounds described in JP-A-2006-259716. These can be used alone or in combination.

  By selecting and combining these polyfunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the resist. In particular, in order to increase sensitivity, it is desirable to use a compound having 3 or more, more preferably 5 or more functional groups, and dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable. In addition, when using a pigment that absorbs ultraviolet rays effective for photocrosslinking, such as resin BM, in addition to dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, the polyfunctional thiol compound, In particular, the combined use of an isocyanurate-based polyfunctional thiol compound or a polyfunctional thiol compound having a fluorene ring having a high aromatic ring in the molecule and high water repellency is more preferable because the pattern can be controlled to a desired shape during development.

  The photosensitive color resist composition for a color filter of the present invention contains a photoinitiator (D) represented by the general formula (4), which is a carbazole compound, as an essential component.

(In the formula, R ⁷ represents a hydrogen atom or a monovalent organic group, and R ⁸ is represented by a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.)
More preferred monovalent organic groups include substituents represented by the following general formula (5) or (6).

Further, a compound represented by the following general formula (7) or (8) wherein R ⁷ is represented by the substituent of the above general formula (5) or (6) and R ⁸ is a methyl group is particularly preferred.

Further, the photoinitiator in the present invention may contain other photoinitiators in addition to the above-mentioned photoinitiator that is an essential component, and specifically includes benzophenone compounds, acetophenone compounds, oxanthone compounds, and imidazole compounds. , Known compounds such as benzothiazole compounds, benzoxazole compounds, oxime ester compounds, carbazole compounds, triazine compounds, phosphorus compounds, and titanates can be used. For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl Ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, Ciba Specialty Chemical “Irgacure (registered trademark)” 369, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, Ciba Specialty Chemical Co., Ltd. CGI-113 2- [4-Methylbenzyl] -2-dimethylamino-1- (4-morpholinophenyl) -butanone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methyl Anthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4 , 5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” OXE01 1,2-octanedione, 1- [4 -(Phenylthio) -2- (O-benzoyl) Oxime)], 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine and the like.

  Two or more kinds of the above photoinitiators can be used in combination with a carbazole-based compound as an essential component. As a preferable specific example, N, N′-tetraethyl-4,4′-diaminobenzophenone and Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered)” are added to the carbazole photoinitiator represented by (7) or (8). (Trademark) "369" or Ciba-Specialty Chemical Co., Ltd. CGI-113 is preferred because a photosensitive resist composition for a color filter having high sensitivity and good pattern shape can be obtained. The addition amount of the photoinitiator is not particularly limited, but is preferably 2 to 50% by mass and more preferably 10 to 50% by mass with respect to the total solid content of the color resist.

  In the photosensitive resist composition for a color filter of the present invention, the resin component (total of polymer, monomer or oligomer and polymer dispersant) and the colorant containing at least the pigment are usually 20% by mass to 95% of the resin component. It is used by mixing in the range of mass%, preferably 25 mass% to 80 mass%. If the amount of the resin component is too small, the adhesion of the colored film to the substrate becomes poor. Conversely, if the amount of the pigment is too small, the color density or the optical density per unit thickness (OD value / μm) in the case of the resin BM. It becomes low and becomes a problem.

  The solvent (E) of the photosensitive resist composition for a color filter of the present invention will be described. As the solvent (E) used in the present invention, esters, aliphatic alcohols, ketones and the like can be used.

  Specific esters include benzyl acetate (boiling point 214 ° C.), ethyl benzoate (boiling point 213 ° C.), γ-butyrolactone (boiling point 204 ° C.), methyl benzoate (boiling point 200 ° C.), diethyl malonate (boiling point 199 ° C.), 2-ethylhexyl acetate (bp 199 ° C.), 2-butoxyethyl acetate (bp 192 ° C.), 3-methoxy-3-methyl-butyl acetate (bp 188 ° C.), diethyl oxalate (bp 185 ° C.), ethyl acetoacetate ( Boiling point 181 ° C.), cyclohexyl acetate (bp 174 ° C.), 3-methoxy-butyl acetate (bp 173 ° C.), methyl acetoacetate (bp 172 ° C.), ethyl-3-ethoxypropionate (boiling point 170 ° C.), 2- Ethyl butyl acetate (boiling point 162 ° C), isopentyl propio (Boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), pentyl acetate (boiling point 150 ° C), propylene glycol monomethyl ether acetate (boiling point 146 ° C) ) And the like, but is not limited thereto.

  Among these solvents, acetate-type or propionate-type solvents include 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and 3-methoxy-butyl. Particularly preferred are acetate and propylene glycol monomethyl ether acetate.

  In addition to the above solvents, propylene glycol monomethyl ether (boiling point 120 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), propylene glycol tertiary butyl ether (boiling point 153 ° C.), dipropylene glycol monomethyl ether (boiling point 188 ° C.) Aliphatic ethers such as propylene glycol derivatives such as, aliphatic esters other than those described above, for example, ethyl acetate (boiling point 77 ° C.), butyl acetate (boiling point 126 ° C.), isopentyl acetate (boiling point 142 ° C.), or butanol ( Boiling point 118 ° C.), aliphatic alcohols such as 3-methyl-2-butanol (boiling point 112 ° C.), 3-methyl-3-methoxybutanol (boiling point 174 ° C.), ketones such as cyclopentanone and cyclohexanone, xylene ( Boiling point 14 ° C.), ethyl benzene (boiling point 136 ° C.), solvent naphtha (petroleum fraction: it is also possible to use a solvent such as boiling point 165 to 178 ° C.).

  Furthermore, since application by a die coating apparatus has become mainstream with the increase in the size of the substrate, it is preferable to use a mixed solvent of two or more components in order to achieve appropriate volatility and drying properties. When the boiling points of all the solvents constituting the mixed solvent are 150 ° C. or less, film thickness uniformity cannot be obtained, the film thickness of the coating end part is increased, and the pigment is applied to the base part for discharging the coating liquid from the slit. Aggregates are formed, causing many problems that streaks occur in the coating film. On the other hand, when the mixed solvent contains a large amount of solvent having a boiling point of 200 ° C. or higher, the surface of the coating film becomes sticky and sticking occurs. Therefore, a mixed solvent containing 30 to 75% by mass of a solvent having a boiling point of 150 ° C. or higher and 200 ° C. is desirable. In particular, as one component of the solvent constituting the mixed solvent, an ester solvent selected from 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and 3-methoxy-butyl acetate Is preferably a mixed solvent containing 30 to 75% by mass.

  Furthermore, it is more preferable to select 3-methoxy-3-methyl-butyl acetate as a component of the mixed solvent because the viscosity of the color resist solution can be increased at the same solid content concentration as compared with other esters.

  The photosensitive resist composition of the present invention may contain various additives as necessary, for example, additives such as adhesion improvers, antioxidants, ultraviolet absorbers, thermal polymerization inhibitors, and aggregation inhibitors. . Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-2 (aminoethyl) as adhesion improvers ) 3-Aminopropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane 2,2-methylenebis- (6-t-butyl-4-methylphenol, 4,4-thiobis- (2-t-butyl-5-methylphenol) and the like as antioxidants are thermal polymerization inhibitors. As hydroquinone, p-me Xylphenol, benzoquinone, di-t-butyl-p-cresol and the like, and 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole and the like as ultraviolet absorbers, Examples of the aggregation inhibitor include sodium polyacrylate.

  These contents are preferably 0.2 to 20% by mass, more preferably 0.5 to 5% by mass, based on the total solid content of the color resist.

  A surfactant can also be added to the photosensitive resist composition for color filters used in the present invention for the purpose of coating properties, smoothness of the colored coating and Benard cell. The addition amount of the surfactant is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass of the pigment. If the amount added is too small, the coating properties, smoothness of the colored coating and Benard cell are not effective, and if too large, the physical properties of the coating film may be poor. Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, and silicones based on polydimethylsiloxane Surfactants, fluorosurfactants and the like can be mentioned. In the present invention, the surfactant is not limited to these, and one or more surfactants can be used.

  The photosensitive resist composition for a color filter of the present invention has a solid content (a ratio of all components other than the solvent contained in the color resist to the color resist solution) of 5 to 30% by mass, more preferably 7 to 25% by mass. A range is desirable. When the viscosity is measured at 25 ° C., the molecular weight of the polymer and / or the type and amount of the solvent are adjusted so that the viscosity is in the range of 1 to 40 (mPa · s), preferably in the range of 2 to 20 (mPa · s). Thus, the coating film can be made more uniform, which is desirable.

The example of the manufacturing method of the color filter by the die coating apparatus using the photosensitive resist composition for color filters of this invention is demonstrated. As the substrate, a transparent substrate such as soda glass, non-alkali glass, or quartz glass is usually used, but is not particularly limited thereto. Examples of the die coating apparatus include a single wafer coating apparatus disclosed in Japanese Patent No. 3139358 and Japanese Patent No. 3139359. With this apparatus, the color resist can be applied onto the substrate by discharging the photosensitive resist composition (coating solution) for the color filter of the present invention from the die and moving the substrate. In this case, since a large number of substrates are applied in a single sheet, when the apparatus is operated for a long time, agglomerates of pigments are formed in the base part for discharging the coating liquid from the slits, which may cause a coating defect and reduce the yield. In this case, by providing a step of wiping the base, which is a discharge port of the apparatus, with a solvent containing 40% by mass or more of the ester solvent having a boiling point of 150 ° C. or higher with respect to the total solvent, the coating defects are eliminated and the base is removed. The rate is improved. After the color resist is applied on the substrate as described above, the solvent is removed by air drying, reduced pressure drying, heat drying or the like to form a color resist coating film. In particular, after providing a vacuum drying step, additional heating and drying in an oven or a hot plate eliminates coating defects caused by convection and improves the yield. The drying under reduced pressure is preferably performed in the range of normal temperature to 100 ° C., 5 seconds to 10 minutes, and a degree of vacuum of 500 to 10 (Pa), and more preferably a pressure of 150 to 50 (Pa). Heat drying is preferably performed using an oven, a hot plate or the like at a temperature of 50 to 120 ° C. for 10 seconds to 30 minutes.
Subsequently, a mask is placed on the coating and irradiated with ultraviolet rays using an exposure apparatus. Next, development is performed with an alkaline developer. It is preferable to use an alkaline developer added with 0.1 to 5% of a surfactant such as a nonionic surfactant because a better pattern can be obtained. Although it does not specifically limit as an alkaline substance used for an alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n- Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines, pyrrole, piperidine, 1,8-dia Bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, organic alkalis such as cyclic amines such as morpholine.

  The concentration of the alkaline substance is 0.01% by mass to 50% by mass. Preferably it is 0.02 mass% to 10 mass%, More preferably, it is 0.02 to 1 mass%. In the case where the developer is an alkaline aqueous solution, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone may be appropriately added to the developer.

Among these developers, an aqueous developer of an alkaline aqueous solution is preferable from the viewpoint of working environment and waste developer treatment.
The development method uses an immersion method, a spray method, a paddle method or the like, but is not particularly limited. After development, a washing process with pure water or the like is added.

  The resulting color resist coating film pattern is then subjected to heat treatment (post-baking) to become a colored filter patterned. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at 150 to 300 ° C, preferably 180 to 250 ° C, continuously or stepwise for 0.25 to 5 hours. Done.

  A color filter for a liquid crystal display device can be prepared by forming a colored pattern successively and repeatedly using the photosensitive resist composition for black, red, green and blue color filters of the present invention by the above method. Here, the patterning order of each color resist is not limited.

  Further, after the manufacturing method of the present invention, a protective film and a transparent conductive film can be formed on the pixel.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Evaluation method and criteria)
1. Pigment residue The unexposed part of the substrate after development post-baking (the part where the pattern is not formed) is wiped by reciprocating twice using "Toraysee (registered trademark)" manufactured by Toray Industries, Ltd., which has been moistened with ethanol. The degree of was investigated. The evaluation criteria were as follows.
○: No coloring, Δ: Lightly colored, ×: Clearly colored Pattern shape About the pattern shape after exposure, development and post-baking (220 ° C. × 30 minutes), planar observation (presence of meandering) using an optical microscope (Olympus Sales Co., Ltd., BH3-MJL) was performed using a scanning electron microscope. Cross-section observation (taper shape) was performed using (S-4800, manufactured by Hitachi, Ltd.).

In cross-sectional observation, the lower width and the upper width were equal, or the lower width was wider than the upper width, and the lower taper was narrower than the upper width, and the reverse taper was lower. A pattern having no forward meandering and a forward taper was determined as a good pattern, and the determination was made according to the following criteria.
◎: Observed about 10 patterns, all are forward tapered and no meandering ○: Observed about 10 patterns, meandering is seen, but the meandering width is all 2 μm or less, and becomes a forward tapered shape 1. What is observed: 10 patterns are observed, and even one meander having a width of 2 μm or more can be seen or reversely tapered. Sensitivity Shows the minimum required exposure required to form a pattern that does not become rough even when developed. Through a photomask (HOYA Co., Ltd., negative mask), the coating film is exposed to ultraviolet rays (at 365 nm) with a maximum exposure amount of 200 mJ / cm ² and the exposure amount is reduced as needed. The minimum exposure amount in a range where no roughening occurs was defined as the minimum required exposure amount.

Reference example 1
Synthesis of acrylic polymer (P1) having carboxyl group and methacryl group in side chain According to the method described in Example 1 of Japanese Patent No. 3120476, methyl methacrylate / methacrylic acid / styrene copolymer (weight composition ratio 30/40 / 30), after adding 40 parts by weight of glycidyl methacrylate, reprecipitation with purified water, filtration and drying, an acrylic polymer having characteristics of an average molecular weight (Mw) of 10,000 and an acid value of 50 (mgKOH / g) ( P1) A powder was obtained.

Reference example 2
A 500 ml separable flask is charged with 296 g of bisphenoxyethanol fluorenediglycidyl ether (epoxy equivalent 296 g / eq), 3.4 g of dimethylbenzylamine, 0.35 g of p-methoxyphenol and 72 g of acrylic acid, and air at a flow rate of 20 ml / min. The temperature was raised while blowing, and the reaction was carried out at a temperature of 110 to 120 ° C. During this time, the acid value was measured, and heating and stirring were continued until it became less than 2.0 mgKOH / g. It took 10 hours for the acid value to reach the target. As a result, bisphenolfluorene acrylate (A1) (hydroxyl equivalent 368 g / eq) was obtained.

Synthesis example 1
A 300 ml separable flask was charged with 100 g of the bisphenolfluorene acrylate (A1) prepared in Reference Example 2, 150 g of 3-methoxy-3-methyl-butyl acetate and 28.8 g of triethylamine, dissolved, and then benzoyl chloride 38. 2 g was slowly added dropwise. The mixture was reacted at room temperature for 2 hours, and the resulting white precipitate was filtered using a filter to obtain compound (A2).

Synthesis example 2
A 300 ml separable flask was charged with 100 g of the compound (A1) prepared in Reference Example 2, 130 g of 3-methoxy-3-methyl-butyl acetate, and 20 g of acrylic acid, and dissolved in a part of the solvent. 55.7 g of dicyclohexylcarbodiimide was added slowly. The mixture was reacted at room temperature for 3 hours, and the resulting white precipitate was filtered with a filter to obtain compound (A3).

Synthesis example 3
In Synthesis Example 2, compound (A4) was obtained in the same manner as in Production Example (A3) except that 20 g of acrylic acid was changed to 16 g of acetic acid.

Reference example 3
A 500 ml separable flask is charged with 231 g of bisphenol fluorenediglycidyl ether (epoxy equivalent 231 g / eq), 3.0 g of dimethylbenzylamine, 0.30 g of p-methoxyphenol and 72 g of acrylic acid, and air is supplied at a flow rate of 20 ml / min. The temperature was raised while blowing, and the reaction was carried out at a temperature of 110 to 120 ° C. The same operation as in Reference Example 2 was performed to obtain bisphenolfluorene acrylate (B1) (hydroxyl equivalent: 303 g / eq).

Synthesis example 4
In a 300 ml separable flask, 100 g of the compound (B1) prepared in Reference Example 3, 150 g of 3-methoxy-3-methyl-butyl acetate and 35.1 g of triethylamine were added and dissolved, and then 46.4 g of benzoyl chloride was added dropwise. Slowly added. The mixture was reacted at room temperature for 2 hours, and the resulting white precipitate was filtered using a filter to obtain compound (B2).

Synthesis example 5
A 300 ml separable flask was charged with 100 g of the compound (B1) prepared in Reference Example 3, 140 g of 3-methoxy-3-methyl-butyl acetate and 24 g of acrylic acid, and N, N′— dissolved in a part of the solvent. 68.1 g of dicyclohexylcarbodiimide was added slowly. The reaction was allowed to proceed at room temperature for 3 hours, and the resulting white precipitate was filtered through a filter to obtain compound (B3).

Reference example 4
A 500 ml separable flask is charged with 258 g of biscresol fluorenediglycidyl ether (epoxy equivalent 258 g / eq), 3.3 g of dimethylbenzylamine, 0.33 g of p-methoxyphenol and 72 g of acrylic acid, and air at a flow rate of 20 ml / min. The temperature was raised while blowing, and the reaction was carried out at a temperature of 110 to 120 ° C. The same operation as in Reference Example 2 was performed to obtain bisphenolfluorene acrylate (C1) (hydroxyl equivalent: 330 g / eq).

Synthesis Example 6
A 300 ml separable flask was charged with 100 g of the compound (C1) prepared in Reference Example 4, 150 g of 3-methoxy-3-methyl-butyl acetate and 32.2 g of triethylamine, dissolved, and then 42.6 g of benzoyl chloride was added dropwise. Slowly added. The mixture was reacted at room temperature for 2 hours, and the resulting white precipitate was filtered using a filter to obtain compound (C2).

Reference Example 5
A 500 ml separable flask is charged with 185 g of bisphenol A type epoxy compound (epoxy equivalent 185 g / eq), 2.6 g of dimethylbenzylamine, 0.26 g of p-methoxyphenol and 72 g of acrylic acid, and air is supplied at a flow rate of 20 ml / min. The temperature was raised while blowing, and the reaction was carried out at a temperature of 110 to 120 ° C. The same operation as in Reference Example 2 was performed to obtain bisphenolfluorene acrylate (D1) (hydroxyl equivalent: 257 g / eq).

Synthesis example 7
A 300 ml separable flask was charged with 100 g of the compound (D1) prepared in Reference Example 5, 150 g of 3-methoxy-3-methyl-butyl acetate and 41.3 g of triethylamine, dissolved, and then 54.7 g of benzoyl chloride was added dropwise. Slowly added. The mixture was reacted at room temperature for 2 hours, and the resulting white precipitate was filtered using a filter to obtain compound (D2).

Example 1
65 g of titanium black 13M-T (titanium nitride) manufactured by Mitsubishi Materials Corporation, 105 g of acid-treated carbon black manufactured by Daido Kasei Co., Ltd., propylene glycol monomethyl ether of “Azisper (registered trademark)” PB821 manufactured by Ajinomoto Fine Techno Co., Ltd. Acetate 20 mass% solution 63 g Acrylic polymer (P1) 3-methoxy-3-methylbutanol 56 g 45 mass% solution, propylene glycol monomethyl ether acetate 560 g and propylene glycol tertiary butyl ether 150 g were weighed and filled with zirconia beads. Using a mill type disperser, dispersion was performed at 2000 rpm for 3 hours to obtain a pigment dispersion (TCB1) having a pigment concentration of 16.84% by mass. To 596 g of this pigment dispersion (TCB1), 6.1 g of a 45% by weight 3-methoxy-3-methylbutanol solution of acrylic polymer (P1), 3 of the bisphenoxyethanol fluorene acrylate type compound (A2) obtained in Synthesis Example 1 -46.9 g of 50% by weight solution of methoxy-3-methyl-butyl acetate, 13.6 g of 50% by weight solution of propylene glycol monomethyl ether acetate of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA) as a polyfunctional monomer CGI-113 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.37 g as a photoinitiator, 14.7 g of a carbazole photoinitiator represented by (7) or (8) and N, N′-tetraethyl- 1.9 g of 4,4′-diaminobenzophenone as an adhesion improver 3-methyl-3-methoxy was added to 2.7 g of a propylene glycol monomethyl ether acetate 50% by mass solution of KBM1003 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 2.7 g of a 10% by mass propylene glycol monomethyl ether acetate solution of a silicone surfactant. -A solution dissolved in a mixed solvent of butyl acetate and propylene glycol monomethyl ether acetate was added and mixed to prepare a black color resist.

The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter, and then applied onto a non-alkali glass substrate with a die coating device so that the film thickness was 1 μm (after post-baking). The coating speed was 3 m / min. The coated substrate is dried under reduced pressure (100 Pa) and then heat-treated for 2 minutes on a hot plate at 90 ° C. to produce a color resist coating film. The coating film is exposed to ultraviolet rays of 200 mJ / cm ² through a resolution test mask. Exposed in quantity.

  Next, in the 0.04 mass% KOH aqueous solution, “Emulgen (registered trademark)” A-60 (HLB12.8, polyoxyethylene derivative) (manufactured by Kao Corporation) as a nonionic surfactant was added to the total amount of the developer On the other hand, a patterning substrate was obtained by spray development with an alkaline developer added in an amount of 0.2% 1.7 times the time required for the unexposed portion to dissolve, followed by washing with pure water. The obtained patterning substrate was held in a hot air oven at 230 ° C. for 30 minutes and post-baked to obtain a patterning substrate. The substrate was examined for the pigment residue, sensitivity, and post-baked pattern shape according to the evaluation method and evaluation criteria. The results are shown in Table 1.

Examples 2-7, Comparative Examples 1-4
A black color resist was prepared in the same manner as in Example 1 except that the type of monomer component in Example 1 was changed to (A3) to (D2) instead of the compound (A2). Evaluation similar to Example 1 was performed about the obtained photosensitive resin composition. The results are shown in Table 1.

  From the comparison between Examples 1 to 7 and Comparative Examples 1 to 4, when the compound shown in the present invention is used for the acrylate compound having a fluorene skeleton or a bisphenol type structure, (A1), (B1), (C1) having a hydroxyl group , (D1), the generation of residues as seen when using (D1) is eliminated, and a better pattern shape can be obtained. In particular, when the compound (A2) is used, a resist composition having the best sensitivity can be obtained.

Comparative Example 5
In Example 1, 1- (4-phenyl-thiophenyl) -octane-1,2-dione-2-oxime-0, which is CGI-124 (manufactured by Ciba Specialty Chemical Co., Ltd.), is used as the initiator component. -A photosensitive resin composition was prepared in the same manner as in Example 1 except that the amount was changed to 14.7 g of benzoate. The evaluation results are shown in Table 1.

  Comparing Comparative Example 5 with the case of using the carbazole photoinitiator represented by (7) or (8), the system using the carbazole photoinitiator is very high about 10 times or more of Comparative Example 5. It turns out that it has sensitivity.

Example 8
240 g of acid-treated carbon black 9930CF manufactured by Daido Kasei Co., Ltd., 120 g of a 20 mass% propylene glycol monomethyl ether acetate solution of “Solsperse (registered trademark)” 24000 (manufactured by Abyssia Co., Ltd.) 3-methoxy- 160 g of 45% by mass solution of 3-methylbutanol and 980 g of propylene glycol monomethyl ether acetate are weighed and dispersed for 3 hours at 2000 rpm using a mill type disperser filled with zirconia beads, and a pigment dispersion having a pigment concentration of 16% by mass (CB1) was obtained. To 543 g of this pigment dispersion (CB1), 23.1 g of a 45% by weight 3-methyl-3-methoxybutanol solution of acrylic polymer (P1), bisphenoxyethanol full orange acrylate type compound (A2) 43. 6 g, 15.6 g of a propylene glycol monomethyl ether acetate 50 mass% solution of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA) as a polyfunctional monomer, CGI-113 (Ciba Specialty Chemical) as a photopolymerization initiator 2.3 g, 14.1 g of the carbazole photoinitiator represented by (8) and 2.3 g of N, N′-tetraethyl-4,4′-diaminobenzophenone, and KBM403 ( Propylene glycol monomethy from Shin-Etsu Chemical Co., Ltd. 2.7 g of a 50% by weight ether acetate solution and 2.7 g of a 10% by weight propylene glycol monomethyl ether acetate solution of a silicone surfactant were mixed with 95.3 g of 3-methyl-3-methoxy-butyl acetate and 3-methyl-3-methoxy. A solution dissolved in 199.6 g of butanol was added and mixed to prepare a black color resist.
The prepared color resist was filtered through a 2 μm Teflon (registered trademark) filter, and then applied onto a non-alkali glass substrate with a die coating device so that the film thickness was 1 μm (after post-baking). Thereafter, a patterned substrate was obtained in the same manner as in Example 1. The substrate was examined for the pigment residue, sensitivity, and post-baked pattern shape according to the evaluation method and evaluation criteria. The results are shown in Table 1.

Comparative Example 6
In Example 8, the photosensitive resin composition was produced by the same operation as Example 8 except having changed the kind of monomer component into (A1) instead of the compound (A2). The evaluation results are shown in Table 1.

Comparative Example 7
In Example 8, 1- (4-phenyl-thiophenyl) -octane-1,2-dione-2-oxime-0 which is CGI-124 (manufactured by Ciba Specialty Chemical Co., Ltd.) is used as the initiator component. -A photosensitive resin composition was prepared in the same manner as in Example 8 except that 14.1 g of benzoate was used. The evaluation results are shown in Table 1.
Even in the system of carbon alone, residues frequently occurred in Comparative Example 6 using (A1), but in the case of Example 8 using (A2), no residue was found as in the mixed system of titanium and carbon. The shape was also good. Further, in Example 8 and Comparative Example 6 (when a carbazole photoinitiator is used), very high sensitivity is obtained as compared with Comparative Example 7.

Claims (8)

In a photosensitive resist composition containing at least a pigment (A), an acrylic polymer (B), a monomer (C), a photoinitiator (D), and a solvent (E), the monomer (C) has the following general formula: A photosensitive resist composition which is a compound represented by (1) and / or general formula (2).

(In the formula, R ¹ , R ⁴ and R ⁵ represent a hydrogen atom or a methyl group, R ² represents an arbitrary organic group. R ³ may have a substituent and has 1 to 10 carbon atoms. It represents an alkylene group, an alkenylene group or alkynylene group having 2 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, an arylene group having 6 to 14 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, where m is 0 to 10. And n is an integer of 1 to 20.) The photosensitive resist composition according to claim 1, wherein R ² is a substituent represented by the following general formula (3).

(In the formula, R ⁶ is represented by any one of an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group, and these may have a substituent.) The photosensitive resist composition according to claim 1, wherein the photoinitiator (D) contains a compound represented by the following general formula (4) as an essential component.

(In the formula, R ⁷ represents a hydrogen atom or a monovalent organic group, and R ⁸ is represented by a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.) The photosensitive resist composition according to claim 3, wherein the monovalent organic group is a substituent represented by the following general formula (5) or (6).

The photosensitive resist composition according to claim 1, wherein the acrylic polymer (B) has a carboxyl group. The photosensitive resist composition according to claim 1, wherein the acrylic polymer (B) has an ethylenically unsaturated group in a side chain. The photosensitive resist composition according to claim 1, wherein the pigment (A) is titanium black and / or carbon black. A color filter using the photosensitive resist composition according to claim 1.