JP2002088136A - Photopolymerizable unsaturated resin and photosensitive resin composition containing the resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new photopolymerizable unsaturated resin capable of forming a resist film having excellent heat resistance, acid resistance, alkali resistance, solvent resistance, surface hardness, etc., to provide a method for producing the resin, to obtain a photosensitive resin composition using the resin and capable of forming a resist film having the excellent properties, and a color filter made of the composition, and to provide a method for producing the color filter. SOLUTION: This photopolymerizable unsaturated resin is represented by general formula (I) (X is a unit represented by general formula (Ia); R is a hydrogen atom or a 1-5C straight-chain or branched-chain alkyl group; Y is an acid anhydride residue; Z is an acid dianhydride residue; n is an integer of 0-20; A is a structure of general formula (Ib); a is an integer of 0-20).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel photopolymerizable unsaturated resin, a method for producing the resin, and a photosensitive resin composition containing the resin. Further, the present invention relates to a color filter using the photosensitive resin composition and a method for producing the color filter.

[0002]

2. Description of the Related Art A photosensitive colored resin composition is used as a resist ink for forming a pattern for producing a color filter used for a color liquid crystal display, a color video camera, an image scanner and the like. Such a photosensitive colored resin composition has excellent light resistance,
Acrylic resin is used because of little color change. However, acrylic resin has insufficient heat resistance, and at an ITO deposition temperature of 200 ° C. or higher,
There is a problem that wrinkles, cracks and the like occur on the surface of the film formed of the resin. As one method for solving these problems, recently, a photopolymerizable resin having a fluorene skeleton has been proposed. Such a resin is characterized in that its cured product is excellent in transparency and heat resistance. Although the above-mentioned problems can be solved to some extent by using these resins, it cannot be said that the required performance can be sufficiently satisfied.

For example, JP-A-4-345,673, JP-A-4-345,608, and JP-A-4-35
JP-A-5,450 and JP-A-4-363,311 disclose the reaction formation between an epoxy acrylate having a bisphenolfluorene structure represented by the following general formula (VI) and a polybasic carboxylic acid or an anhydride thereof. A heat-resistant liquid resist and a color filter material using a material are disclosed.

[0004]

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[0005] However, sticking occurs after film formation and prebaking using these materials, causing mask contamination. Therefore, there is a problem that a contact exposure method that is advantageous for improving the contrast of the pattern shape cannot be applied. In addition, no significant improvement in heat resistance and solvent resistance could be achieved.

Further, for example, see Japanese Patent Application Laid-Open No. 5-399,356.
JP, JP-A-6-1938, and JP-A-7-938
No. 3,122 discloses an epoxy acrylate compound having a bisphenol fluorene structure, an acid anhydride, and an acid dianhydride simultaneously reacting with each other, thereby increasing the molecular weight and introducing a carboxyl group. A method for obtaining a resin represented by the formula (VII) is disclosed. When this method is employed, sticking after prebaking is eliminated, but heat resistance and solvent resistance are insufficient to satisfy recently required high performance.

[0007]

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Here, X ¹ is a unit represented by the general formula (VIIa):

[0009]

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Y ¹ is a residue of an acid anhydride, Z ¹ is a residue of an acid dianhydride, and m ¹ : n ¹ is a molar ratio of 1/99 to 1/99.
The ratio is 90/10. Here, the molar ratio is a molar ratio based on the molecular weight.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, and an object of the present invention is to have the above-mentioned conventional disadvantages when used in a photosensitive resin composition. It is another object of the present invention to provide a novel photopolymerizable resin and a method for producing the resin. Another object of the present invention is a photosensitive colored resin composition containing such a resin, a composition excellent in various performances, that is, a coating film becomes sticking-free after prebaking, and after light irradiation and curing baking. Is heat resistance (250 ° C or higher),
An object of the present invention is to provide a photosensitive resin composition having excellent characteristics such as excellent transparency, adhesion, hardness, solvent resistance, and alkali resistance, and which can be developed with a weak alkaline aqueous solution and has high resolution. Still another object of the present invention is to provide a color filter having excellent performance obtained by using the above composition, and a method for producing the color filter.

[0012]

The present inventors have made an epoxy acrylate having a phenyl-substituted bisphenolfluorene skeleton by reacting with tetracarboxylic dianhydride to form an oligomer, and then blocking the terminal hydroxyl group with a carboxylic anhydride. By using a step reaction, a photopolymerizable unsaturated resin having a carboxyl group was obtained.

Further, by using a composition based on this photopolymerizable unsaturated compound and containing an epoxy compound, a photopolymerization initiator or a sensitizer, and a pigment, high resolution and light irradiation can be achieved. After heat resistance, transparency, adhesion,
The inventors have found that a color filter having excellent hardness, solvent resistance, and alkali resistance can be obtained, and have completed the present invention.

The photopolymerizable unsaturated resin of the present invention is represented by the following general formula (I):

[0015]

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Here, X is a unit represented by the general formula (Ia),

[0017]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group, Y is a residue of an acid anhydride, Z is a residue of an acid dianhydride, and n is an integer from 0 to 20. Show.

The present invention includes a method for producing the photopolymerizable unsaturated resin represented by the above general formula (I), the method comprising the following steps: represented by the following general formula (II) Bisphenylphenol fluorene type epoxy compound is reacted with acrylic acid,

[0020]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group.) Step of obtaining a bisphenylphenol fluorene type epoxy acrylate compound represented by the general formula (III):

[0022]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group); The bisphenylphenol fluorene type epoxy acrylate compound has the general formula (I
Step of reacting the tetracarboxylic dianhydride represented by V):

[0024]

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(Where Z is a residue of a tetracarboxylic dianhydride); and a step of reacting a dicarboxylic anhydride represented by the general formula (V):

[0026]

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(Where Y is the residue of a dicarboxylic anhydride).

The photosensitive resin composition of the present invention contains the photopolymerizable unsaturated resin represented by the general formula (I).

The alkali-soluble photosensitive colored resin composition of the present invention comprises (A) a photopolymerizable unsaturated resin represented by the general formula (I) of claim 1, (B) a compound having an epoxy group,
It contains (C) a photopolymerization initiator and (D) a pigment.

In a preferred embodiment, in the alkali-soluble photosensitive colored resin composition, the compound having an epoxy group and the photopolymerization initiation are added to 100 parts by weight of the photopolymerizable unsaturated compound (I). 5 to 50 parts by weight, 0.1 to 30 parts by weight, and 10 to 2 parts by weight of an agent and a pigment, respectively.
It is contained in a proportion of 00 parts by weight.

In a further preferred embodiment, in the alkali-soluble photosensitive colored resin composition, at least one selected from the group consisting of photopolymerizable monomers and oligomers in addition to the above-mentioned components is used. It is contained in an amount of 50 parts by weight or less based on 100 parts by weight of the photopolymerizable unsaturated compound (I).

The color filter of the present invention is a color filter in which a colored layer is formed in a pattern on a substrate, and the colored layer is obtained by photo-curing the alkali-soluble photosensitive colored resin composition. It is a colored layer.

The method for producing a color filter of the present invention comprises:
A step of applying the alkali-soluble photosensitive colored resin composition on a substrate to form a photosensitive colored layer; a step of patternwise exposing the colored layer and photocuring the exposed portion of the photosensitive colored resin composition; And developing the pattern-exposed colored layer to remove the unexposed portion of the colored layer and leave the photocured colored layer as a pattern on the substrate.

In a preferred embodiment, the development is performed with a dilute aqueous alkaline solution.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable unsaturated resin of the present invention comprises
It is represented by the following general formula (I):

[0036]

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Here, X is a unit represented by the general formula (Ia),

[0038]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group, Y is a residue of an acid anhydride, Z is a residue of an acid dianhydride, and n is an integer of 0 to 20. Show.

The unit of the general formula (Ia) is represented by the following formula (II)
The residues derived from the bisphenylphenol fluorene type epoxy acrylate resin of I) are:

[0041]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group).

This bisphenylphenol fluorene type epoxy acrylate resin is obtained by reacting a bisphenylphenol fluorene type epoxy compound (II) synthesized from bisphenylphenol fluorene with acrylic acid:

[0044]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group).

Y in the above general formula (I) is derived from an acid anhydride. Examples of the acid anhydride include maleic anhydride,
Succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, succinic anhydride, glutaric anhydride, And trimellitic anhydride. Z is derived from an acid dianhydride. Examples of the acid dianhydride include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenylethertetracarboxylic dianhydride, diphenylsulfone. Acid tetracarboxylic dianhydride, 4,
Examples include polycarboxylic anhydrides such as 4′-hexafluoropropylidenebisphthalic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

The photopolymerizable unsaturated resin represented by the general formula (I) is produced, for example, as follows.

For example, first, a substituted or unsubstituted bisphenylphenolfluorene is allowed to act on epichlorohydrin to obtain a bisphenylphenolfluorene epoxy compound (II).

[0049]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group).

The bisphenylphenol fluorene type epoxy acrylate compound (III) is synthesized by reacting the above bisphenylphenol fluorene type epoxy compound (II) with acrylic acid.

[0052]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group).

Next, the bisphenylphenol fluorene type epoxy acrylate compound (III) and the carboxylic dianhydride having a group corresponding to Z are mixed with ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, The reaction is performed by heating in an alkylene glycol monoalkyl ether acetate-based solvent such as methoxybutyl-1-acetate. Further, the unsaturated resin (I) is produced by reacting a carboxylic anhydride having a group corresponding to Y.

The reaction temperature in the production of the photopolymerizable unsaturated resin (I) may be a temperature at which the acid dianhydride and the acid anhydride compound quantitatively react with the hydroxyl group present in the epoxy acrylate resin. preferable. Bisphenylphenol fluorene type epoxy acrylate compound (II
The reaction temperature between I) and the acid dianhydride is preferably from 80 to 130 ° C, more preferably from 90 to 110 ° C. For the subsequent reaction with the acid anhydride, 80-110 ° C.
Is preferable, and 80 to 90 ° C is more preferable. The obtained unsaturated resin (I) has a different molecular weight, an acid value and the like depending on the reaction conditions, and the reaction temperature in the above range is adopted for the preparation thereof.

In the reaction between the bisphenylphenol fluorene type epoxy acrylate compound (III) and the acid dianhydride, when the reaction temperature exceeds 130 ° C., polymerization of the acrylate partially occurs, and the molecular weight rapidly increases. On the other hand, when the temperature is lower than 80 ° C., the reaction does not proceed smoothly, and unreacted acid dianhydride remains.

In the reaction between the above reaction product and the acid anhydride, if the reaction temperature exceeds 110 ° C., condensation of a carboxyl group and a hydroxyl group occurs, and the molecular weight increases. When the temperature is lower than 80 ° C., the reaction does not proceed smoothly, and an acid anhydride of an unreacted acid remains.

In the above reaction, the total of the acid anhydride groups of the acid dianhydride and the acid anhydride is 0.6 to 1 equivalent, preferably 0 to 1 equivalent of the hydroxyl group of the bisphenylphenol fluorene type epoxy acrylate compound. .75 equivalent or more 1
The reaction is performed at a ratio of less than the equivalent. When the amount of the acid dianhydride and the acid anhydride is less than 0.6 equivalent, the polymerizable dianhydride required to sufficiently increase the molecular weight of the resulting photopolymerizable unsaturated resin (I) to achieve high sensitivity. The heavy bonding group cannot be sufficiently introduced. Conversely, if the acid anhydride group exceeds 1 equivalent, the molecular weight cannot be similarly increased. Further, unreacted acid dianhydride and acid anhydride remain. In such a case, when a resist film is formed using the photosensitive composition containing the obtained resin, the developability decreases.

In the above reaction, the ratio of the acid anhydride to the acid dianhydride is from 1/99 to 90/10, preferably from 5/90 by mole ratio.
95-80 / 20. When the proportion of the acid anhydride is less than 1 mol%, the molecular weight becomes too large, so that the resin viscosity increases and the workability deteriorates. Further, when a resist film is formed using a photosensitive composition containing the obtained resin,
The unexposed portion does not dissolve in the developing solution, and a desired pattern cannot be obtained. On the other hand, when the amount of the acid anhydride exceeds 90 mol%, the average molecular weight of the obtained resin becomes small. Therefore, when a resist film is formed using the photosensitive composition containing the obtained resin, sticking remains in the coating film after prebaking.

Thus, the photopolymerizable unsaturated resin represented by the above formula (I) is obtained. The molecular weight and acid value of this resin are controlled by changing the above reaction conditions,
By changing the number of n in the formula (I), it is possible to substantially control. The value of n is set to 0 to 20 depending on the reaction conditions.

The photopolymerizable photosensitive resin composition of the present invention contains the photopolymerizable unsaturated resin (I). This photopolymerizable unsaturated resin (I) can be used alone or as a mixture of two or more.

The composition of the present invention is preferably an alkali-soluble photosensitive colored resin composition, wherein (A) a photopolymerizable unsaturated compound (I), (B) a compound having an epoxy group,
It contains (C) a photopolymerization initiator and (D) a pigment (hereinafter, these may be referred to as A to D components).

Examples of the compound having an epoxy group (component B) that can be contained in the photopolymerizable photosensitive resin composition of the present invention include phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A
Epoxy resins such as epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin and alicyclic epoxy resin; phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate , Allyl glycidyl ether,
Compounds having at least one epoxy group such as glycidyl methacrylate are exemplified.

The photopolymerization initiator (component (C)) which can be contained in the composition of the present invention includes the above-mentioned component (A) and, if necessary, a photopolymerization initiator of a photopolymerizable monomer or oligomer (described later). And / or a compound having a sensitizing effect. Examples of the component C include the following compounds: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-
Acetophenones such as dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzyl, benzoin, benzoinmethyl Benzoin ethers such as ether, benzoin isopropyl ether and benzoin isobutyl ether; benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone,
Sulfur compounds such as 2,4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone; azobis Isobutyronitrile, benzoyl peroxide,
Organic peroxides such as cumene peroxide; and thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole.

One of these compounds may be used alone, or two or more of them may be used in combination. In addition, a compound which does not act as a photopolymerization initiator by itself, but can be used in combination with the above compound, can increase the ability of the photopolymerization initiator. Such compounds include:
For example, a tertiary amine such as triethanolamine, which is effective when used in combination with benzophenone, can be mentioned.

As the pigment (D component) contained in the photosensitive colored resin composition of the present invention, any of an organic pigment and an inorganic pigment can be used. Specific examples of organic pigments include
For example, azo lake-based, insoluble azo-based, phthalocyanine-based, quinacdrine-based, dioxazine-based, isoindolinone-based, verinone-based, anthraquinone-based, perylene-based pigments, and mixtures thereof. Specific examples of the inorganic pigment include, for example, miril blue, iron oxide, cobalt-based pigment, manganese-based pigment, ultramarine, navy blue, cobalt blue, cerulean blue, pyridian, emerald green, cobalt green, and mixtures thereof.

These pigments have a particle size of 0.4 μm or less, which is the lower limit of the wavelength of visible light, in order to color the coating film while maintaining the transparency of the coating film. It is preferred that they are uniformly dispersed in The average particle size of the pigment is practically more preferably 0.2 to 0.3 μm.

In the composition of the present invention, a photopolymerizable monomer and / or oligomer other than the component A may be used as a viscosity modifier or a photocrosslinking agent within a predetermined range depending on the physical properties required for the composition. Can be blended. As the photopolymerizable monomer or oligomer, for example,
Monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; and ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate , Can be exemplified dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate such as a (meth) acrylic acid esters.

One of these compounds can be used alone, or two or more of them can be used in combination.

The composition of the present invention may further contain additives such as an epoxy group curing accelerator, a thermal polymerization inhibitor, an adhesion aid, an antifoaming agent, a surfactant, and a plasticizer, if necessary. it can.

Among these, examples of the epoxy group curing accelerator include amines, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds. Let these contain a small amount,
By heating the coating film after applying the composition, various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties, and hardness of the resulting resist film can be made the same.

Examples of the thermal polymerization inhibitor include hydroquinone,
Hydroquinone monomethyl ether, pyrogallol, t
tert-butylcatechol, phenothiazine and the like.

The cohesive rib is added for the purpose of improving the adhesion of the obtained composition to the substrate. As the adhesion aid, preferably, a carboxyl group, a methacryloyl group,
A silane compound having a reactive substituent such as an isocyanate group or an epoxy group (functional silane coupling agent) is used. Specific examples of such a functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

As the antifoaming agent, for example, silicone-based,
Fluorine-based and acrylic-based compounds are exemplified.

The surfactant is added for the purpose of facilitating the application of the resulting composition and improving the flatness of the resulting coating film. Examples of the surfactant include silicone-based, fluorine-based, and acrylic-based compounds. Specifically, for example, BM-1000
[BM Heme Company]; MegaFac F142D, F17
2, F173 and F183 [manufactured by Dainippon Ink and Chemicals, Inc.]; Florad FC-135, FC-17
0C, Florado FC-430 and FC-431
[Sumitomo 3M Ltd.]; Surflon S-112,
S-113, S-131, S-141 and S
-145 [manufactured by Asahi Glass Co., Ltd.]; SH-28PA, SH-
190, SH-193, SZ-6032, SF-842
8, DC-57 and DC-190 [Toray Silicone
Co., Ltd.].

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl and the like.

The photosensitive resin composition of the present invention is used as a liquid material obtained by dissolving or dispersing the above components in an appropriate solvent, for example, a photosensitive resist ink. As a solvent that can be used here, does not react with each component in the composition,
There is no particular limitation as long as they are mutually soluble. For example, the following solvents are used: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether;
Glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate; diethylene glycol monomethyl ether, diethylene glycol diethyl ether and diethylene glycol dimethyl Diethylene glycols such as Edel, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; propylene glycol such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate Roh alkyl ether acetates;
Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; and ethyl 2-hydroxypropionate and 2-hydroxy Methyl-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate,
Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-
Esters such as ethyl ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate.

Of these, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferred, and in particular, ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate, ethylene Glycol monoethyl ether acetate and methyl amyl ketone are preferred. One of these solvents may be used alone,
Two or more kinds may be used as a mixture.

The photosensitive resin composition of the present invention contains the above-mentioned photopolymerizable unsaturated resin (component A). Usually, in addition to the component A, a compound having an epoxy group (component B) and a photopolymerization initiator (component C), and if necessary, a photopolymerizable monomer and / or oligomer other than the component A, Agents and the like are uniformly contained in the solvent.

The alkali-soluble photosensitive colored resin composition of the present invention contains a pigment (D component) in addition to the above components A, B and C. This composition is useful, for example, as a resist ink for a color filter.

In the above-mentioned alkali-soluble photosensitive colored resin composition, the amount of the component B is 5
Component C is contained in a proportion of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight; and Component C is contained in a proportion of 10 to 200 parts by weight.

When the content of the component B is less than 5 parts by weight, when the composition is used, for example, as a resist ink, the properties of the resin component in the ink after curing, particularly the alkali resistance, are insufficient. Become. Conversely, if it exceeds 50 parts by weight,
Cracking occurs at the time of curing, and the adhesion to the base material tends to decrease. When the content of the component C is less than 0.1 part by weight,
The speed of photopolymerization is slowed due to the reduced sensitivity. Conversely 3
If the amount exceeds 0 parts by weight, it is difficult for the light to reach the substrate when the light is irradiated, so that the adhesion between the substrate and the coating film deteriorates. If the content of the component D is less than 10 parts by weight, desired spectral characteristics cannot be obtained, and if it exceeds 200 parts by weight, the adhesion of the coating film is undesirably reduced.

When the composition contains a photopolymerizable monomer and / or oligomer other than the component A, the content thereof may be within a range not to impair the properties of the composition. Usually, it is contained in an amount of 50 parts by weight or less based on 100 parts by weight of the photopolymerizable unsaturated resin of the general formula (I). If the content exceeds 50 parts by weight, sticking may occur after prebaking.

A photosensitive layer is formed by applying the photosensitive resin composition of the present invention on a substrate and drying the composition. A desired pattern is formed by selectively exposing by light irradiation, curing the exposed portion, and dissolving and removing (developing) the unexposed portion with an alkali solution or the like. As the coating method, a usual method such as a solution immersion method; a spray method; a coating method using a roll coater, a slit coater, a bar coater, a spinner, or the like can be employed. The coating film is formed to have a thickness after drying of about 0.2 to 100 μm, preferably 1 to 10 μm. As light (radiation) used for light irradiation, visible light, ultraviolet light, electron beam, X-ray, α-ray, β-ray, γ-ray, or the like is used. It is also possible to cure the composition by heat. Ultraviolet rays are preferred in terms of economy and efficiency. For UV irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an arc lamp, a xenon lamp, or the like is used.

The photosensitive layer made of the resin composition of the present invention provided on the substrate is selectively exposed using the above-mentioned light, and then developed using a developing solution to remove the unirradiated portions. Then, the coating film is patterned. Examples of the developing method include a puddle method, a dipping method, and a rocking immersion method.

Examples of the developer for patterning using the composition of the present invention include, for example, an alkaline aqueous solution, a water-soluble organic solvent, a mixed solution thereof, and a mixed solution in which a surfactant is added thereto. Can be Preferably, an aqueous alkaline solution or a mixture of an aqueous alkaline solution and a surfactant is used.

The alkali (base) used in the above developer
Examples thereof include alkali metal hydroxides, alkali metal and alkaline earth metal carbonates, and amines. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyl Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo
[5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane and the like are used. Examples of the water-soluble organic solvent include methanol, ethanol, acetone and the like.

The concentration of these alkalis is not particularly limited, but is usually 0.01 to 5% by weight, preferably 0.1 to 3% by weight.
% By weight. The development of the composition of the present invention with an alkaline solution can be carried out at a temperature of usually 10 to 50 ° C, preferably 20 to 40 ° C, using a commercially available developing machine or ultrasonic cleaning machine.

After the alkali development, in order to improve the alkali resistance, it is preferable to heat-treat the obtained pattern to carry out epoxy curing. By such a heat treatment, the durability against strong alkaline water is improved, and various properties required for the solder resist, such as adhesion to glass and metals such as copper, heat resistance, and surface hardness are also improved. The heat treatment is preferably performed at a temperature in the range of 80 to 250 ° C, more preferably 120 to 220 ° C, for example,
1-30 minutes on hot plate, 1 in oven
Performed for 0 to 120 minutes.

The alkali-soluble photosensitive colored resin composition of the present invention can be suitably used for a color filter for a color liquid crystal display and the like.

Next, a description will be given of a resist ink using the alkali-soluble photosensitive colored resin composition of the present invention and a method of manufacturing a color filter using the same.

In order to produce a resist ink using the composition of the present invention, for example, first, a photopolymerizable unsaturated resin represented by the general formula (I) (A component) and a compound having an epoxy group (B component) , And a pigment (D component), and if necessary, a photopolymerizable monomer and / or oligomer, an additive, a solvent, and the like are mixed with stirring. Next, by adding a photopolymerization initiator (C component) and mixing under stirring,
A desired alkali-soluble photosensitive colored resist ink is obtained. The resist ink thus prepared is preferably used after being filtered through, for example, a millipore filter having a pore size of about 1.0 to 0.2 μm.

In order to manufacture a color filter using this ink, first, a black matrix is provided on a substrate which is a medium on which the color filter is formed, and then a red matrix
One of green and blue resist inks is applied over the entire surface using a spinner, a roll coater, or the like, prebaked, and the solvent is evaporated.

Next, exposure is performed with ultraviolet light or the like through a photomask on which a desired pattern is formed. The unexposed area is set to 0.
Develop with an alkali developing solution such as a 4% aqueous sodium carbonate solution and wash with water. And a suitable temperature, for example 200
Post cure at 0 ° C. to dry the coating completely. This forms the first pixel of the color filter.
Next, a pixel of the second color filter is formed adjacent to the pixel of the first color filter by using a similar ink containing a pigment of any one of the remaining two colors and following the same steps as above. I do. Further, the same color ink containing the remaining one-color pigment is used, and the pixels of the third color filter are formed by the same process. In this way, pixels of a color filter composed of three primary colors are obtained.

On these surfaces, a transparent electrode layer made of, for example, ITO (indium-tin oxide) is provided to obtain a color filter. Since the used resist ink contains the specific photopolymerizable unsaturated resin of the present invention, it has excellent heat resistance. Therefore, sputtering at a high temperature of 250 ° C. is possible even when forming the above-mentioned protective film such as ITO. On the other hand, since the resist used conventionally has poor heat resistance, the sputtering temperature is 2
00 ° C was the limit.

The color filter thus obtained is excellent in transparency, adhesion, hardness, solvent resistance, alkali resistance and the like in addition to heat resistance.

The alkali-soluble photosensitive colored resin composition of the present invention can be used not only for the above-mentioned color filters used for color liquid crystal displays and the like but also for various types used for color liquid crystal displays, color facsimile machines, image sensors and the like. It is also used for preparing a multicolor display.

In this case, as in the case of the color filter, first, a coating film is formed by applying a resist ink comprising the composition of the present invention on the surface of the substrate. Next, a negative film is applied to the coating film, and the exposed portion is cured by irradiating active light such as ultraviolet rays, and the unexposed portion is eluted with a weak alkaline aqueous solution. After this alkali development, it is desirable to carry out an epoxy curing treatment by heating to improve the alkali resistance. By using a resist ink comprising the composition of the present invention and performing heat treatment, not only the durability against strong alkaline water is remarkably improved, but also the adhesion to metals such as glass and copper, heat resistance, surface hardness and the like. Various properties required for the solder resist are also improved.

[0099]

According to the present invention, a novel photopolymerizable unsaturated resin, a method for producing the resin, and a photosensitive resin composition containing the resin are provided. This photosensitive resin composition is an alkali-soluble photosensitive colored resin composition useful as, for example, a resist ink for a color filter. When such a composition is used as a resist ink, a coating film is formed on a base material, cured by pattern exposure using ultraviolet light, and developed with a dilute alkaline aqueous solution to easily form a desired resist containing a pigment. It becomes possible. This resist ink is excellent in ultraviolet curability and developability. The present invention includes a method for producing a color filter by such a method. In the present invention, since a specific photopolymerizable unsaturated resin is used, the resulting heat-cured coating film is extremely excellent in heat resistance. Furthermore, for example, a coating film after applying and prebaking a resist ink made of the composition of the present invention containing this resin on a substrate is free of sticking. Therefore, it is possible to expose the pattern in close contact with each other, and to obtain an extremely high resolution. The obtained color filter is excellent in heat resistance, acid resistance, alkali resistance, solvent resistance, surface hardness and the like. Such a color filter is useful as a multi-color display used for a color liquid crystal display device (for example, a television, a video monitor or a computer display), a color facsimile, an image sensor, a color video camera, an image scanner, and the like.

The cured film obtained by photocuring the composition of the present invention is excellent in heat resistance, transparency, adhesion to a substrate, acid resistance, alkali resistance, solvent resistance, surface hardness and the like. Further, since this cured film is an organic coating film, it has a low dielectric constant.
Therefore, the composition of the present invention can be used for many uses other than the above color filters. For example, a material for a protective film of an electronic component (for example, a material for forming a protective film used for a liquid crystal display device including a color filter, an integrated circuit device, a solid-state imaging device, etc.); a material for forming an interlayer insulating and / or planarizing film A solder resist used in the manufacture of a printed wiring board; or an alkali-soluble photosensitive composition suitable for forming a columnar spacer as a substitute for a bead spacer in a liquid crystal display element. Further, the composition of the present invention comprises a material for various optical components (lens, LED, plastic film, substrate, optical disk, etc.); a coating agent for forming a protective film on the optical component; an adhesive for optical components (adhesive for optical fiber) Etc.); a coating agent for producing a polarizing plate; suitably used as a photosensitive resin composition for hologram recording.

[0101]

The present invention will be specifically described below based on examples and comparative examples. In the following, “parts” indicates “parts by weight”.

Example 1 In a 500 ml four-necked flask, a bisphenylphenol fluorene type epoxy resin represented by the formula (II) (R
= H; the abundance of the resin with a = 0 was 95%) 31
2 g (epoxy equivalent 312), 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-di-isobutylphenol, and 72.0 of acrylic acid
g, and 500 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were further mixed and mixed, and air was blown at a rate of 25 ml / min.
Heated at 0-100 ° C. Although this mixture was cloudy, the temperature was gradually raised as it was and heated to 120 ° C. to obtain a solution in which the contents were completely dissolved. This gradually became a clear and viscous solution, but continued stirring as it was,
The acid value was measured over time. Acid value is 2.0mgKO
Heating and stirring were continued until the amount became less than H / g. It took 12 hours for the acid value to reach the target. Thereafter, the mixture is cooled to room temperature, and a colorless and transparent bisphenylphenol fluorene type epoxy acrylate resin represented by the formula (III) (R =
H; the abundance ratio of the resin of a = 0 was 90% or more).

[0103] 300 g of PGMEA was further added to 584 g of a solution containing the thus obtained bisphenylphenol fluorene type epoxy acrylate resin [resin of the general formula (III); R = H], and the mixture was stirred. 80.5 g of dianhydride and 1 g of tetraethylammonium bromide were added and mixed, and the mixture was gradually heated and reacted at 110 to 115 ° C for 4 hours.

After confirming the disappearance of the acid anhydride group in the reaction mixture, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was obtained.
Was added and mixed, and reacted at 90 ° C. for 6 hours to obtain an unsaturated resin of the general formula (I). In this resin, R is H; Y is a group derived from 1,2,3,6-tetrahydrophthalic anhydride, Z is a group derived from benzophenonetetracarboxylic dianhydride; and Y / Z = 50 / 50
(Molar ratio). The resin was a mixture of several compounds. The abundance ratio of the compound in which a = 0 and n is the following value is as follows. Compound with n = 0: 27
%, Compound with n = 1: 25%, compound with n = 2: 19
%, Compound with n = 3: 12%. Other compounds are 17
% (All analyzed by GPC). The disappearance of the acid anhydride during the reaction was confirmed from the IR spectrum.

Comparative Example 1 The following formula (VIII) was placed in a 500 ml four-necked flask.

[0106]

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231 g of a bisphenol fluorene type epoxy resin represented by the following formula (epoxy equivalent: 231; the proportion of the resin having b = 0 was 95%); 450 mg of triethylbenzylammonium chloride; 100 mg of 2,6-di-isobutylphenol; Acrylic acid 72.
0 g was charged and mixed, and heated at 90 to 100 ° C. while blowing air at a rate of 25 ml per minute.

Although the mixture was cloudy, the temperature was gradually raised as it was and heated to 120 ° C. to obtain a solution in which the contents were completely dissolved. This gradually became a transparent and viscous solution, but stirring was continued as it was, and the acid value was measured over time. Heating and stirring were continued until the acid value was less than 2.0 mgKOH / g. It took 12 hours for the acid value to reach the target. Then, the mixture is cooled to room temperature,
And a colorless and transparent PGMEA solution of a bisphenol fluorene type epoxy acrylate resin represented by the formula:

303 g of the bisphenol fluorene type epoxy acrylate resin (VI) thus obtained
Was dissolved in 600 g of propylene glycol monomethyl ether acetate. To this, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added and mixed, and the mixture was gradually heated and reacted at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was added, mixed and reacted at 90 ° C. for 6 hours to obtain a resin represented by the general formula (IX) ( Y ² / Z ² = 50
/ 50 (molar ratio)). The disappearance of the acid anhydride was confirmed from the IR spectrum.

[0110]

Embedded image

Here, X ² is a unit represented by the general formula (IXa):

[0112]

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Y ² is a group derived from 1,2,3,6-tetrahydrophthalic anhydride, and Z ² is a group derived from benzophenonetetracarboxylic dianhydride. The resin is also a mixture of products and several compounds in the same manner in Example 1 was substantially consistent with the numerical values of a and n be in Example 1 for the values of b and n ^2.

Example 2 A photosensitive resin composition 1 was obtained by mixing the photopolymerizable unsaturated resin obtained in Example 1 (hereinafter referred to as "photopolymerizable unsaturated resin 1") and the following components. Photosensitive resin composition 1 (parts by weight) Photopolymerizable unsaturated resin 1 20.0 Dipentaerythritol hexaacrylate 8.6 Tetramethylbiphenyl epoxy resin 4.4 Michler's ketone 0.2 Irgacure 907 1.2 Propylene glycol monomethyl ether Acetate 65.6 Total 100.0

Example 1 of JP-A-8-262221
According to the methods of Nos. To 3, red, green, blue and black pigments were obtained. These are preliminarily dispersed in propylene glycol monomethyl ether acetate, mixed with the above resin composition 1, and subjected to dispersion treatment to obtain a composition having the composition shown in Table 1.
Kinds of color filter inks (RED, GRE
EN, BLUE and BLACK). At the time of the above-mentioned dispersion treatment, treatment was carried out such that the pigment particle diameter was 0.3 μm or less for each color. Table 1 shows the composition of the obtained ink. Table 1 also shows the ink composition of Comparative Example 2 described below.

Next, a transparent glass substrate washed with a neutral detergent, water, isopropyl alcohol and chlorofluorocarbon was prepared as a substrate. First, a black matrix is formed on this glass substrate using BLACK ink, and then R
Using ED, GREEN, and BLUE inks,
Pixels were formed at predetermined positions in the order of red (R) -green (G) -blue (B). In the pixel formation process, after each ink was applied, exposure was performed at the exposure amount shown in Table 1, and prebaking was performed at 80 ° C. for 5 minutes. Development was performed using a 0.4% by weight aqueous solution of sodium carbonate. The film thickness of each pixel is 2 ± for each of R, G, B and black matrix.
It was set to 0.1 μm.

The performance of the obtained color filter ink and color filter was evaluated by the following methods. Table 2 shows the evaluation results. Table 2 also shows the results of Comparative Example 1 described later.
Shown in

(1) Sticking Property Each color filter ink was applied to the above glass substrate by a spin coater and dried to obtain a coating film. Test chart (line width 0.5-50.0 μm) on this coating film
Was placed and irradiated with ultraviolet rays at a predetermined exposure amount through the test chart. After irradiation, remove the test chart,
The stain on the test chart was visually observed. The evaluation results are shown by the following criteria. ：: no stain, Δ: slight stain observed, ×: marked stain.

(2) Resolution The ink for each color filter was applied on the above glass substrate by a spin coater and dried to obtain a coating film. Test chart (line width 0.5-50.0 μm) on this coating film
Was placed and irradiated with ultraviolet rays at a predetermined exposure amount through the test chart. The substrate after irradiation was immersed in a 0.4% aqueous solution of sodium carbonate for 60 seconds to develop, and then the resolution was evaluated.

(3) Light transmittance The substrate containing the patterned resist prepared in the section of measuring the resolution was heated in a circulating drier at 230 ° C. for 60 minutes, and the light of the obtained cured coating film was measured. The transmittance was measured with a spectrophotometer (manufactured by Hitachi, Ltd.). The measurement was performed with light having a wavelength of 700 nm for a red resist, 510 nm for a green resist, and 460 nm for a blue resist.

(4) Heat Resistance The substrate containing the cured coating film prepared in the section of light transmittance measurement was placed in a hot air convection type drying furnace and heated at 250 ° C. for 60 minutes. The decrease in transmittance at the same wavelength as above before and after heating was measured. The evaluation results are shown by the following criteria.
：: 5% or less, Δ: 5 to 10%, ×: 10% or more.

(5) Chemical resistance Six substrates containing a patterned resist prepared in the section of measuring the resolution were prepared, immersed in the following chemical solution under the following conditions, and the substrate was immersed. The appearance was evaluated. The evaluation results are shown by the following criteria: ：: No abnormality in the appearance of the coating film, Δ: Slight peeling or cracking is observed in the appearance of the coating film for at least one chemical solution, ×: At least one chemical solution In addition, remarkable peeling or cracks are observed in the coating film. (A) Acid resistance: immersed in 5 wt% HCl aqueous solution at room temperature for 24 hours (b) Alkali resistance: immersed in 5 wt% NaOH aqueous solution at room temperature for 24 hours 1 immersed in 4 wt% KOH aqueous solution at 50 ° C. for 10 minutes 1 weight (C) Solvent resistance: 3% at 40 ° C. in N-methylpyrrolidone
0 minute immersion in N-methylpyrrolidone at 80 ° C for 15 minutes

Comparative Example 2 The photopolymerizable unsaturated resin obtained in Comparative Example 1 (m / n = 5 /
5; photopolymerizable unsaturated resin 2) and the following components were mixed to obtain photosensitive resin composition 2. Photosensitive resin composition 2 (parts by weight) Photopolymerizable unsaturated resin 2 (m / n = 5/5) 20.0 Dipentaerythritol hexaacrylate 8.6 Tetramethylbiphenyl epoxy resin 4.4 Michler's ketone 0.2 Irga Cure 907 1.2 Propylene glycol monomethyl ether acetate 65.6 Total 100.0

Using this photosensitive resin composition 2, an ink for a color filter and a color filter were prepared and tested in the same manner as in Example 2.

[0125]

[Table 1]

[0126]

[Table 2]

[0127]

As described above, according to the present invention, a novel photopolymerizable unsaturated resin, a method for producing the resin, and a photosensitive resin composition containing the resin are provided. This photosensitive resin composition is, for example, an alkali-soluble photosensitive colored resin composition useful as a photoresist ink for a color filter. When such a composition is used as a resist ink, the ink is excellent in ultraviolet curability and developability. Therefore, after the coating film is formed, a desired resist containing a pigment can be easily formed by exposure to ultraviolet light and development using a diluted alkaline aqueous solution.

In the present invention, since a specific photopolymerizable unsaturated resin is used, the resulting heat-cured coating film is extremely excellent in heat resistance. Furthermore, for example, a coating film after applying and prebaking a resist ink made of the composition of the present invention containing this resin on a substrate is free of sticking. Therefore, it is possible to expose the pattern in close contact,
Extremely high resolution is obtained.

Therefore, the color filter obtained from the composition containing the above resin is excellent in heat resistance, acid resistance, alkali resistance, solvent resistance, surface hardness and the like. Such a color filter is useful as a multi-color display used for a color liquid crystal display device (for example, a television, a video monitor or a computer display), a color facsimile, an image sensor, a color video camera, an image scanner, and the like. Further, the composition of the present invention can be used for many uses other than the above color filters. For example, a material for a protective film of an electronic component; a material for forming an interlayer insulating and / or planarizing film; a solder resist; or an alkali-soluble photosensitive composition suitable for forming a columnar spacer in a liquid crystal display element. Used. Further, the composition of the present invention includes materials for various optical components, a coating agent for forming a protective film on the optical components, an adhesive for optical components, a coating agent for producing a polarizing plate, a photosensitive resin composition for hologram recording, and the like. It is preferably used as

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/20 101 G02B 5/20 101 4J036 G03F 7/004 501 G03F 7/004 501 505 505 7/027 502 7/027 502 515 515 7/028 7/028 (72) Inventor Kei Kitano 236 Nakai, Tatsuno-cho, Tatsuno-shi, Hyogo Nagase Kasei Kogyo Co., Ltd. Harima Plant F-term (reference) 2H025 AA00 AA04 AA06 AA07 AA08 AA10 AA14 AB13 AC01 AD01 BC14 BC31 BC51 BC74 CA01 CA18 CA30 CC12 CC20 FA03 FA17 2H048 BA45 BA48 BB02 BB42 4J011 QA03 QA12 QA13 QA23 QA24 QA33 QA34 QB13 QB19 SA01 SA04 SA05 SA06 SA07 SA21 SA27 SA31 SA41 SA63 SA03 SA01 SA63 SA01 SA03 SA64 SA83 SA01 AC03 AC06 AE04 BA08 BA10 BA20 BA25 BA26 BA28 CB10 CC05 CD10 4J029 AA03 AB01 AB02 AC01 AE04 AE18 BD09B BD09C FC14 JE152 4J036 AA01 AD03 AD12 CB08 CB15 FA01 FA12

Claims (9)

[Claims] 1. A photopolymerizable unsaturated resin represented by the general formula (I): Here, X is a unit represented by the general formula (Ia): R is a hydrogen atom or a C1-5 linear or branched alkyl group, Y is a residue of an acid anhydride, Z is a residue of an acid dianhydride, and n is an integer from 0 to 20. 2. The method for producing a photopolymerizable unsaturated resin represented by the general formula (I) according to claim 1, wherein the bisphenylphenol fluorene type epoxy compound represented by the following general formula (II) is acrylic Reacting the acid to R is a hydrogen atom or a C1-5 linear or branched alkyl group), and a step of obtaining a bisphenylphenol fluorene type epoxy acrylate compound represented by the general formula (III): R is a hydrogen atom or a C1-5 linear or branched alkyl group); a step of reacting the bisphenylphenol fluorene type epoxy acrylate compound with a tetracarboxylic dianhydride represented by the general formula (IV): Formula 5 (Where Z is a residue of a tetracarboxylic dianhydride); and a step of reacting a dicarboxylic anhydride represented by the general formula (V): Wherein Y is the residue of a dicarboxylic anhydride. 3. A photosensitive resin composition containing the photopolymerizable unsaturated resin represented by the general formula (I) according to claim 1. 4. A photopolymerizable unsaturated resin represented by the general formula (I) according to claim 1, (B) a compound having an epoxy group, (C) a photopolymerization initiator, and (D) a pigment. An alkali-soluble photosensitive colored resin composition comprising: 5. The photopolymerizable unsaturated compound (I) 100
The compound having an epoxy group, the photopolymerization initiator, and the pigment were each 5 to 50 parts by weight, and 0.1 part by weight, and 0.1 part by weight.
The alkali-soluble photosensitive colored resin composition according to claim 4, which is contained in a proportion of 1 to 30 parts by weight and 10 to 200 parts by weight. 6. The photopolymerizable unsaturated compound (I) further contains at least one selected from the group consisting of photopolymerizable monomers and oligomers in an amount of 50 parts by weight or less based on 100 parts by weight of the photopolymerizable unsaturated compound (I). The alkali-soluble photosensitive colored resin composition according to claim 5. 7. A color filter in which a colored layer is formed in a pattern on a substrate, wherein the colored layer is formed by applying the alkali-soluble photosensitive colored resin composition according to claim 4 to light. A color filter, which is a colored layer obtained by curing. 8. A step of applying the alkali-soluble photosensitive colored resin composition according to any one of claims 4 to 6 on a substrate to form a photosensitive colored layer, and pattern-exposing the colored layer, A step of photo-curing the exposed colored photosensitive resin composition, and a step of developing the pattern-exposed colored layer to remove the unexposed colored layer and leaving the photo-cured colored layer as a pattern on the substrate A method for producing a color filter. 9. Development with a dilute aqueous alkaline solution,
The method according to claim 8.