TW201635028A - Photosensitive coloring resin composition, black matrix, color filter, and display element - Google Patents

Abstract

The objective of the present invention is to provide a photosensitive coloring resin composition that has excellent coating properties and is capable of reducing the load on the environment. The objective of the present invention is to further provide a black matrix, a color filter, and a display element which are obtained by using the photosensitive coloring resin composition. The present invention is a photosensitive coloring resin composition that contains: a water-soluble and alkali-soluble polymer compound having a segment derived from at least one substance selected from the group consisting of carboxylic acids, dicarboxylic acid anhydrides, and carboxylates; a compound having a molecular weight of 1000 or less and having a polymerizable unsaturated double bond and a hydroxyl group; a photopolymerization initiator; a black pigment; and water.

Description

Colored photosensitive resin composition, black matrix, color filter, and display element

The present invention relates to a colored photosensitive resin composition which is excellent in coatability and which can reduce the load on the environment. Further, the present invention relates to a black matrix, a color filter, and a display element which are obtained by using the colored photosensitive resin composition.

In order to improve display contrast and color rendering effect, a display matrix such as a liquid crystal display element is provided with a black matrix at a boundary portion between the color layers of R, G, and B of the color filter, and is used as a material for the black matrix in recent years. A colored photosensitive resin composition of a black pigment or dye.

As such a coloring photosensitive resin composition, a photocurable resin containing a film which is cured by irradiation with light to form a film is usually used. In other words, a colored photosensitive resin composition applied to the surface of a transparent substrate such as a glass substrate is placed with a mask in which a portion that transmits light and a portion that does not transmit light are placed, and light is irradiated from above the mask. The colored photosensitive resin composition of the portion irradiated with light is cured, and the uncured colored photosensitive resin composition remaining in the portion where the light is not transmitted is removed to form a film of a desired shape.

As a coloring photosensitive resin composition, for example, Patent Document 1 and 2 disclose a light-shielding black photoresist composition containing a binder resin and having a molecule in the molecule. a compound having one less polymerizable unsaturated double bond, a photopolymerization initiator, a black pigment, a solvent, and a thiol compound having a specific structure; and Patent Document 3 discloses a photopolymerizable unsaturated compound having a specific structure. a photopolymerization initiator, a color material, and a solvent-colored alkali-developable photosensitive resin composition; and Patent Document 4 discloses a polymer having thermoplastic or uncrosslinked polymer and/or having ethylenic unsaturation A photosensitive composition of a bond compound, a specific photopolymerization initiator, a pigment, and a solvent.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-325734

Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-325735

Patent Document 3: International Publication No. 2008/139924

Patent Document 4: Japanese Laid-Open Patent Publication No. 2003-252918

An object of the present invention is to provide a colored photosensitive resin composition which is excellent in coatability and can reduce the load on the environment. Moreover, an object of the present invention is to provide a black matrix, a color filter, and a display element which are obtained by using the colored photosensitive resin composition.

The present invention relates to a colored photosensitive resin composition comprising: a water-soluble and alkali-soluble polymer compound, a compound having a molecular weight of 1,000 or less and having a polymerizable unsaturated double bond and a hydroxyl group, a photopolymerization initiator, a black pigment, And water, the water solubility and high alkali solubility The molecular compound has a segment derived from at least one selected from the group consisting of a carboxylic acid, a dicarboxylic anhydride, and a carboxylate.

Hereinafter, the present invention will be described in detail.

Since the conventional colored photosensitive resin composition disclosed in Patent Documents 1 to 4 contains an organic solvent, there is a possibility that the organic solvent volatilized by drying is released into the environment, which may impair the health of the operator or cause The problem of environmental pollution. Therefore, the inventors considered reducing the load on the environment by using water instead of such an organic solvent as a solvent. However, the alkali-soluble component or the photocurable component which is conventionally used for coloring a photosensitive resin composition is insoluble in water or extremely insoluble in water, and thus it is not possible to obtain a uniform coating liquid. Therefore, the present inventors have made further efforts to carry out research and found that by combining a specific alkali-soluble polymer compound and a specific photocurable compound, it is possible to form a coating property even when water is used as a solvent. The present invention is excellent in coloring a photosensitive resin composition.

The colored photosensitive resin composition of the present invention contains a water-soluble and alkali-soluble polymer compound having a segment derived from at least one selected from the group consisting of a carboxylic acid, a dicarboxylic anhydride, and a carboxylate. Hereinafter, it is also referred to as "the alkali-soluble polymer compound of the present invention"). The alkali-soluble polymer compound of the present invention exhibits water solubility and alkali solubility by having a chain derived from at least one selected from the group consisting of a carboxylic acid, a dicarboxylic anhydride, and a carboxylate in the molecular chain.

Since the alkali-soluble polymer compound of the present invention is water-soluble, it is not only soluble in water as a solvent, but also has an effect of improving the affinity of a compound having a molecular weight of 1,000 or less and having a polymerizable unsaturated double bond and a hydroxyl group with water. Further, since it is alkali-soluble, it has solubility in an alkaline developing solution for general alkali development which is developed as a photoresist.

In the present specification, the term "water-soluble" as used herein means that an aqueous solution is obtained in a substantially neutral range of pH 6 to pH 9, and the above-mentioned "alkali-soluble" means a pH of 10 to pH 12. An aqueous solution can be obtained in the alkaline range.

Examples of the alkali-soluble polymer compound of the present invention include a copolymer obtained by copolymerizing a carboxyl group-containing monofunctional unsaturated compound with a monofunctional compound having an unsaturated double bond, and a dicarboxylic acid having an unsaturated double bond. A copolymer obtained by copolymerizing an acid compound with a monofunctional compound having an unsaturated double bond, a copolymer obtained by copolymerizing a carboxylate having an unsaturated double bond with a monofunctional compound having an unsaturated double bond, and the like. The copolymers may be any of a random copolymer, a block copolymer, and a graft copolymer.

Further, the alkali-soluble polymer compound of the present invention may be a copolymer obtained by copolymerizing a monofunctional unsaturated compound having a carboxyl group and a monofunctional compound having an unsaturated double bond by a base, or A copolymer obtained by copolymerizing a dicarboxylic acid compound having an unsaturated double bond and a monofunctional compound having an unsaturated double bond is neutralized to prepare a carboxylate.

Examples of the carboxyl group-containing monofunctional unsaturated compound include acrylic acid, methacrylic acid, β-carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, and crotonic acid. Among them, from the viewpoint of crosslinkability and dispersion stability, methacrylic acid or β-carboxyethyl acrylate is preferred.

The dicarboxylic acid compound having an unsaturated double bond may, for example, be maleic anhydride or the like.

Examples of the carboxylate having an unsaturated double bond include acrylic acid, methacrylic acid, β-carboxyethyl acrylate, fumaric acid, itaconic acid, and maleic acid by a weak base such as ammonia. a carboxylate compound obtained by neutralization treatment with crotonic acid or the like.

Examples of the monofunctional compound having an unsaturated double bond include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. 2-ethylhexyl acrylate, hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate A (meth) acrylate monomer such as a ethyl ester, isodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate or benzyl (meth) acrylate.

In the present specification, the above "(meth)acrylic acid" means acrylic acid or methacrylic acid.

As the above base, an amine is preferred.

Examples of the amines include triethylamine, ethanolamine, dimethylethanolamine, diethanolamine, triethanolamine, and ammonia.

Further, the alkali-soluble polymer compound of the present invention may have an aromatic vinyl monomer derived from styrene, α-methylstyrene, p-methylstyrene or p-chlorostyrene, or acrylonitrile or methyl group. A vinyl cyanide compound such as acrylonitrile, or phenyl maleimide, benzyl maleimide, naphthyl maleimide, o-chlorophenyl-butylene Aromatic substitution of maleic acid such as maleimide, or methyl maleimide, ethyl maleimide, propyl maleimide, isopropyl butene A segment such as a quinone imine substituted with a maleimide or the like.

Further, the alkali-soluble polymer compound of the present invention may have a segment derived from a hydroxyl group-containing monofunctional unsaturated compound for the purpose of controlling solubility during development and the like.

Examples of the monofunctional unsaturated compound having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and acrylic acid 4- Hydroxybutyl ester, 4-hydroxybutyl methacrylate, and the like.

The alkali-soluble polymer compound of the present invention is preferably a (meth)acrylic copolymer having a (meth)acryl fluorenyl group and a carboxyl group in a side chain.

In the present specification, the above "(meth)acryl fluorenyl group" means an acryl fluorenyl group or a methacryl fluorenyl group.

The (meth)acrylic copolymer having a (meth)acryl fluorenyl group and a carboxyl group in the side chain is preferably a polymer having at least a constituent unit having an acidic functional group and a constituent unit having a hydroxyl group. The main chain, the (meth)acrylonitrile-containing isocyanate compound forms a guanamine bond at least a part of the acidic functional group via the isocyanate group, and/or forms an urethane bond at least a part of the hydroxyl group.

The (meth)acrylic copolymer having a (meth)acryl fluorenyl group and a carboxyl group in the side chain is preferably adjusted so that the equivalent ratio (NCO/OH) of the isocyanate group is 1.0 to 2.0. The amount of the thiol isocyanate compound added is obtained.

By adjusting the equivalent ratio (NCO/OH) of the above isocyanate group to 1.0 or more, the (meth)acryl fluorenyl group can be introduced into the side chain of the obtained (meth)acrylic copolymer at a high ratio. Made of high sensitivity. Moreover, since the content ratio of the constituent unit having an acidic functional group can be appropriately adjusted, the water solubility and alkali solubility (developability) of the obtained (meth)acrylic copolymer can be freely adjusted. Further, the (meth)acrylic copolymer having a (meth)acryl fluorenyl group and a carboxyl group in the side chain is more preferably a hydroxyl group except that the equivalent ratio (NCO/OH) of the isocyanate group is adjusted to 1.0 or more. The content ratio of the constituent units is set to be 14 mol% or more in terms of the addition amount. By adjusting the equivalent ratio (NCO/OH) of the above isocyanate group to 1.0 or more, the introduction ratio of the isocyanate group can be increased, and the content ratio of the constituent unit having a hydroxyl group can be further set to 14 mol% in terms of the addition amount. Above, isocyanate group Since the part in which the reaction is carried out is increased, a (meth) acrylonitrile group can be introduced in a large amount in the side chain of the obtained (meth)acrylic acid copolymer, and it is possible to produce a particularly high sensitivity.

On the other hand, by suppressing the equivalent ratio (NCO/OH) of the above isocyanate group to 2.0 or less, the unreacted (meth)acrylonitrile-containing isocyanate compound is prevented from remaining in a large amount in the obtained (meth)acrylic acid. Among the copolymers, the physical properties are more excellent.

In the alkali-soluble polymer compound of the present invention, a preferred lower limit of the content ratio of the segment derived from at least one selected from the group consisting of a carboxylic acid, a dicarboxylic anhydride, and a carboxylate is 10% by weight. The upper limit is 40% by weight. The content ratio of the segment derived from at least one selected from the group consisting of a carboxylic acid, a dicarboxylic anhydride, and a carboxylate is 10% by weight or more, whereby water solubility or alkali solubility can be sufficiently imparted. When the content ratio of the segment derived from at least one selected from the group consisting of a carboxylic acid, a dicarboxylic anhydride, and a carboxylate is 40% by weight or less, swelling or dissolution during development can be suppressed from becoming conspicuous. And form a finer pattern. The lower limit of the content ratio of the segment derived from at least one selected from the group consisting of a carboxylic acid, a dicarboxylic anhydride, and a carboxylate is 15% by weight, and more preferably 30% by weight.

The method for producing the alkali-soluble polymer compound of the present invention may, for example, be a method of using a radical polymerization initiator and an optional molecular weight modifier by bulk polymerization, solution polymerization, suspension polymerization, or dispersion polymerization. A monomer component constituting the copolymer, such as a carboxyl group-containing monofunctional unsaturated compound or a monofunctional compound having an unsaturated double bond, is polymerized by a conventionally known method such as emulsion polymerization. Among them, it is suitable for solution polymerization.

Examples of the solvent used in the case of producing the alkali-soluble polymer compound of the present invention by the solution polymerization include aliphatic alcohols such as methanol, ethanol, isopropanol and ethylene glycol; Kesai Lu Su and other races; carbitol, butyl carbitol, etc. Carbitol; esters such as celecoxib acetate, carbitol acetate, propylene glycol monomethyl ether acetate; ethers such as diethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran, cyclohexanone, methyl ethyl Ketones such as ketones and methyl isobutyl ketone; polar organic solvents such as dimethyl hydrazine and dimethylformamide.

In the case of producing the alkali-soluble polymer compound of the present invention by the suspension polymerization, the dispersion polymerization, the emulsion polymerization or the like, for example, a liquid hydrocarbon such as benzene, toluene, hexane or cyclohexane may be mentioned. Or other non-polar organic solvents, etc.

When an organic solvent is used in the above solution polymerization, it is preferred to add an appropriate amount of water to the obtained alkali-soluble polymer solution, and then to distill off the organic solvent by pressure reduction or the like.

The radical polymerization initiator used in the production of the alkali-soluble polymer compound of the present invention may, for example, be a peroxide or an azo initiator.

Moreover, examples of the molecular weight modifier include an α-methylstyrene dimer, a thiol-based chain transfer agent, and the like.

A preferred lower limit of the weight average molecular weight of the alkali-soluble polymer compound of the present invention is 3,000, and a preferred upper limit is 100,000. When the weight average molecular weight of the alkali-soluble polymer compound of the present invention is 3,000 or more, the developability of the black matrix pattern is more excellent when the colored photosensitive resin composition of the present invention is used. When the weight average molecular weight of the alkali-soluble polymer compound of the present invention is 100,000 or less, the resolution of the black matrix pattern produced by using the colored photosensitive resin composition of the present invention is more excellent. The lower limit of the weight average molecular weight of the alkali-soluble polymer compound of the present invention is 5,000, and the upper limit is more preferably 50,000.

In the present specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) and is determined by polystyrene conversion. As a column for measuring the weight average molecular weight obtained by polystyrene conversion by GPC, for example, Shodex LF-804 (Shodex LF-804) And electrician company manufacturing) and so on. Further, examples of the solvent used in GPC include tetrahydrofuran and the like.

In the solid content component of the colored photosensitive resin composition of the present invention, a preferred lower limit of the content of the alkali-soluble polymer compound of the present invention is 10% by weight, and a preferred upper limit is 90% by weight. When the content of the alkali-soluble polymer compound of the present invention is 10% by weight or more, alkali solubility can be sufficiently imparted to the obtained colored photosensitive resin composition. When the content of the alkali-soluble polymer compound of the present invention is 90% by weight or less, the swelling of the developer due to the developer during alkaline development can be suppressed, and the shape of the black matrix pattern can be made more uniform. A more preferred lower limit of the content of the alkali-soluble polymer compound of the present invention is 20% by weight, and a more preferred upper limit is 60% by weight.

In the present specification, the above-mentioned "solid content component" means the sum of components other than the solvent.

The colored photosensitive resin composition of the present invention contains a compound having a molecular weight of 1,000 or less and having a polymerizable unsaturated double bond and a hydroxyl group (hereinafter also referred to as "the polymerizable compound of the present invention"). By using the polymerizable compound of the present invention in combination with the above-described alkali-soluble polymer compound of the present invention, the colored photosensitive resin composition of the present invention can be used as a uniform coating liquid although water is used as a solvent.

When the molecular weight of the polymerizable compound of the present invention is 1,000 or less, a solution which is stable to water as a solvent can be obtained, and an undissolved product at the time of alkaline development is less likely to occur. The molecular weight of the polymerizable compound of the present invention is preferably 800 or less, more preferably 600 or less.

In addition, the molecular weight of the polymerizable compound of the present invention is represented by a weight average molecular weight of a compound or the like which is not specific to a modified portion or a degree of modification.

As the polymerizable compound of the present invention, a compound represented by the following formula (1) and/or a compound represented by the following formula (2) are preferably used.

In the formula (1), R represents a hydrogen atom or a methyl group, and X represents an oxygen atom, -OC ₂ H ₄ O- or -OC ₃ H ₆ O-. l means 1 or 2.

In the formula (2), R represents a hydrogen atom or a methyl group, and X represents an oxygen atom, -OC ₂ H ₄ O- or -OC ₃ H ₆ O-. m is an integer from 1 to 3, n is an integer from 0 to 3, and m+n is an integer from 1 to 4.

Specific examples of the polymerizable compound of the present invention include pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, and trimethylolpropane di(methyl). a bifunctional (meth) acrylate such as acrylate, ditrimethylolpropane di(meth)acrylate or glycerol di(meth)acrylate; pentaerythritol tri(meth)acrylate, two new Pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate A trifunctional or higher (meth) acrylate or the like. Among them, a trifunctional or higher (meth) acrylate is preferable in that the polymerization reaction proceeds rapidly and the exposure sensitivity is easily improved.

These polymerizable compounds of the present invention may be used singly or in combination of two or more kinds.

In the present specification, the above "(meth) acrylate" means acrylate or methyl propyl acrylate. Oleate.

Further, as the polymerizable compound of the present invention, a polyfunctional (meth) acrylate modified with ethylene oxide and/or propylene oxide is also suitably used.

The polyfunctional (meth) acrylate may, for example, be a compound obtained by modifying the above-mentioned trifunctional or higher hydroxy group-containing (meth) acrylate with ethylene oxide and/or propylene oxide. Among them, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol are preferred. Tetrakis (meth) acrylate or dipentaerythritol penta (meth) acrylate is obtained by modifying ethylene oxide and/or propylene oxide.

The degree of modification in the case where the above polyfunctional (meth) acrylate is modified with ethylene oxide and/or propylene oxide, and the number of functional groups of the polyfunctional (meth) acrylate to be a base When it is set to n, it is preferably 15 n mol or less with respect to the polyfunctional (meth)acrylate 1 mol. By the above modification degree being 15 nM or less, the swelling by the alkaline developing solution can be suppressed, and the shape of the black matrix pattern can be made more uniform. The above modification is more preferably 10 n mol or less.

As a method of modifying the above polyfunctional (meth) acrylate to ethylene oxide and/or propylene oxide, for example, a method in which a polyol is reacted with ethylene oxide and/or propylene oxide is exemplified. a method of reacting ethylene oxide and/or propylene oxide modified alcohol with (meth)acrylic acid after reacting ethylene oxide to reform and/or propylene oxide to modify alcohol; The ethylene oxide is modified by reacting (meth)acrylic acid with ethylene oxide and/or propylene oxide to synthesize ethylene oxide and/or propylene oxide to modify (meth)acrylic acid. And/or a method in which propylene oxide is modified by (meth)acrylic acid with an alcohol; (meth) propylene Acid, ethylene oxide and/or propylene oxide, and a method for one-time reaction of a polyol.

In the solid content component of the colored photosensitive resin composition of the present invention, a preferred lower limit of the content of the polymerizable compound of the present invention is 10% by weight, and a preferred upper limit is 90% by weight. When the content of the polymerizable compound of the present invention is 10% by weight or more, the obtained colored photosensitive resin composition can be sufficiently photocured, and the black matrix can be more easily formed by a photolithograph method. pattern. When the content of the polymerizable compound of the present invention is 90% by weight or less, the solubility of the alkaline developer used in the production of the black matrix using the obtained colored photosensitive resin composition is not insufficient, and the black matrix pattern produced is used. The developability is more excellent. A more preferred lower limit of the content of the polymerizable compound of the present invention is 20% by weight, and a still more preferred upper limit is 80% by weight.

In addition to the polymerizable compound of the present invention, the colored photosensitive resin composition of the present invention may contain a compound having a polymerizable unsaturated double bond having no hydroxyl group in the range of non-destructive developability or the like (hereinafter also referred to as "others". Polymeric compound").

Examples of the two functional groups among the other polymerizable compounds include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylic acid. Polyethylene glycol di(meth)acrylate such as ester, hexaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, or neopentyl glycol di(meth)acrylate , 3-methyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,4-butane Alcohol diacrylate, 1,6-hexanediol diacrylate, hydroxytrimethylacetate neopentyl glycol diacrylate, and the like.

Examples of the trifunctional or higher of the other polymerizable compounds include trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ditrimethylolpropane. Tetrakis (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, A polyfunctional (meth) acrylate such as dipentaerythritol hexa(meth)acrylate or the like.

In the case where the colored photosensitive resin composition of the present invention contains the above other polymerizable compound, the content of the other polymerizable compound is preferably 40% by weight of the total amount of the polymerizable compound of the present invention and the other polymerizable compound. %. By the content of the above other polymerizable compound being less than 40% by weight, a more uniform coating film can be obtained. A more preferable upper limit of the content of the other polymerizable compound is 30% by weight.

Further, in the solid content component of the colored photosensitive resin composition of the present invention, a preferred lower limit of the content of the other polymerizable compound is 5% by weight, and a preferred upper limit is 50% by weight. By setting the content of the other polymerizable compound in the above range, it is easy to obtain a balance between sensitivity, developability, and resolution of the obtained colored photosensitive resin composition. A more preferred lower limit of the content of the other polymerizable compound is 10% by weight, and a more preferred upper limit is 40% by weight.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator.

Examples of the photopolymerization initiator include benzoin, benzophenone, diphenylethylenedione, and 9-oxosulfuric acid. A previously known photopolymerization initiator such as (thioxanthone), and derivatives thereof.

Specific examples thereof include (4-(methylphenylthio)phenyl)phenyl ketone and 2,2-dimethoxy-1,2-diphenylethane-1-one, and 1 -hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2 -hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, double (2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide , 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane- 1-keto, bis(4-dimethylaminophenyl)one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzhydrylhydrazine) , O-Ethyl-1-(6-(2-methylbenzylidene)-9-ethyl-9H-indazol-3-yl)ethanone oxime, 2,4,6-trimethyl Benzhydryldiphenylphosphine oxide, 4-benzylidene-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4 -two Ethyl benzyl benzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate , benzyl-β-methoxyethyl acetal, diphenylethylenedione dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) fluorene, Methyl O-benzhydrylbenzoate, 2,4-diethyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 1-chloro-4-propoxy 9-oxosulfur 9-oxosulfur 2-methyl 9-oxosulfur 2-isopropyl 9-oxosulfur ,sulfur (thioxanthen), 2-chlorosulfur 2,4-diethyl sulphide 2-methylsulfide 2-isopropylsulfur , 2-ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl fluorene, azobisisobutyronitrile, benzammonium peroxide, isopropyl peroxide Benzene, 2-mercaptobenzimidazole, 2-mercaptobenzoene Oxazole, 2-mercaptobenzothiazole, 2-(O-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobiphenyl Ketone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3- Dimethyl-4-methoxybenzophenone, diphenylethylenedione, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, phenyl b Ketone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tertiary butyl phenyl b Ketone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, Dibenzocycloheptanone, amyl 4-dimethylaminobenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9 -Acridine)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxy III , 2,4,6-tris(trichloromethyl) symmetry three 2-methyl-4,6-bis(trichloromethyl) symmetry three 2-(2-(5-methylfuran-2-yl)vinyl)-4,6-bis(trichloromethyl)symmetric three 2-(2-(furan-2-yl)vinyl)-4,6-bis(trichloromethyl) symmetry three 2-(2-(4-Diethylamino-2-methylphenyl)vinyl)-4,6-bis(trichloromethyl)symmetric three 2-(2-(3,4-dimethoxyphenyl)vinyl)-4,6-bis(trichloromethyl)symmetric three 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) symmetry three 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)symmetric three 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)symmetric three 2,4-bistrichloromethyl-6-(3-bromo-4-methoxy)phenyl symmetric three 2,4-bistrichloromethyl-6-(2-bromo-4-methoxy)phenyl symmetric three 2,4-bistrichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl symmetrical three 2,4-bistrichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl symmetry III Wait. Among them, from the viewpoint of sensitivity, it is preferred to contain an α-aminoalkylphenone photopolymerization initiator and/or an oxime ester photopolymerization initiator. These photopolymerization initiators may be used singly or in combination of two or more.

In the solid content component of the colored photosensitive resin composition of the present invention, a preferred lower limit of the content of the photopolymerization initiator is 0.5% by weight, and a preferred upper limit is 20% by weight. By setting the content of the photopolymerization initiator to the above range, sufficient curability can be obtained to form a favorable black matrix pattern. A more preferred lower limit of the content of the photopolymerization initiator is 1% by weight, and a more preferred upper limit is 10% by weight.

The colored photosensitive resin composition of the present invention contains a black pigment.

The above black pigment is not particularly limited, and a previously known black pigment for a black matrix can be used. Specific examples thereof include titanium black, carbon black, chromium oxide, iron oxide, aniline black, and an anthraquinone pigment. Further, a composite oxide of titanium, manganese, iron, copper, cobalt or the like can be suitably used. Among them, titanium black is preferable, and titanium black and carbon black are more preferable from the viewpoint of dispersibility in the coating film.

From the viewpoint of more uniform dispersion and improved light blocking properties, the titanium black is preferably subjected to surface treatment. The previously known black pigment for the black matrix has a case where aggregation occurs in the case of using water as a solvent, and a portion where the concentration of the black pigment is low locally, that is, a so-called optical pinhole, and the light-shielding property is lowered, but by Titanium black subjected to surface treatment is used, and the dispersibility is improved, and the generation of optical pinholes is suppressed, and a high-quality black matrix which is uniform and highly opaque can be formed.

The method of surface-treating the said titanium black, for example, the surface-treatment of the surface of powder-like titanium black by surface-treatment agent previously, or the surface-treatment agent in the aqueous dispersion of titanium black is processed. Method and so on.

The surface treatment agent is not particularly limited as long as it can react with the surface of titanium black to improve dispersibility, and is preferably a coupling agent such as a titanate coupling agent or an aluminate coupling agent, and more preferably a titanate. A coupling agent. For example, Plenact (registered trademark) 44, Plenact (registered trademark) ET (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), and the like are exemplified as the commercially available ones of the titanate-based coupling agents.

The amount of the surface treatment agent to be added is preferably 0.1 part by weight, and preferably 5 parts by weight, based on 100 parts by weight of the titanium black. The amount of the above surface treatment agent added is 0.1 When the amount is more than the weight, the surface can be sufficiently treated, and the effect of improving the dispersibility can be further exerted. When the amount of the surface treatment agent added is 5 parts by weight or less, phase separation of the surface treatment agent can be suppressed, and a more uniform coating film can be obtained. A more preferred lower limit of the amount of the surface treatment agent added is 0.3 parts by weight, and a more preferred upper limit is 2 parts by weight.

A preferred lower limit of the average primary particle diameter of the above titanium black is 20 nm, and a preferred upper limit is 200 nm. When the average primary particle diameter of the above titanium black is within this range, it can be easily and uniformly dispersed in the coating film. A more preferred lower limit of the average primary particle diameter of the above titanium black is 50 nm, and a more preferable upper limit is 150 nm.

In the present specification, the average primary particle diameter refers to a particle diameter (D50) of 50% of the cumulative particle size in the volume-based cumulative particle size distribution measured by the laser diffraction type particle size distribution measuring apparatus.

From the viewpoint of more uniform dispersion and improved light-shielding property, the above carbon black is preferably one which has been subjected to a hydrophilic surface treatment. By combining the carbon black having the hydrophilic surface treatment and the titanium black described above, the generation of optical pinholes can be suppressed, and a high-quality black matrix having uniform and high light-shielding properties can be formed.

Examples of the hydrophilic surface treatment include an oxidation treatment using various oxidizing agents, or a treatment of introducing an acidic group such as a sulfonic acid group, a phosphoric acid group, a carboxyl group or a phosphate group by a coupling reaction of a diazonium salt. Among them, a treatment in which a carboxyl group and a hydroxyl group are introduced as a hydrophilic group is preferred.

Examples of the oxidation treatment method using the oxidizing agent include a method of oxidizing untreated carbon black by contact with free oxygen at a high temperature, a method of oxidizing by ozone, NO ₂ or the like, and bromine and A method of treating water under normal pressure or under pressure; a method of oxidizing by an oxidizing solution such as hydrogen peroxide, nitric acid or sulfuric acid; a method of combining the methods, and the like. Further, the carbon black whose surface has been oxidized may be further neutralized by using relative ions.

For example, AquaBlack (registered trademark) 162, AquaBlack (registered trademark) 164 (all manufactured by Tokai Carbon Co., Ltd.), CAB-O, may be mentioned as a commercially available carbon black which is subjected to the hydrophilic surface treatment. - JET200, CAB-O-JET300, CAB-O-JET400 (all manufactured by Cabot Specialty), and the like.

A preferred lower limit of the average particle diameter of the above carbon black is 50 nm, and a preferred upper limit is 180 nm. When the average particle diameter of the carbon black is within this range, it can be easily uniformly dispersed in the coating film. A more preferred lower limit of the average particle diameter of the carbon black is 60 nm, a more preferred upper limit is 150 nm, a still more preferred lower limit is 70 nm, and a still more preferred upper limit is 120 nm.

When the black black and the carbon black are contained as the black pigment, the content of the carbon black is preferably 1 part by weight, and preferably 10 parts by weight, based on 100 parts by weight of the titanium black. When the content of the carbon black is 1 part by weight or more, the optical pinhole can be sufficiently suppressed. When the content of the carbon black is 10 parts by weight or less, sufficient light blocking properties can be exhibited without impairing developability and the like. A more preferred lower limit of the content of the above carbon black is 2 parts by weight, and a still more preferred upper limit is 7 parts by weight.

In the solid content component of the colored photosensitive resin composition of the present invention, the content of the black pigment is preferably more than 30% by weight and not more than 70% by weight. By setting the content of the above black pigment to more than 30% by weight, a black matrix excellent in light shielding properties can be formed. When the content of the black pigment is 70% by weight or less, the sensitivity of the obtained colored photosensitive resin composition, the heat resistance of the coating film after curing, and the chemical resistance can be favorably maintained. The content of the above black pigment is more preferably 40% by weight or more, still more preferably 50% by weight or more.

When the content of the black pigment is within the above preferred range, a colored photosensitive resin composition having more excellent light-shielding properties can be obtained. Specifically, when the content of the black pigment is more than 30% by weight, the optical density (OD value) when the black matrix having a thickness of 5 μm is formed using the colored photosensitive resin composition of the present invention is 2.0 or more. The preferred value. The OD value is more preferably 3.0 or more, further preferably 4.0 or more.

Further, the above OD value can be measured using a transmission densitometer.

Moreover, in order to increase the electric resistance or to adjust the color tone, the coloring photosensitive resin composition of the present invention may contain other coloring agents such as an organic pigment or a dye in addition to the black pigment, insofar as the light-shielding performance is not lowered. Specifically, for example, in order to suppress the reddish color tone derived from carbon black and to make the overall black color better, it is also possible to contain a "purple dispersion liquid (containing purple pigment 10%) manufactured by MIKUNI COLOR Co., Ltd. "" Blue pigment dispersion CF BLUE (containing 20% of blue pigment)" manufactured by Yuki Co., Ltd., etc.

The colored photosensitive resin composition of the present invention contains water as a solvent.

By using the above water as a solvent, it is possible to reduce the environmental load on the application of the colored photosensitive resin composition and the discharge of the organic chemical substance during drying.

In the colored photosensitive resin composition of the present invention, the content of the water is not particularly limited, and is appropriately set so as to be suitable for the viscosity of the coating method, etc., and the concentration of the solid content is preferably 1 to 50% by weight or less. More preferably, it is 10 to 40% by weight or less.

For the purpose of improving the dispersibility of the black pigment, the colored photosensitive resin composition of the present invention may contain other solvents such as an organic solvent in addition to the water, but the object of the present invention is to reduce the load on the environment. It is preferably free of other solvents. In the case of containing the above other solvent, the content thereof is preferably 30% by weight or less, more preferably 10% by weight based on the entire solvent. The amount is below %.

Examples of the other solvent include propylene glycol such as propylene glycol monomethyl ether acetate or an organic solvent having low toxicity such as an alcohol such as ethanol or isopropyl alcohol.

In order to alleviate the reaction disorder caused by oxygen, the colored photosensitive resin composition of the present invention may further contain a reaction auxiliary. By using the above-mentioned reaction auxiliary together with the hydrogen abstraction type photopolymerization initiator, the hardening speed at the time of light irradiation can be improved.

As the above reaction assistant, for example, n-butylamine, di-n-butylamine, triethylamine, tri-ethyltetramine, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoprene can be used. An amine-based reaction aid such as an ester or a phosphine-based reaction aid such as tri-n-butylphosphine or a sulfonic acid-based reaction aid such as a s-benzyl isothiouronium or a toluene sulfinate. These reaction assistants may be used singly or in combination of two or more.

The colored photosensitive resin composition of the present invention may contain a coupling agent, a thermal polymerization inhibitor, an antifoaming agent, a leveling agent, a sensitizer, a hardening accelerator, and a photocrossing as needed within the scope of the object of the present invention. A known various additives such as a crosslinking agent, a photosensitizer, a dispersing agent, a dispersing aid, a filler, a adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomerating agent.

As the dispersing agent, a polymer dispersing agent such as an amine ester resin dispersing agent is preferably used.

The method of producing the colored photosensitive resin composition of the present invention includes, for example, an alkali-soluble polymer compound of the present invention, a polymerizable compound of the present invention, the photopolymerization initiator, the black pigment, and the water, using a stirrer. And a method of mixing according to an additive or the like to be used. Further, it is preferred to filter using a filter after stirring to form a homogeneous mixture.

The colored photosensitive resin composition of the present invention is suitably used as a black constituting a color filter Matrix material. Further, the black matrix composed of the colored photosensitive resin composition of the present invention is also one of the inventions. Further, a color filter having the black matrix of the present invention is also one of the inventions.

Hereinafter, an example of a method of forming the black matrix of the present invention using the colored photosensitive resin composition of the present invention will be described.

First, a roll coater, a reverse coater, and a gravure coater are used on a substrate made of glass, polyethylene terephthalate, acrylic resin, polycarbonate, or the like. Contact coating device such as gravure coater), comma coater, bar coater, or spin coater, slit coater, shower curtain A non-contact type coating device such as a curtain flow coater is applied to the colored photosensitive resin composition of the present invention.

Next, for example, the applied colored photosensitive resin composition is dried under reduced pressure at room temperature using a vacuum drying device, and then heated at 80 ° C or higher and 120 ° C or lower, preferably 90 ° C or higher, by a hot plate or an oven. The film is dried at a temperature of 100 ° C or lower for 60 seconds or longer and 180 seconds or shorter, and dried by the above method to form a coating film.

The obtained coating film is partially exposed to light by irradiating an active energy ray such as ultraviolet rays or excimer laser light through a negative mask. The amount of the energy ray to be irradiated also varies depending on the composition of the colored photosensitive resin composition of the present invention to be used, and is preferably from 100 to 2,000 mJ/cm ² .

The exposed coating film is developed by an aqueous alkaline solution to be patterned into a desired shape. As the development method using the alkaline aqueous solution, for example, a dipping method, a spray method, or the like can be used. Examples of the alkaline aqueous solution used as the developing solution include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, tetramethylammonium hydroxide, and quaternary ammonium salts.

If necessary, the pattern after development is about 220 ° C ~ 250 ° C, preferably 230 ° C ~ 240 ° C Post-baking left and right. At this time, it is preferred to perform full-surface exposure on the formed pattern.

With the above, a black matrix having a specific pattern shape can be formed.

Further, the colored photosensitive resin composition in which the red pigment is dispersed, the colored photosensitive resin composition in which the green pigment is dispersed, and the colored photosensitive resin composition in which the blue pigment is dispersed are also subjected to the formation of the black matrix of the present invention described above. The operation of the method forms a pixel pattern of each color, whereby the color filter of the present invention can be formed.

The colored photosensitive resin composition in which the red pigment is dispersed, the colored photosensitive resin composition in which the green pigment is dispersed, and the colored photosensitive resin composition in which the blue pigment is dispersed can be used as previously known.

Furthermore, the color filter of the present invention can also eject inks of various colors of red, green, and blue from inkjet nozzles to regions partitioned by the black matrix of the present invention, and store the ink by heat or light. Manufactured by hardening.

Further, a display element having the color filter of the present invention is also one of the inventions.

Examples of the display element of the present invention include liquid crystal display elements and the like.

In the liquid crystal display device, an electrode, a spacer, or the like is sequentially formed by forming a color filter of the present invention on a substrate, and is bonded to another substrate on which an electrode or the like is formed, and the obtained empty cell is implanted with a specific The liquid crystal is sealed and sealed by a conventionally known method.

According to the present invention, it is possible to provide a colored photosensitive resin composition which is excellent in coatability and can reduce the load on the environment. Moreover, according to the present invention, it is possible to provide a black matrix, a color filter, and a display element which are formed using the colored photosensitive resin composition.

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

(Production of surface treatment titanium black A)

100 parts by weight of titanium black ("Mitsubishi Synthetic Material Co., Ltd.", "13M-C") was added to 100 parts by weight of pure water, and the mixture was stirred by a disperser to be uniformly dispersed, and then a titanate couple was added while stirring. 1.0 parts by weight of a mixture ("Plenact 44" manufactured by Ajinomoto Fine-Techno Co., Ltd.) was further stirred for 30 minutes to obtain an aqueous dispersion of surface-treated titanium black A.

(Production of surface treatment titanium black B)

An aqueous dispersion of the surface-treated titanium black B was obtained in the same manner as in "(Production of surface-treated titanium black A)" except that the amount of the titanate-based coupling agent was changed to 0.2 part by weight.

(Production of surface treatment titanium black C)

0.5 parts by weight of a titanate-based coupling agent ("Plenact ET" manufactured by Ajinomoto Fine-Techno Co., Ltd.) was used instead of 1.0 part by weight of a titanate coupling agent ("Plenact 44" manufactured by Ajinomoto Fine-Techno Co., Ltd.). An aqueous dispersion of the surface-treated titanium black C was obtained in the same manner as in "(Production of Surface Treatment Titanium Black A)".

(Example 1)

(1) Preparation of alkali-soluble polymer compound A of the present invention

A four-port separable flask equipped with a capacity of 1000 mL is equipped with a stirrer, a reflux cooler, A reaction device for a thermometer, a nitrogen introduction tube, and a dropping funnel. 50 parts by weight of tetrahydrofuran was placed in the flask, and nitrogen gas was introduced and foamed to remove dissolved oxygen. 20 parts by weight of acrylic acid, 60 parts by weight of methyl methacrylate, 30 parts by weight of 2-hydroxyethyl acrylate, 1.3 parts by weight of tert-butyl peroxy-2-ethylhexanoate, and 50 parts by weight of tetrahydrofuran. The monomer solution was prepared by mixing, and the monomer solution was added dropwise for 1 hour while stirring in a flask charged with tetrahydrofuran, and then refluxed at 80 ° C for 3 hours to carry out a copolymerization reaction to obtain a resin solution. The copolymer resin was isolated and purified from the obtained resin solution by methanol, and then dried under reduced pressure to obtain a resin solid.

Then, 37 parts by weight of a 1 mol/L aqueous ammonia solution and 43 parts by weight of water were added to 20 g of the obtained resin solid matter, and the mixture was heated and stirred at 80 ° C while being neutralized, and dissolved to obtain a water-soluble and alkali-soluble polymer compound ( An aqueous solution of the alkali-soluble polymer compound A) of the present invention.

(2) Preparation of coloring photosensitive resin composition

To 100 parts by weight of the aqueous solution of the alkali-soluble polymer compound A of the present invention (solid content ratio: 20.6% by weight), 20 parts by weight of neopentyl alcohol triacrylate as the polymerizable compound of the present invention is added as 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one of α-aminoalkylphenone photopolymerization initiator (Manufactured by BASF Corporation, "IRGACURE907") 1 part by weight, 30 parts by weight of titanium black (manufactured by Mitsubishi Materials Corporation, "13M-C") as a black pigment, and a self-dispersing carbon black which is subjected to hydrophilic surface treatment to introduce a carboxyl group on the surface (Tokai Carbon Co., Ltd.) Manufactured, "Aqua-Black 162", 19.2% by weight of aqueous dispersion), 1 part by weight, as a coupling agent, 3-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") 1 After the mixture was mixed for 2 hours with a weight of 200 parts by weight of water, the mixture was filtered through a membrane filter having a pore size of 5 μm to prepare a colored photosensitive resin composition.

(3) Formation of coating film

The obtained colored photosensitive resin composition was applied onto a glass substrate of 150 mm × 150 mm by a spin coating method, dried under reduced pressure at 66 Pa for 30 seconds, and then prebaked at 100 ° C for 180 seconds to obtain about 5.0. Film thickness of μm film.

(Examples 2 to 14)

A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the materials of the blending ratios shown in Tables 1 and 2 were used, and a coating film was obtained.

Further, "Acrit 3401MA" and "Acrit 3401MA modified (Acrit 3SQ-424)" in the table are aqueous solutions of the alkali-soluble polymer compound of the present invention.

(Comparative Example 1)

(1) Preparation of water-insoluble alkali-soluble polymer compound A

A four-port separable flask having a capacity of 1000 mL was provided with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube, and a reaction device for dropping the funnel. 50 parts by weight of tetrahydrofuran was placed in the flask, and nitrogen gas was introduced and foamed to remove dissolved oxygen. 20 parts by weight of acrylic acid, 20 parts by weight of methyl methacrylate, 30 parts by weight of n-butyl methacrylate, 30 parts by weight of 2-ethylhexyl acrylate, and tertiary butyl peroxy-2-ethylhexanoate 1.3 parts by weight and 50 parts by weight of tetrahydrofuran were mixed to prepare a monomer solution, and the monomer solution was added dropwise for 1 hour while stirring in a flask charged with tetrahydrofuran, followed by refluxing at 80 ° C for 3 hours to carry out copolymerization. The reaction was carried out to obtain a resin solution. The copolymer resin was isolated and purified from the obtained resin solution by methanol, and then dried under reduced pressure to obtain a resin solid.

Next, 37 parts by weight of 1 mol/L of ammonia water and 43 parts by weight of water were added to 20 g of the obtained resin solids, and while heating, stirring was carried out at 80 ° C to dissolve, but it was impossible to dissolve. Dissolved. Therefore, 80 parts by weight of propylene glycol monomethyl ether acetate was added to 20 g of the obtained resin solid content to prepare a propylene glycol monomethyl ether acetate solution of an alkali-soluble polymer compound (water-insoluble alkali-soluble polymer compound A).

(2) Preparation of coloring photosensitive resin composition

A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the obtained propylene glycol monomethyl ether acetate solution of the water-insoluble alkali-soluble polymer compound A was used, but the formation was impossible. A uniform composition of the coating liquid.

(Comparative examples 2 to 4)

The colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the materials of the blending ratios shown in Table 3 were used. However, in Comparative Examples 2 and 3, a coating liquid could not be obtained. A uniform composition.

<evaluation>

Each of the colored photosensitive resin compositions and coating films obtained in the examples and the comparative examples was evaluated as follows. The results are shown in Tables 1 to 3.

Further, in Comparative Examples 1 to 3, a uniform composition capable of forming a coating liquid could not be obtained, and thus the following evaluation could not be performed.

(shading)

For each of the coating films obtained in the examples and the comparative example 4, the OD value was measured using a transmission densitometer (manufactured by X-Rite Co., Ltd., "Model 361T").

The case where the OD value is 4.0 or more is set to "○", the case where the OD value is 3.0 or more and less than 4.0 is set to "△", and the case where the OD value is less than 3.0 is set to "x", and the opacity is set. Conduct an evaluation.

(developability)

On each of the coating films obtained in the examples and the comparative example 4, a negative mask having a line pattern capable of being exposed in a line width of 2 μm to 2 μm was used, and a 200 μm proximity exposure apparatus was used. It is manufactured by a Japanese research company, "MA-10 type", and exposed to ultraviolet light having a wavelength of 365 nm at an exposure amount of 1000 mJ/cm ² .

Thereafter, development was carried out by a developing device (manufactured by ACCESS Co., Ltd.) by spraying with a 0.05% by weight aqueous potassium hydroxide solution for 40 seconds, followed by rinsing with pure water for 30 seconds. The development pattern of the black matrix.

When the development pattern of the line width of 10 μm and 20 μm was confirmed, the case where the black matrix pattern was obtained with a line width of 10 μm was set to “○”, and the black matrix pattern could not be obtained with a line width of 10 μm, but the pattern was obtained with a line width of 20 μm. In the case of "△", the case where the pattern cannot be obtained even with a line width of 20 μm is "x", and the developability is evaluated.

(Sensitivity)

In the above evaluation of "(developability)", the exposure amount was changed to 500 mJ/cm ² and exposure was performed to obtain a development pattern.

When the development pattern of the line width of 20 μm was confirmed, the pattern of obtaining a line width of 20 μm at an exposure amount of 500 mJ/cm ² was set to "○", and a line width of 20 μm was obtained at an exposure amount of 1000 mJ/cm ² . In the case of a pattern in which a line width of 20 μm is not obtained with an exposure amount of 500 mJ/cm ^{2 ,} it is set to "Δ", and a pattern of a line width of 20 μm cannot be obtained even with an exposure amount of 1000 mJ/cm ² . For "X", the sensitivity is evaluated.

[Industrial availability]

According to the present invention, it is possible to provide a colored photosensitive resin composition which is excellent in coatability and can reduce the load on the environment. Moreover, according to the present invention, it is possible to provide a black matrix, a color filter, and a display element which are formed using the colored photosensitive resin composition.

Claims (12)

A colored photosensitive resin composition comprising a water-soluble and alkali-soluble polymer compound, a compound having a molecular weight of 1,000 or less and having a polymerizable unsaturated double bond and a hydroxyl group, a photopolymerization initiator, a black pigment, and water. The water-soluble and alkali-soluble polymer compound has a segment derived from at least one selected from the group consisting of a carboxylic acid, a dicarboxylic anhydride, and a carboxylate. The colored photosensitive resin composition of the first aspect of the invention, wherein the compound having a molecular weight of 1,000 or less and having a polymerizable unsaturated double bond and a hydroxyl group is a compound represented by the following formula (1) and/or the following formula. (2) the compound represented, In the formula (1), R represents a hydrogen atom or a methyl group, and X represents an oxygen atom, -OC ₂ H ₄ O- or -OC ₃ H ₆ O-; 1 is 1 or 2; In the formula (2), R represents a hydrogen atom or a methyl group, X represents an oxygen atom, -OC ₂ H ₄ O- or -OC ₃ H ₆ O-; m is an integer of 1 to 3, and n is an integer of 0 to 3 , m+n is an integer from 1 to 4. The colored photosensitive resin composition of claim 1 or 2, wherein photopolymerization The initiator contains an α-aminoalkylphenone photopolymerization initiator and/or an oxime ester photopolymerization initiator. The colored photosensitive resin composition of claim 1, 2 or 3, wherein the black pigment contains titanium black. The colored photosensitive resin composition of claim 4, wherein the titanium black is subjected to surface treatment. The colored photosensitive resin composition of claim 4 or 5, wherein the black pigment contains titanium black and carbon black. The colored photosensitive resin composition of claim 6, wherein the carbon black is subjected to a hydrophilic surface treatment. The colored photosensitive resin composition of the sixth or seventh aspect of the invention, which contains 1 to 10 parts by weight of carbon black per 100 parts by weight of titanium black. The colored photosensitive resin composition of claim 1, 2, 3, 4, 5, 6, 7, or 8 wherein the content of the black pigment in the solid content exceeds 30% by weight and is 70% by weight or less . A black matrix comprising a colored photosensitive resin composition of the first, second, third, fourth, fifth, sixth, seventh, eighth or ninth aspect of the patent application. A color filter having a black matrix of claim 10th. A display element having a color filter of claim 11 of the patent application.