KR20140083909A - Colored photosensitive resin composition, color filter and liquid crystal display - Google Patents

Abstract

Provided are a colored photosensitive resin composition with superior chromaticity, contrast ratio, heat resistance, and adhesion to a glass substrate, a color filter comprising a coloring layer formed using the colored photosensitive resin composition, and a color liquid crystal display device comprising the color filter. The colored photosensitive resin composition of the present invention contains an alkali soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by chemical formula (1), and an organic pigment. In chemical formula (1), R1 and R2 are independently a hydrogen atom or an organic group, and either R1 or R2 is an organic group, R1 and R2 can form a cyclic structure by being coupled or comprises the bond of hetero atoms, R3 is a single bond or an organic group, R4 to R9 are independently a hydrogen atom or an organic group, neither R6 nor R7 is a hydroxyl group, and R10 is a hydrogen atom or an organic group.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter, and a color liquid crystal display

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

A color filter used for a liquid crystal panel or an image sensor is generally manufactured by a lithography method. In this lithography method, a black photosensitive resin composition is first applied to a glass substrate, followed by exposure and development to form a black matrix. Next, coating, exposure and development are repeated for each photosensitive resin composition to which an organic pigment of each color of rust, blue, and red is added to form a pattern of each color at a predetermined position to produce a color filter.

At this time, if the heat resistance of the photosensitive resin composition to which the organic pigment is added is low, foreign matters are formed in the heating step, and irregularities are formed on the surface, resulting in deteriorated contrast. Therefore, a composition having high heat resistance is desired. For example, in Patent Document 1, it has been proposed to use a coloring composition to which a compound having a specific cyclic amidine structure is added.

The compound having a cyclic amidine structure used herein has a cyclic amidine moiety that improves the affinity with the colorant and a characteristic group that enhances the affinity between the cyclic amidine moiety and the binder component. Therefore, the colored photosensitive resin composition to which the cyclic amidine structure is added has high dispersion stability, The addition amount of the dispersing agent such as the dispersing agent can be reduced, and it is reported that the color and the contrast ratio are excellent and the heat resistance is improved.

International Publication No. 2011/13318

However, in the colored photosensitive resin composition to which the compound having a cyclic amidine structure is added, there is a problem that the adhesion to the glass substrate is insufficient.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a colored photosensitive resin composition which is excellent in chromaticity characteristics, contrast ratio, and heat resistance and has improved adhesion to a glass substrate, a color filter formed using the colored photosensitive resin composition, And a display element.

As a result of intensive research, the inventors of the present invention have found that the above problems can be solved by containing a specific compound, thereby completing the present invention.

A first aspect of the present invention is a colored photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by the following formula (1), and an organic pigment.

(Shown in, R ¹ and R ² are a hydrogen atom or an organic each independently formula: provided that at least one of R ¹ and R ² represents an organic group. R ¹ and R ² and year they are bonded form a cyclic structure It may be, or may include a combination of the hetero atom. R ³ represents a single bond or an organic. R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group , silanol group, represents a nitro group, alcohol pinot group, sulfo group, sulfonate group, phosphino group, a phosphine P group, a phosphono group, phosphonate group, or an organic. R ^6, R ^7, R ⁸ and R ⁹ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, , A phosphinyl group, a phosphono group, a phosphonate group, an amino , Coming ammonia, or represents an organic group. However, R ⁶ and R ⁷ is optionally, and there is no case where the hydroxyl group. R ^6, R ^7, R ⁸ and R ⁹ form a cyclic structure by combining more than these two, And R ¹⁰ represents a hydrogen atom or an organic group.

A second aspect of the present invention is a color filter comprising a colored layer formed using the colored photosensitive resin composition according to the present invention, and the third aspect of the present invention is a color liquid crystal display element comprising the color filter according to the present invention.

According to the present invention, a colored photosensitive resin composition having excellent color and contrast ratio, excellent heat resistance, and high adhesion to a glass substrate can be obtained. Therefore, the colored photosensitive resin composition of the present invention is very useful for the production of various color filters including a color filter for a color liquid crystal display element, a color filter for color separation of a solid-state image pickup element, a color filter for an organic EL display element, It can be suitably used.

«Colored photosensitive resin composition»

The colored photosensitive resin composition of the present invention contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by the above formula (1), and an organic pigment. First, these constituent components will be described.

<Alkali-soluble resin>

The alkali-soluble resin according to the present invention is not particularly limited, and conventionally known alkali-soluble resins can be used. The alkali-soluble resin may have an ethylenic unsaturated group or may not have an ethylenic unsaturated group.

In the present specification, the alkali-soluble resin is a resin film having a thickness of 1 占 퐉 formed on a glass substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass and a 2.38% Refers to a material which is dissolved in an aqueous solution of ammonium hydroxide (TMAH) for 1 minute to be dissolved in a film thickness of 0.01 탆 or more.

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

Among them, a resin represented by the following formula (a-1) is preferable. The resin represented by the formula (a-1) is preferable in view of its high photocurability.

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

The formula (a2) of, R ^a1 are each independently a hydrogen atom, a hydrocarbon group, or a halogen atom with a carbon number of 1 ~ 6, R ^a2 are each independently a hydrogen atom or a methyl group, W is ^a single Or a group represented by the following formula (a-3).

In the formula (a-1), Y ^a represents a residue other than an acid anhydride group (-CO-O-CO-) from ^a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl and methylene tetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, And glutaric acid.

In the above formula (a-1), Z ^a represents a residue other than the two acid anhydride groups in the tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

In the above formula (a-1), m represents an integer of 0 to 20.

Examples of the alkali-soluble resin having an ethylenic unsaturated group include polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid; (Meth) acrylate obtained by reacting a compound having a hydroxyl group and a (meth) acrylic acid and then reacting the compound with a (meth) acrylic acid; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol or cresol novolak type epoxy resin , Epoxy resin such as resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin and dihydroxybenzene type epoxy resin And (meth) acrylic acid, Epoxy (meth) acrylate resin and the like may be used.

In the present specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" means both acrylate and methacrylate.

On the other hand, as the alkali-soluble resin having no ethylenic unsaturated group, a resin obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated compound containing an alicyclic group, which does not have an alicyclic group, and an epoxy group-containing unsaturated compound can be used.

Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids. Among these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the resin to be obtained, ease of obtaining water, and the like. These unsaturated carboxylic acids may be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (Meth) acrylic acid epoxyalkyl esters such as methyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α- -Cyclohexyl acrylate, glycidyl acrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, glycidyl methacrylate, glycidyl methacrylate, glycidyl methacrylate, glycidyl methacrylate, Glycidyl ethers such as glycidyl ether; and the like. Of these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o -Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether are preferable. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

The unsaturated alicyclic group-containing compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobonyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulas.

R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^a4 is preferably a single bond, a straight chain or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene or hexamethylene. As R ^a5, for example, methyl group and ethyl group are preferable.

The proportion of the constituent unit derived from the unsaturated carboxylic acid in the alkali-soluble resin is preferably 3 to 25% by mass, more preferably 5 to 25% by mass. The proportion of the structural unit derived from the epoxy group-containing unsaturated compound is preferably 71 to 95% by mass, and more preferably 75 to 90% by mass. The proportion of the constituent unit derived from the alicyclic group-containing unsaturated compound is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, and still more preferably 5 to 15% by mass. Within the above range, the adhesion of the colored photosensitive resin composition to the glass substrate and the strength of the colored photosensitive resin composition after curing can be increased while making the alkali solubility of the obtained resin appropriate.

The mass average molecular weight of the alkali-soluble resin is preferably from 1,000 to 40,000, and more preferably from 2,000 to 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while satisfactory developability is obtained.

The content of the alkali-soluble resin is preferably from 10 to 50 mass%, more preferably from 20 to 40 mass%, based on the solid content of the colored photosensitive resin composition. The solid content referred to herein is a component other than the solvent. When the content of the alkali-soluble resin is too small, for example, the alkali developability is lowered or the storage stability of the obtained colored photosensitive resin composition is lowered. On the other hand, when the content is too large, It may be difficult to achieve the intended color density.

<Photopolymerizable Monomer>

The colored photosensitive resin composition of the present invention contains a photopolymerizable monomer. Photopolymerizable monomers include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy (Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, maleic anhydride, maleic anhydride, Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl ) Acrylate, 2-phenoxy-2-hydroxypropyl (Meth) acrylate, trimethylolpropane tri (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate of 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and phthalic acid derivatives, And the like. These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, butyleneglycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate A reaction product of hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, a reaction product of methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol And condensates such as condensates of polyfunctional monomers and triacryl amides. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable monomer in the present invention is preferably 10 to 50 mass%, more preferably 20 to 40 mass%, based on the solid content of the colored photosensitive resin composition. In this case, if the content of the photopolymerizable monomer is too small, sufficient curability may not be obtained. If the content is too large, the alkali developability is lowered and greasing is caused on the glass substrate or the light- , Film residue and the like tend to occur easily.

<Photopolymerization initiator>

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator. Thus, the radiation sensitivity can be imparted. Here, the term "radiation" is a concept including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, and the like.

The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of a photopolymerizable monomer by exposure to visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray radiation.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, imidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, - diketone compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds and the like.

In the present invention, an oxime ester compound represented by the following formula (2) can be given as a preferable photopolymerization initiator.

( ^Wherein R ^b1 and R ^b2 are a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group and a cyano group, R ^b3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, S or O, n is an integer of 0 to 4, p is 0 or 1, and q is an integer of 0 to 4.)

In the formula (2), when R ^b1 is a monovalent organic group, R ^b1 is not particularly limited within the range not impairing the object of the present invention, and is suitably selected from various organic groups. Preferred examples of when R ^b1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, , A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, 1 Or an amino group substituted with an organic group of 2, a morpholin-1-yl group, and a piperazin-1-yl group. When n is an integer of 2 to 4, R ^b1 may be the same or different. The carbon number of the substituent does not include the carbon number of the substituent further having a substituent.

When R ^b1 is an alkyl group, the number of carbon atoms thereof is preferably from 1 to 20, more preferably from 1 to 6. When R ^b1 is an alkyl group, it may be straight chain or branched chain. When R ^b1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain.

When R ^b1 is an alkoxy group, its carbon number is preferably from 1 to 20, more preferably from 1 to 6. When R ^b1 is an alkoxy group, it may be a straight chain or a branched chain. When R ^b1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain.

When R ^b1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms thereof is preferably from 3 to 10, more preferably from 3 to 6.

When R ^b1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms thereof is preferably from 2 to 20, more preferably from 2 to 7.

When R ^b1 is an alkoxycarbonyl group, the number of carbon atoms thereof is preferably from 2 to 20, more preferably from 2 to 7.

When R ^b1 is a phenylalkyl group, the number of carbon atoms thereof is preferably 7 to 20, more preferably 7 to 10. When R ^b1 is a naphthylalkyl group, the number of carbon atoms thereof is preferably from 11 to 20, more preferably from 11 to 14. When R ^b1 is a phenylalkyl group or a naphthylalkyl group, R ^b1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^b1 is a heterocyclyl group, the heterocyclyl group may be a 5-membered or 6-membered monocyclic ring containing one or more N, S or O, or a heterocyclyl group formed by condensation of such monocyclic ring and a benzene ring. And when the heterocyclyl group is a condensed ring, the number of rings is 3. When R ^b1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^b1 is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, A phenyl group which may have a substituent, a benzyl group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthylalkyl group, and a heterocyclyl group. Specific examples of these preferred organic ^groups are the same as R ^b1 .

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^b1 have a further substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, A saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, 1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^b1 further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group and heterocyclyl group contained in R ¹ have plural substituents, the plural substituents may be the same or different.

R ^b1 in the case of the top position bonded to the phenyl group R ^b1 combine to 2, a phenyl group and the position of the coupling the position of the hand over the first, and the methyl groups of the main skeleton of the oxime ester compound with respect to the phenyl group, 4-up or 5 Is preferable, and the fifth is more preferable. N is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

When R ^b2 in the formula (2) is an organic group, it can be selected from a variety of organic groups within the range not hindering the object of the present invention. In the formula (2), R ^b2 is an organic group, and examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, A saturated aliphatic acyloxy group of 1 to 7 carbon atoms, a phenyl group, a naphthyl group, a benzoyl group, a naphthoyl group, an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin- A monoalkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen group, a nitro group, a cyano group Anger can be heard.

R ^b2 is preferably a benzoyl group substituted by a group selected from the group consisting of a benzoyl group, a naphthoyl group, an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group and a phenyl group; , A benzoyl group, a naphthoyl group, a 2-methylphenylcarbonyl group, a 4- (piperazin-1-yl) phenylcarbonyl group and a 4- (phenyl) phenylcarbonyl group are more preferable.

In the formula (2), q is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. when q is 1, the binding position of R ^b2 is a group that is R ^b2 combine for bonding hands binding to the sulfur atom, it is preferred that the para great.

When the phenyl group, naphthyl group and heterocyclyl group contained in R ^b2 further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, A saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, 1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^b2 further have a substituent, the number of the substituent is not limited within the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group and heterocyclyl group contained in R ^b2 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^b3 in the formula (2) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. When R ^b3 is a methyl group, the photopolymerization initiator made of the compound represented by the formula (2) is particularly excellent in sensitivity.

Of the oxime ester compounds represented by the formula (2), particularly preferred compounds are the following compounds.

Examples of the photopolymerization initiator used in the present invention include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6-trimethylbenzoyl Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino- 2-ethyl Benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedion-2- (o-ethoxycarbonyl) oxime, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone, 2- 2-isopropylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2-benzanthraquinone, 2-benzoanthraquinone, , 3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) A dimer of 4,5-diphenylimidazole, a dimer of 2,4,5-triarylimidazole, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (that is, Ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethylmihiraaz ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p- Acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tert- butyltrichloroacetophenone, p- Dichloroacetophenone,?,? -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) heptane, (Trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6- ] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -Triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxy) 4-methoxy) phenyl-s-triazine, 2 (3-bromo-4-methoxyphenyl) , 4-bis-trichloromethane Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s Triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine. These photopolymerization initiators may be used alone or in combination of two or more.

In the present invention, the content of the photopolymerization initiator is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, based on the solid content of the colored photosensitive resin composition. In this case, if the content of the photopolymerization initiator is too small, the curing by exposure may become insufficient, while if too large, the formed colored layer tends to be easily peeled off from the glass substrate at the time of development.

&Lt; Compound represented by formula (1) &gt;

The colored photosensitive resin composition according to the present invention contains a compound represented by the following formula (1). This compound has good solubility in an organic solvent and can generate a base by irradiation or heating to improve color, contrast ratio, heat resistance, and adhesion to a glass substrate.

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group.

Examples of the organic group for R ¹ and R ² include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic. This organic group is usually monovalent, but in the case of forming a cyclic structure, it may be a divalent or higher-valent organic group.

R ¹ and R ² may combine to form a cyclic structure or may further contain a bond of a heteroatom. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired and includes a bond containing a hetero atom such as an oxygen atom, a nitrogen atom or a silicon atom . Specific examples thereof include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (-R) R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond.

From the viewpoint of heat resistance, examples of the bond other than the hydrocarbon group in the organic group of R ¹ and R ² include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, (-N═C (-R) -, -C (═NR) -: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond and a sulfinyl bond.

Substituents other than the hydrocarbon groups in the organic group of R ¹ and R ² are not particularly limited as long as the effect of the present invention is not impaired and examples thereof include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyanato groups A silyl group, an alkoxyl group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxyl group, a carboxyl group, An acyl group, an acyl group, a sulfo group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkenyl ether (-NH ₂ , -NHR, -NRR ': R and R' each independently represent a hydrocarbon group), or the like, and the like, . The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of straight chain, branched chain and cyclic.

Examples of substituents other than the hydrocarbon groups in the organic group of R ¹ and R ² include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyanato groups, cyanate groups, isocyanate groups, thiocyanate groups, A nitro group, a nitro group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, a sulfino group, an acyloxy group, an acyloxy group, an acyloxy group, an acyloxy group, A sulfonyl group, a sulfonyl group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an alkylthioether group, an alkenylthioether group, An ether group, and an aryl thioether group are preferable.

Of these, at least one of R ¹ and R ² is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or may be bonded to each other to form a heterocycloalkyl group or a heteroaryl group having 2 to 20 carbon atoms Do. Examples of the heterocycloalkyl group include a piperidino group and a morpholino group. Examples of the heteroaryl group include an imidazolyl group and a pyrazolyl group.

In the above formula (1), R ³ represents a single bond or an organic group.

Examples of the organic group for R ³ include a group excluding one hydrogen atom from an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group. This organic group may contain a substituent in the organic group. Examples of the substituent include those exemplified as R ¹ and R ² . The organic group may be either straight chain or branched chain.

Among them, R ³ is preferably a single bond, or an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, in which one hydrogen atom is excluded.

Wherein R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, , A sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group.

^Examples of the organic group for R ⁴ and R ^{5 include} those ^exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

Among them, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, An aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, An acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group), an aryl group having 6 to 20 carbon atoms, an electron donating group and / Is an aryl group having 6 to 20 carbon atoms which is substituted, a benzyl group substituted with an electron-donating group and / or an electron-withdrawing group, a cyano group, or a methylthio group. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, A sulfonyl group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group or an organic group.

Examples of the organic group for R ⁶ , R ⁷ , R ⁸ and R ⁹ include those exemplified as R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

In the above formula (1), R ⁶ and R ⁷ do not form a hydroxyl group.

R ⁶ , R ⁷ , R ⁸ and R ⁹ may combine with each other to form a cyclic structure or may contain a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used. For example, R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded to each other by two or more of them, and R ⁶ , R ⁷ , R ^8, and R ⁹ may bond to each other to form a benzene ring atom to which naphthalene, anthracene, Condensed rings such as indene may be formed.

Of the above groups, R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, An aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, An alkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, an electron donating group and / A benzyl group substituted with an aryl group, an electron-donating group and / or an electron-withdrawing group, a cyano group, a methylthio group and a nitro group.

As R ⁶ , R ⁷ , R ⁸ and R ^9, two or more of these are bonded to each other, and the atoms of the benzene ring to which R ⁶ , R ⁷ , R ⁸ and R ⁹ are bonded are bonded to form an naphthalene, anthracene, phenanthrene, Condensed ring is also formed from the viewpoint that the absorption wavelength becomes longer.

More preferably, all of R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, or any one of R ⁶ , R ⁷ , R ⁸ and R ⁹ is a nitro group, and the remaining three are hydrogen atoms.

In the above formula (1), R ¹⁰ represents a hydrogen atom or an organic group.

Examples of the organic group for R ¹⁰ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

Since the compound represented by the above formula (1) has an -OR ¹⁰ group on the para of the benzene ring, the solubility in a solvent is good.

Among them, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a methyl group.

Particularly preferred specific examples among the compounds represented by the above formula (1) include compounds represented by the following formulas.

In the present invention, the compounds represented by the above formula (1) may be used singly or in combination of two or more.

The content of the compound represented by the formula (1) is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator. By using the compound represented by the formula (1) in such a range, a colored photosensitive resin composition excellent in contrast ratio and heat resistance and having high adhesion to a glass substrate can be obtained.

<Organic pigment>

The colored photosensitive resin composition of the present invention contains an organic pigment. The organic pigment is not particularly limited. For example, a compound classified as a pigment in a color index (CI, published by The Society of Dyers and Colourists), specifically, a color index (CI) number It is preferable to use the one with the attached information.

C.I. 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60 (hereafter, &quot; CI Piecement Yellow &quot; , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

C.I. Peak Orange 1 (hereinafter, "CI Peak Orange" is the same and only the numbers are described below), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 55, 59, 61, 63, 64, 71, 73;

C.I. Peak Violet 1 (hereinafter, "C.I. Peak Violet" is the same and only the numbers are described below), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

C.I. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 (hereafter, &quot; CI Piecement Red &quot; 48: 3, 48: 4, 49: 1, 49: 1, 48, : 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: : 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217 , 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

C.I. 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;

C.I. Peak Green 7, C.I. Picment Green 36, C.I. &Lt; SEP &gt; Peak &lt; SEP &gt; Green &

C.I. PICKMENT BROWN 23, C.I. PICKMENT BROWN 25, C.I. PICKMENT BROWN 26, C.I. Peak Brown 28;

C.I. Piecemeal Black 1, C.I. Peak black 7.

In the present invention, the organic pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum superheating method, or a combination thereof.

The content of the organic pigment is preferably 10 to 200% by mass, more preferably 50 to 150% by mass, based on the solid content of the colored photosensitive resin composition, from the viewpoint of forming pixels having excellent transparency and color purity.

The organic pigment is preferably added to the colored photosensitive resin composition after preparing a dispersion in which the organic pigment is dispersed at a suitable concentration using a dispersant. The known dispersing agent is preferably a polymer dispersing agent, and examples thereof include an acrylic copolymer dispersing agent, a polyurethane dispersing agent, a polyester dispersing agent, a polyethylene imine dispersing agent and a polyallylamine dispersing agent. Among them, a polyurethane dispersant is preferred. When these polymer dispersants are used, the dispersibility and dispersion stability of the organic pigment can be improved and the color, contrast ratio, and heat resistance can be improved.

<Solvent>

The colored photosensitive resin composition of the present invention may contain a solvent. The solvent used in the present invention is not particularly limited as long as it can disperse or dissolve the compound represented by the formula (1) and an organic pigment described below or other components described below and does not react with these components and has appropriate volatility.

Such solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono- Tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like ) Alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as ether acetate, and other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as hexane, 2-heptane and 3-heptane, alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, Methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropyl Methyl 3-methoxybutylacetate, 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy- Propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, Other esters such as methyl isobutyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; And amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Toxobutylacetate is preferable because it exhibits excellent solubility in the compound represented by the above formula (1) and can make the dispersibility of the organic pigment excellent, and propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate Is particularly preferable.

The content of the solvent is preferably such that the total concentration of the total solids content of the colored photosensitive resin composition is 5 to 30 mass%, preferably 10 to 20 mass%, from the viewpoint of coatability, stability, etc. of the obtained colored photosensitive resin composition Is more preferable.

The colored photosensitive resin composition of the present invention may contain various additives as required.

Examples of the additive include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); surfactants such as fluorinated surfactants and silicone surfactants; vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like, adhesion promoters such as 2,2 -Oxidation of thiobis (4-methyl-6-t-butylphenol), 2,6-di-t- Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; antiredeposition agents such as sodium polyacrylate; Amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1-propanol, Amino-1,3-propanediol, 4-amino-1,2-butanediol, and the like.

In the present invention, the colored photosensitive resin composition can be prepared by an appropriate method. A preferred method for preparing the colored photosensitive resin composition is a method in which an organic pigment is dissolved in a solvent in the presence of a compound represented by the formula (1) and, if necessary, another dispersant, if necessary, together with a part of an alkali- And the resulting mixture is mixed and dispersed while being pulverized using a bead mill, roll mill or the like to prepare a dispersion, and then an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator and, if necessary, a solvent or an additive agent And the like.

According to the colored photosensitive resin composition thus prepared, it is possible to form a pixel having good color tone, high contrast ratio, excellent heat resistance and improved adhesion to a glass substrate, and furthermore, the colored photosensitive resin composition is excellent in storage stability, Sung is also excellent.

«Color filter, color liquid crystal display»

The color filter according to the present invention comprises a colored layer formed using the colored photosensitive resin composition according to the present invention. A pixel of a color filter can be formed by forming a coating film on a glass substrate or a glass substrate on which a light-shielding layer of a desired pattern is formed in advance by using a colored photosensitive resin composition, irradiating the coating film with radiation in a predetermined pattern, have.

The color liquid crystal display device according to the present invention includes the color filter of the present invention.

Example

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples at all.

&Lt; Compound represented by the above formula (1) &gt;

As the compound represented by the above formula (1), Compound 1 represented by the following formula was prepared. The synthesis method of the compound 1 is shown below.

5.90 g (30 mmol) of 3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of diethylamine and 2.41 ml (equivalent ratio 1.1) Stirring time. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using ethyl hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 1 (4.65 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

<Synthesis of alkali-soluble resin>

1 part by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, and then 15 parts by mass of methacrylic acid, 15 parts by mass of styrene, 35 parts by mass of benzyl methacrylate, 10 parts by mass of glycerol monomethacrylate, 25 parts by mass of N-phenylmaleimide, and 2.5 parts by mass of? -Methylstyrene dimer as a chain transfer agent. Thereafter, the temperature of the reaction solution was raised to 80 캜 with gentle stirring, and the polymerization was maintained at this temperature for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚, and 0.5 part by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to polymerize for 1 hour to obtain a binder resin solution (solid content concentration = 33.0 %). The resin thus obtained had Mw = 10,000 and Mn = 6,000. This resin is referred to as an alkali-soluble resin (D1).

[Example 1]

&Lt; Preparation of organic pigment dispersion &gt;

15 parts by mass of Pigment Red 254 as an organic pigment, 5 parts by mass of Compound 1, 5 parts by mass (in terms of solid content) of a commercially available dispersant S76500 (manufactured by Lubrizol Corporation), propylene glycol monomethyl ether acetate Was treated with a bead mill to prepare an organic pigment dispersion (A-1).

&Lt; Preparation of colored photosensitive resin composition &gt;

100 parts by mass of the obtained organic pigment dispersion (A-1), 50 parts by mass (in terms of solid content) of an alkali-soluble resin (D1), 30 parts by mass of dipentaerythritol hexaacrylate as a photopolymerizable monomer, 10 parts by mass of an ester compound and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored photosensitive resin composition (CR1) having a solid content concentration of 15% by mass.

&Lt; Evaluation of chromaticity characteristics and contrast ratio &gt;

The colored photosensitive resin composition (CR1) was coated on a glass substrate using a spin coater, and then prebaked with a hot plate at 80 DEG C for 10 minutes to form a coating film. The number of revolutions of the spin coater was changed and three coating films having different film thicknesses were formed by the same operation.

Next, after cooling the substrates to room temperature, each coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 2,000 J / m 2 using a high-pressure mercury lamp. Subsequently, a developer consisting of 0.04 mass% aqueous potassium hydroxide solution at 23 占 폚 was ejected onto these substrates at a developing pressure of 1 kgf / cm2 (nozzle diameter of 1 mm) to perform showering for 90 seconds. Thereafter, this substrate was washed with ultra-pure water, dried in air, and then post-baked in a clean oven at 220 캜 for 30 minutes to form a cured film for evaluation.

The obtained three cured films were measured for chromaticity coordinate values (x, y) in a CIE light source using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) and in a CIE colorimetric system at two degrees of view. From the measurement result, the chromaticity coordinate value y and the stimulus value (Y) at the chromaticity coordinate value x = 0.650 were determined. The evaluation results are shown in Table 1.

Further, the base on which the cured film was formed was irradiated with a fluorescent lamp (wavelength range of 380 nm to 780 nm) from the rear side with two polarizing plates sandwiched therebetween, and the front side deflecting plate was rotated to measure the luminance meter LS-100 (manufactured by Minolta Co., ) Were measured for the maximum value and the minimum value of the light intensity transmitted. Then, for each of the cured films, a value obtained by dividing the maximum value by the minimum value was defined as a contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value x = 0.650 was determined. The evaluation results are shown in Table 1.

&Lt; Evaluation of heat resistance &

The colored photosensitive resin composition (CR1) was coated on a glass substrate using a spin coater and then pre-baked on a hot plate at 80 DEG C for 10 minutes to form a coating film having a thickness of 2.5 mu m.

Subsequently, after cooling the substrate to room temperature, each coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 2,000 J / m 2 using a high-pressure mercury lamp. Subsequently, a developer consisting of 0.04 mass% potassium hydroxide aqueous solution at 23 占 폚 was ejected onto these substrates at a developing pressure of 1 kgf / cm2 (nozzle diameter of 1 mm) for 90 seconds. Thereafter, this substrate was washed with ultrapure water, dried in the air, and further baked in a 270 ° C clean oven for 60 minutes to form a cured film for evaluation.

Three different sites on the obtained cured film were observed under an optical microscope (magnification: 200 times) to confirm the presence of foreign matter. Table 1 shows the number of foreign objects observed in one field of view. If foreign matter adheres to the pixels, for example, deterioration of the chromaticity characteristic and deterioration of contrast may occur.

<Evaluation of Storage Stability>

The viscosity of the colored photosensitive resin composition (CR1) immediately after preparation was measured using an E-type clay system (manufactured by TOKYO KAGAKU KOGYO CO., LTD.). The colored photosensitive resin composition (CR1) was filled in a light-shielding glass container and allowed to stand in a closed state at 23 DEG C for 14 days, and then the viscosity was measured again using an E-type clay system. "A" represents a case where the increase rate is less than 5%, "B" represents a case where the increase rate is less than 10% and "C" when the increase rate is 10% or more, And evaluated it. The evaluation results are shown in Table 1.

&Lt; Evaluation of adhesion to glass substrate &gt;

The adhesion of the colored photosensitive resin composition (CR1) to the glass substrate was evaluated by the size of the minimum adhesion pattern size after development. A &quot;, &quot; B &quot;, &quot; C &quot;, and &quot; C &quot; when the minimum adhesion pattern size after development is less than 1 μm and less than 5 μm is "A" Quot; D &quot;. The evaluation results are shown in Table 1.

[Comparative Example 1]

The procedure of Example 1 was repeated except that the compound 1 used in the preparation of the organic pigment dispersion was changed to 1,8-diazabicyclo [5.4.0] undeca-7-ene to prepare an organic pigment dispersion ( A-2) was prepared. Next, a colored photosensitive resin composition (CR2) was prepared in the same manner as in Example 1 except that (A-2) was used in place of the organic pigment dispersion (A-1). The chromaticity characteristics, contrast ratio, heat resistance, storage stability, and adhesion to a glass substrate were evaluated for the colored photosensitive resin composition (CR2) in the same manner as in (CR1). The evaluation results are shown in Table 1.

As can be seen from Table 1, the colored photosensitive resin composition containing the compound represented by the above formula (1) was excellent in chromaticity characteristics, contrast ratio, heat resistance, storage stability, and high adhesion to a glass substrate.

Claims (3)

An alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by the following formula (1), and an organic pigment.

(Shown in, R ¹ and R ² are a hydrogen atom or an organic each independently formula: provided that at least one of R ¹ and R ² represents an organic group. R ¹ and R ² and year they are bonded form a cyclic structure It may be, or may include a combination of the hetero atom. R ³ represents a single bond or an organic. R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group , silanol group, represents a nitro group, alcohol pinot group, sulfo group, sulfonate group, phosphino group, a phosphine P group, a phosphono group, phosphonate group, or an organic. R ^6, R ^7, R ⁸ and R ⁹ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, , A phosphinyl group, a phosphono group, a phosphonate group, an amino , Coming ammonia, or represents an organic group. However, R ⁶ and R ⁷ is optionally, and there is no case where the hydroxyl group. R ^6, R ^7, R ⁸ and R ⁹ form a cyclic structure by combining more than these two, And R ¹⁰ represents a hydrogen atom or an organic group. A color filter comprising a colored layer formed using the colored photosensitive resin composition according to claim 1. A color liquid crystal display device comprising the color filter according to claim 2.