Colored curable resin composition, color filter, and display device

Abstract

To provide a colored curable resin composition or the like that can provide a color filter having excellent hyperchromic effect.SOLUTION: A colored curable resin composition contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the resin (B) is a polymer having, as constitutional units, a tertiary carbon-containing (meth)acrylate unit (a1) and an acid radical-bearing unsaturated monomer unit (b1).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a colored curable resin composition, a color filter, and a display device.

Background Art

[0002] In recent years, display devices have been developed to expand the color reproduction range that can be displayed. As part of this, color filters are also required to be darker. As a method for darkening a color filter, a method of increasing the concentration of a colorant in the color filter can be mentioned. However, when the concentration of the colorant is increased, the performance such as the deterioration of the pattern shape is not sufficient. In addition, in order to have the target color characteristics, it is necessary to produce the color filter as a thick film. However, when applied to a liquid crystal display device, color mixing of light with adjacent pixels occurs, so thickening is not preferable.

[0003] For example, although Patent Document 1 describes a colored curable resin composition containing a colorant, a resin, a predetermined polymerizable compound, a polymerization initiator, and a thiol compound, it is desired to further improve darkening (dark color effect).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Therefore, an object of the present invention is to provide a colored curable resin composition and the like that can provide a color filter excellent in dark color effect.

Means for Solving the Problems

[0006] That is, the colored curable resin composition, color filter, and display device according to the present invention have the gist in the following points. [1] It contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and as the resin (B), the colored curable resin composition is characterized in that the constituent units include a polymer composed of a tertiary carbon-containing (meth)acrylate unit (a1) and an unsaturated monomer unit (b1) having an acid group. [2] The colored curable resin composition according to [1], wherein the unsaturated monomer having an acid group, which becomes the (b1), is at least one selected from acrylic acid and methacrylic acid. [3] The colored curable resin composition according to [1] or [2], wherein the resin (B) has an acid value of more than 80 mgKOH / g and a weight average molecular weight of 9000 or less. [4] The colored curable resin composition according to any one of [1] to [3], wherein the colorant (A) contains at least a green colorant. [5] The colored curable resin composition according to [4], wherein the green colorant is at least one selected from C.I. Pigment Green 58 and C.I. Pigment Green 59. [6] The colored curable resin composition according to any one of [1] to [5], wherein the colorant (A) further contains a yellow colorant, and the yellow colorant is at least one selected from C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185. [7] A color filter formed from the colored curable resin composition according to any one of [1] to [6]. [8] A display device including the color filter according to [7].

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a colored curable resin composition that provides a color filter excellent in a dark color effect.

Embodiments for Carrying Out the Invention

[0008] The colored curable resin composition of the present invention contains a colorant (hereinafter sometimes referred to as colorant (A)) and a resin (hereinafter sometimes referred to as resin (B)). The colored curable resin composition of the present invention may contain a polymerizable compound (hereinafter sometimes referred to as polymerizable compound (C)), a polymerization initiator (hereinafter sometimes referred to as polymerization initiator (D)), a solvent (hereinafter sometimes referred to as solvent (E)), and a polymerization initiation aid (hereinafter sometimes referred to as polymerization initiation aid (D1)). The colored curable resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)). In the present invention, the dark color effect means that a difference in color change occurs between the colored composition layer after pre-baking and the color filter after post-baking, and the color per a predetermined film thickness becomes darker.

[0009] The colored curable resin composition according to the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and as the resin (B), a polymer comprising a constituent unit of a tertiary carbon-containing (meth)acrylate unit (a1) and an unsaturated monomer unit (b1) having an acid group is included. In the present specification, “(meth)acrylate” represents at least one selected from the group consisting of acrylate and methacrylate. Expressions such as “(meth)acryloyl” and “(meth)acrylic acid” have the same meaning.

[0010] Unless otherwise specified, the compounds exemplified as each component in the present specification can be used alone or in combination of two or more.

[0011] <Colorant (A)> The colored curable resin composition according to the present invention contains a colorant (A), and the colorant (A) preferably contains at least a green colorant. The green colorant may be either a pigment or a dye, but is preferably a pigment, more preferably zinc phthalocyanine, still more preferably polyhalogenated zinc phthalocyanine, even more preferably polychlorinated zinc phthalocyanine or polybrominated zinc phthalocyanine, and particularly preferably selected from C.I. Pigment Green 58 and C.I. Pigment Green 59.

[0012] The green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) may, if necessary, be subjected to surface treatment using rosin treatment, pigment derivatives having an acidic group or a basic group introduced, graft treatment of the pigment surface with a polymer compound, etc., micronization treatment by a sulfuric acid micronization method, etc., or cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment by an ion exchange method for ionic impurities, etc.

[0013] The green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) is preferably used in the form of a dispersion uniformly dispersed in a solvent, and the dispersion can be obtained by mixing the green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) in a solvent. If necessary, a dispersant may be mixed.

[0014] As the dispersant, any of cationic, anionic, nonionic and amphoteric dispersants may be used, and examples thereof include dispersants such as polyester-based, polyamine-based, and acrylic-based dispersants. These dispersants may be used alone or in combination of two or more. Examples of the dispersant include those with trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Ltd.), EFKA (manufactured by BASF), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (manufactured by BYK-Chemie GmbH), etc. As the dispersant, from the viewpoints of the dispersibility of the colorant and the compatibility with the resin (B) described later, the resin (B) (preferably resin (B1)) may be used. When using a dispersant, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion in which the pigment is uniformly dispersed in the solvent tends to be obtained.

[0015] The solvent is not particularly limited, and examples thereof include the same solvents as the solvent (E) in the colored curable resin composition of the present invention. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc. are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, etc. are more preferable. The amount of the solvent used is not particularly limited, but the solvent is preferably used so that the solid content concentration in the pigment dispersion can be adjusted to 3 to 30% by mass, more preferably 5 to 25% by mass.

[0016] The colorant (A) may contain a pigment and / or a dye such as a yellow colorant, a blue colorant, etc., which are second colorants other than a green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine). The colorant (A) preferably further contains a yellow colorant.

[0017] Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Examples of the organic pigment include yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214; blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60; violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; green pigments other than polyhalogenated zinc phthalocyanine such as C.I. Pigment Green 7, 36; and the like.

[0018] Among them, the pigment preferably contains at least one selected from the group consisting of green pigments other than zinc phthalocyanine, yellow pigments, and blue pigments. As the green colorant (preferably a green pigment) and the blue colorant (preferably a blue pigment), C.I. Pigment Blue 15:3, 15:6, C.I. Pigment Green 7, 36 are preferable. As the yellow colorant (preferably a yellow pigment), it is preferably selected from C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185. These pigments may be used in combination of two or more.

[0019] The pigment may, if necessary, be subjected to surface treatment using rosin treatment, a pigment derivative or a pigment dispersant into which an acidic group or a basic group has been introduced, graft treatment of the pigment surface with a polymer compound or the like, micronization treatment by a sulfuric acid micronization method or the like, or cleaning treatment with an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for ionic impurities, etc. Further, the pigment preferably has a uniform particle size. By performing a dispersion treatment containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

[0020] As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and acrylic-based surfactants. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. In addition, there are also those with trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Ltd.), EFKA (manufactured by BASF Japan Ltd.), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (manufactured by BYK-Chemie GmbH), etc. These can be used alone or in combination of two or more.

[0021] When using a pigment dispersant, its usage amount is preferably 100% by mass or less, more preferably 1 to 50% by mass, based on the pigment. When the usage amount of the pigment dispersant is within the above range, a pigment dispersion in a uniform dispersion state tends to be obtained.

[0022] The dye is not particularly limited, and known dyes can be used. For example, solvent dyes, acid dyes, direct dyes, mordant dyes, etc. can be mentioned. As dyes, for example, compounds classified as having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in the Dyeing Notes (Color Dyeing Co., Ltd.) can be mentioned. Also, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, etc. can be mentioned. Among these, organic solvent-soluble dyes are preferred.

[0023] From the viewpoint of the dark color effect, the content of the total colorant is 45.5% by mass or more, preferably 46.0% by mass or more, more preferably 46.5% by mass or more, based on the solid content of the colored curable resin composition. Also, it is preferably 65% by mass or less, more preferably 63% by mass or less, and even more preferably 61% by mass or less.

[0024] The content of the green colorant can be appropriately adjusted so as to obtain a desired chromaticity. From the viewpoint of the dark color effect, it is preferably 35% by mass or more and 99.9% by mass or less based on the solid content of the total colorant. The lower limit value of the content of the green colorant is more preferably 40% by mass or more, even more preferably 50% by mass or more, and still more preferably 60% by mass or more. Also, the upper limit value of the content of the green colorant is more preferably 98% by mass or less, even more preferably 95% by mass or less, and still more preferably 90% by mass or less. From the viewpoint of the dark color effect, the content of the green colorant is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 55% by mass or less, even more preferably 15% by mass or more and 50% by mass or less, and still more preferably 20% by mass or more and 45% by mass or less, based on the solid content of the colored curable resin composition.

[0025] When the colorant contains both C.I. Pigment Green 59 and C.I. Pigment Green 58, the content ratio of C.I. Pigment Green 59 and C.I. Pigment Green 58 expressed as "Content of C.I. Pigment Green 59: Content of C.I. Pigment Green 58" may be in the range of 0.1 - 99.9:99.9 - 0.1, preferably 1 - 99:99 - 1. These content ratios can be appropriately adjusted according to the desired color.

[0026] When containing a green pigment other than zinc phthalocyanine, the amount of the green pigment other than zinc phthalocyanine is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, still more preferably 10 parts by mass or more, preferably 2000 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 100 parts by mass or less with respect to 100 parts by mass of zinc phthalocyanine.

[0027] The yellow colorant may be either a yellow pigment or a yellow dye, and a yellow pigment is preferred. The content ratio of the total yellow pigment is preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more, still more preferably 15% by mass or more, and even more preferably 20% by mass or more with respect to the solid content of the total colorant. The content ratio of the total yellow pigment is preferably 1% by mass or more and 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less with respect to the solid content of the total colored curable resin composition.

[0028] The blue colorant may be either a blue pigment or a blue dye, and a blue pigment is preferred. The content ratio of the total blue pigment is preferably 0.1% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 25% by mass or less, and still more preferably 3% by mass or more and 20% by mass or less with respect to the solid content of the total colorant. The content ratio of the total blue pigment is preferably 1% by mass or more and 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less with respect to the solid content of the total colored curable resin composition. When the colorant (A) contains both a green colorant and a yellow colorant, the content of the yellow colorant is preferably 1 to 100 parts by mass, more preferably 2 to 80 parts by mass, still more preferably 5 to 60 parts by mass, and even more preferably 8 to 40 parts by mass with respect to 100 parts by mass of the green colorant.

[0029] The total amount of the colorant (A) is preferably 25 to 65% by mass, more preferably 30 to 60% by mass, and still more preferably 35 to 55% by mass in 100% by mass of the solid content of the color-curable resin composition.

[0030] <Resin (B)> The resin (B) used in the present invention may be an alkali-soluble resin. As the resin (B), the structural unit includes a polymer (B1) composed of a tertiary carbon-containing (meth)acrylate unit (a1) and an unsaturated monomer unit (b1) having an acid group (hereinafter, may be referred to as resin (B1)).

[0031] The resin (B1) is a resin that does not contain both a monomer unit having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond and a unit derived therefrom.

[0032] The tertiary carbon-containing (meth)acrylate that becomes the tertiary carbon-containing (meth)acrylate unit (a1) is, for example, the following general formula (1): CH2=C(R)-C(=O)-O-C(R 1 )(R 2 )(R 3 ) (1) (R represents a hydrogen atom or a methyl group. R 1 , R 2 and R 3 represent a monovalent organic group having a carbon atom at the bonding position with a carbon atom, and at least one of R 1 , R 2 and R 3 has one or more hydrogen atoms at the carbon atom at the bonding position with a carbon atom. Among R 1 , R 2 and R 3 , R 1 and R 2 , R2 and R 3 or R 1 and R 3 may together form a ring. It may be a compound represented by ().

[0033] Said R 1 R 2 and R 3 are the same or different, preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 15 carbon atoms, still more preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, even more preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

[0034] R 1 R 2 and R 3 As the hydrocarbon group having 1 to 30 carbon atoms represented by R, R, and R, linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, etc.; Branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 3-methylbutyl group, neopentyl group, 1,1-dimethylpropyl group, 2-methylpentyl group, 3-ethylpentyl group, 2-propylpentyl group, 1-methylpentyl group, 4-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylhexyl group, 1-methylhexyl group, 1-ethylpentyl group, 1-propylbutyl group, 3-ethylheptyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-butylpentyl group, 1-methylnonyl group, 1-ethyloctyl group, 1-propylheptyl group and 1-butylhexyl group; Cycloalkyl groups such as cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group and 4-cyclohexylcyclohexyl group, alicyclic hydrocarbon groups such as decahydronaphthyl group, norbornyl group, adamantyl group, bicyclo[2.2.2]octyl group; Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 1-naphthyl group, 2-naphthyl group, 6-methyl-2-naphthyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthryl group, 2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group, perylenyl group, chrysenyl group and pyrenyl group, etc. may be mentioned. R 1 , R 2 and R 3 The hydrocarbon group having 1 to 30 carbon atoms represented by may be a combination of two selected from the above linear alkyl group, branched alkyl group, alicyclic hydrocarbon group, and aromatic hydrocarbon group. Among them, a linear alkyl group, a branched alkyl group, and an alicyclic hydrocarbon group are preferable, and a branched alkyl group and an alicyclic hydrocarbon group are more preferable.

[0035] R 1 and R 2 , R 2 and R 3 , or R 1 and R 3 The ring that may be formed together by may be the same as the groups mentioned as the above alicyclic hydrocarbon group.

[0036] Specific examples of the tertiary carbon-containing (meth) acrylate unit (a1) include the following structural units (a1-0) to (a1-2).

[0037]

Chemical formula

[0038] R a01 , R a4 and R a5 is preferably a hydrogen atom. L a01 , L a1 and L a2 is preferably an oxygen atom or *-O-(CH2) k01 It is -CO-O- (wherein k01 is preferably an integer of any one of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a02, R a03 , R a04 , R a6 and R a7 The alicyclic hydrocarbon groups in R

[0039] [Chemical formula]

[0040] R a02 , R a03 , R a04 , R a6 and R a7 Examples of the group formed by combining the alkyl group and the alicyclic hydrocarbon group in R

[0041] R a02 , R a03 , and R a04 The number of carbon atoms of the alkyl group in R R a6 and R a7 The number of carbon atoms of the alkyl group in R R a02 , R a03 , and R a04 The number of carbon atoms of the alicyclic hydrocarbon group in R The combined group of the alkyl group and the alicyclic hydrocarbon group preferably has a total number of carbon atoms of 18 or less when these alkyl groups and alicyclic hydrocarbon groups are combined.

[0042] R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, and still more preferably an ethyl group or an isopropyl group.

[0043] m1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1’ is preferably 0 or 1.

[0044] Examples of the structural unit (a1-0) include structural units represented by any of Formula (a1-0-1) to Formula (a1-0-12) and Formula (a1-0-13) to Formula (a1-0-24).

[0045]

Chemical formula

[0046]

Chemical formula

[0047] Examples of the structural unit (a1-1) include structural units represented by any of Formula (a1-1-1) to Formula (a1-1-4) and Formula (a1-1-5) to Formula (a1-1-8).

[0048]

Chemical formula

[0049]

Chem.

[0050] Examples of the structural unit (a1-2) include structural units represented by any of Formula (a1-2-1) to Formula (a1-2-6) and Formula (a1-2-7) to Formula (a1-2-12).

[0051]

Chem.

[0052]

Chem.

[0053] Among them, the tertiary carbon-containing (meth)acrylate unit (a1) is preferably a structural unit represented by Formula (a1-0), more preferably a structural unit represented by Formula (a1-0-1) to (a1-0-24), still more preferably a structural unit represented by Formula (a1-0-13) to (a1-0-24), and even more preferably a structural unit represented by Formula (a1-0-13).

[0054] The content of the tertiary carbon-containing (meth)acrylate unit (a1) is preferably 1% by mass or more and less than 100% by mass in 100% by mass of the constitutional units of the resin (B1). Further, as the resin (B1), a polymer containing the tertiary carbon-containing (meth)acrylate unit (a1) in an amount exceeding 80% by mass in 100% by mass of the constitutional units of the resin (B1) may be contained.

[0055] The unsaturated monomer having an acid group, which becomes the unsaturated monomer unit (b1) having an acid group, is preferably at least one selected from acrylic acid and methacrylic acid, and more preferably acrylic acid.

[0056] The content rate of the unsaturated monomer unit (b1) having an acid group is preferably more than 0% by mass and 99% by mass or less in 100% by mass of the constituent units of the resin (B1).

[0057] The resin (B) (preferably the resin (B1)) preferably has an acid value of more than 80 mgKOH / g and a weight average molecular weight of 9000 or less.

[0058] The acid value of the resin (B1) is preferably more than 80 mgKOH / g, more preferably 85 mgKOH / g or more, still more preferably 95 mgKOH / g or more, even more preferably 105 mgKOH / g or more, preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, still more preferably 200 mgKOH / g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0059] The weight average molecular weight of the resin (B1) in terms of polystyrene is preferably 9000 or less, more preferably 8500 or less, still more preferably 8000 or less, even more preferably 7500 or less, preferably 1000 or more, more preferably 1500 or more, still more preferably 2000 or more, even more preferably 2500 or more.

[0060] The content rate of the resin (B1) is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, still more preferably 60 to 90% by mass in 100% by mass of the resin (B). The content rate of the resin (B1) is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, still more preferably 5 to 40% by mass, even more preferably 8 to 35% by mass in 100% by mass of the solid content of the colored curable resin composition.

[0061] The resin (B) may contain a resin (B2) different from the resin (B1) (hereinafter, may be referred to as the resin (B2)). Examples of the resin (B2) include the following resins [K1] to [K6] and the like. Resin [K1]; a copolymer having a structural unit derived from at least one (a2) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter sometimes referred to as “(a2)”) and a structural unit derived from a monomer (b2) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenic unsaturated bond (hereinafter sometimes referred to as “(b2)”). Resin [K2]; a copolymer having a structural unit derived from (a2), a structural unit derived from (b2), and a structural unit derived from a monomer (c2) copolymerizable with (a2) (provided that it is different from (a2) and (b2)) (hereinafter sometimes referred to as “(c2)”). Resin [K3]; a copolymer having a structural unit derived from (a2) and a structural unit derived from (c2). Resin [K4]; a copolymer having a structural unit obtained by adding (b2) to a structural unit derived from (a2) and a structural unit derived from (c2). Resin [K5]; a copolymer having a structural unit obtained by adding (a2) to a structural unit derived from (b2) and a structural unit derived from (c2). Resin [K6]; a copolymer having a structural unit obtained by adding (a2) to a structural unit derived from (b2) and further adding a carboxylic anhydride and a structural unit derived from (c2).

[0062] Specific examples of (a2) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, etc.; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, etc.; Bicyclic unsaturated compounds containing carboxy groups such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Anhydrides of unsaturated dicarboxylic acids such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; Unsaturated mono[(meth)acryloyloxyalkyl] esters of polyvalent carboxylic acids with a valency of 2 or more such as succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl]; Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the viewpoints of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.

[0063] (b2) refers to a polymerizable compound having, for example, a cyclic ether structure with 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b2) is preferably a monomer having a cyclic ether with 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0064] (b2) includes, for example, a monomer (b2-1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2-1)"), a monomer (b2-2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2-2)"), and a monomer (b2-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2-3)").

[0065] (b2-1) includes, for example, a monomer (b2-1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b2-1-1)"), and a monomer (b2-1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b2-1-2)").

[0066] (b2-1-1) includes glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

[0067] Examples of (b2-1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), the compound represented by formula (I), the compound represented by formula (II), and the like.

[0068] [Chemical formula]

[0069] [In formula (I) and formula (II), R a and R b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X a and X b represent a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c -NH-. R c represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.]

[0070] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and the like. Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, and the like. Ra and R b Examples thereof preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably include a hydrogen atom and a methyl group.

[0071] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. X a and X b Examples thereof preferably include a single bond, a methylene group, an ethylene group, *-CH2-O- and *-CH2CH2-O- (* represents a bond to O), and more preferably include a single bond and *-CH2CH2-O-.

[0072] Examples of the compound represented by formula (I) include compounds represented by any of formula (I-1) to formula (I-15). Among them, compounds represented by formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) are preferred, and compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) are more preferred.

[0073]

Chemical formula

[0074]

Chemical formula

[0075] Examples of the compound represented by formula (II) include compounds represented by any of formula (II-1) to formula (II-15). Among them, compounds represented by formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) are preferred, and compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) are more preferred.

[0076]

Chem.

[0077]

Chem.

[0078] The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When the compound represented by formula (I) and the compound represented by formula (II) are used in combination, their content ratios [compound represented by formula (I): compound represented by formula (II)] are preferably 5:95 to 95:5, more preferably 20:80 to 80:20, on a molar basis.

[0079] (b2-2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of (b2-2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane and the like.

[0080] (b2-3) is more preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group. Specifically, examples of (b2-3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

[0081] As (b2), (b2-1) is preferable in that the reliability such as heat resistance and chemical resistance of the resulting color filter can be made higher. Further, (b2-1-2) is more preferable in that the storage stability of the coloring curable resin composition is excellent.

[0082] (c2) includes methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 decane-8-yl (meth)acrylate (in the art, it is commonly referred to as "dicyclopentanyl (meth)acrylate". It may also be referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 2,6 decen-8-yl (meth)acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate and other (meth)acrylic acid esters; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxy group-containing (meth)acrylic acid esters; Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; Bicyclo unsaturated compounds such as bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, etc.; Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl 3-maleimidobenzoate, N-succinimidyl 4-maleimidobutyrate, N-succinimidyl 6-maleimidocaproate, N-succinimidyl 3-maleimidopropionate, N-(9-acridinyl)maleimide, etc.; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. can be mentioned. Among these, from the viewpoints of copolymerization reactivity and heat resistance, 2-hydroxyethyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferable.

[0083] In resin [K1], the ratio of the structural units derived from each is among all the structural units constituting resin [K1], Structural units derived from (a2); 2 to 60 mol% Structural units derived from (b2); 40 to 98 mol% It is preferably that, Structural units derived from (a2); 10 to 50 mol% Structural units derived from (b2); 50 to 90 mol% is more preferable. When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter can be excellent.

[0084] The resin [K1] can be produced, for example, with reference to the methods described in the document "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Publishing Co., Ltd., 1st edition, 1st printing, issued on March 1, 1972) and the cited references described in the document.

[0085] Specifically, a method of putting predetermined amounts of (a2) and (b2), a polymerization initiator, a solvent, etc. into a reaction vessel, replacing oxygen with nitrogen, for example, to create a deoxygenated atmosphere, and heating and keeping warm while stirring can be mentioned. The polymerization initiator, solvent, etc. used here are not particularly limited, and those commonly used in the art can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) can be mentioned. As the solvent, any one that can dissolve each monomer may be used, and solvents such as those described later as the solvent (E) of the colored curable resin composition of the present invention can be mentioned.

[0086] In addition, the obtained copolymer may be used as the reaction solution as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as the solvent during this polymerization, the reaction solution can be used as it is for the preparation of the colored curable resin composition of the present invention, so the manufacturing process of the colored curable resin composition of the present invention can be simplified.

[0087] In the resin [K2], the ratio of the structural units derived from each is among all the structural units constituting the resin [K2], structural units derived from (a2); 2 to 45 mol% Structural unit derived from (b2); 2 to 95 mol% Structural unit derived from (c2); 1 to 65 mol% It is preferably that, Structural unit derived from (a2); 5 to 40 mol% Structural unit derived from (b2); 5 to 80 mol% Structural unit derived from (c2); 5 to 60 mol% it is more preferably that. When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the resulting color filter can be excellent.

[0088] The resin [K2] can be produced, for example, in the same manner as the method described as the production method of the resin [K1].

[0089] In the resin [K3], the ratio of the structural units derived therefrom is among all the structural units constituting the resin [K3], Structural unit derived from (a2); 2 to 60 mol% Structural unit derived from (c2); 40 to 98 mol% it is preferably that, Structural unit derived from (a2); 10 to 50 mol% Structural unit derived from (c2); 50 to 90 mol% it is more preferably that. The resin [K3] can be produced, for example, in the same manner as the method described as the production method of the resin [K1].

[0090] The resin [K4] can be produced by obtaining a copolymer of (a2) and (c2) and adding a cyclic ether having 2 to 4 carbon atoms that (b2) has to the carboxylic acid and / or carboxylic anhydride that (a2) has. First, a copolymer of (a2) and (c2) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural units derived therefrom is preferably the same ratio as that mentioned for the resin [K3].

[0091] Next, a cyclic ether having 2 to 4 carbon atoms in (b2) is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a2) in the copolymer. Following the production of the copolymer of (a2) and (c2), the atmosphere in the flask is replaced from nitrogen to air, and (b2), a carboxylic acid or carboxylic anhydride, a reaction catalyst for the reaction with the cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are put into the flask, and reacted at, for example, 60 to 130°C for 1 to 10 hours, whereby resin [K4] can be produced. The usage amount of (b2) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting it within this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern can be made good. Since the reactivity of the cyclic ether is high and unreacted (b2) hardly remains, (b2-1) is preferable as (b2) used for resin [K4], and further (b2-1-1) is preferable. The usage amount of the reaction catalyst is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a2), (b2), and (c2). The usage amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a2), (b2), and (c2). Reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment, the heat generation amount due to polymerization, etc. In addition, similar to the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the heat generation amount due to polymerization, etc.

[0092] As a first step, resin [K5] is obtained in the same manner as the production method of resin [K1] described above to obtain a copolymer of (b2) and (c2). Similar to the above, the obtained copolymer may be used as the reaction solution as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. The ratios of the structural units derived from (b2) and (c2) are, respectively, based on the total number of moles of all the structural units constituting the copolymer, Structural unit derived from (b2); 5 to 95 mol% Structural unit derived from (c2); 5 to 95 mol% It is preferably that, Structural unit derived from (b2); 10 to 90 mol% Structural unit derived from (c2); 10 to 90 mol% More preferably, it is that.

[0093] Furthermore, under the same conditions as the production method of resin [K4], by reacting the carboxylic acid or carboxylic acid anhydride that (a2) has with the cyclic ether derived from (b2) that the copolymer of (b2) and (c2) has, resin [K5] can be obtained. The amount of (a2) used for reacting with the said copolymer is preferably 5 to 80 moles with respect to 100 moles of (b2). Since the cyclic ether has high reactivity and unreacted (b2) hardly remains, (b2-1) is preferable as (b2) used for resin [K5], and further (b2-1-1) is preferable.

[0094] Resin [K6] is a resin obtained by further reacting a carboxylic acid anhydride with resin [K5]. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether and the carboxylic acid or carboxylic acid anhydride. Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mole with respect to 1 mole of the amount of (a2) used.

[0095] As the resin (B2), specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid copolymer, etc. [K1]; glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer, etc. [K2]; (meth)acrylate / (meth)acrylic acid copolymer, benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, etc. [K3]; resin obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymer, resin obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, resin obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, etc. [K4]; resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate, etc. [K5]; resin obtained by reacting tetrahydrophthalic anhydride with a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, etc. [K6], etc. can be mentioned. Among them, as the resin (B2), resin [K1] and resin [K2] are preferable, and resin [K1] is particularly preferable.

[0096] The weight average molecular weight of the resin (B2) in terms of polystyrene is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000, and even more preferably from 9,500 to 30,000. When the molecular weight is within the above range, the solubility of the unexposed portion in the developer is high, and the residual film ratio and hardness of the resulting pattern tend to be high. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B2) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

[0097] The solid content acid value of the resin (B2) is preferably 85 mgKOH / g or more, more preferably 100 mgKOH / g or more, still more preferably 110 mgKOH / g or more. Also, the solid content acid value is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, still more preferably 160 mgKOH / g or less. When the solid content acid value of the resin (B2) is within the above range, a colored pattern with good shape tends to be obtained from the colored curable resin composition. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0098] The content of the resin (B2) is preferably from 0 to 60% by mass, more preferably from 5 to 50% by mass, still more preferably from 10 to 40% by mass in 100% by mass of the resin (B). The content of the resin (B2) is preferably from 1 to 40% by mass, more preferably from 2 to 35% by mass, still more preferably from 3 to 30% by mass in 100% by mass of the solid content of the colored curable resin composition.

[0099] The content of resin (B) (preferably the content of resin (B1) and resin (B2)) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass in 100% by mass of the solid content of the colored curable resin composition. When the content of resin (B) is within the above range, the solubility of the unexposed portion in the developer tends to be high.

[0100] <Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D). Examples of the polymerizable compound (C) include compounds having a polymerizable ethylenically unsaturated bond and a hydroxyl group.

[0101] Specific examples of the polymerizable compound (C) include pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol mono(meth)acrylate, ethylene glycol-modified pentaerythritol tri(meth)acrylate, propylene glycol-modified pentaerythritol triacrylate, trimethylolpropane di(meth)acrylate, ethylene glycol-modified trimethylolpropane di(meth)acrylate, ethylene glycol-modified glycerin di(meth)acrylate, propylene glycol-modified glycerin di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ethylene glycol-modified ditrimethylolpropane tri(meth)acrylate, propylene glycol-modified ditrimethylolpropane triacrylate, dipentaerythritol pentaacrylate, Trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. can be mentioned.

[0102] The content of the polymerizable compound (C) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, with respect to the total amount of the solid content of the colored curable resin composition, and is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.

[0103] <Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and can initiate polymerization, and known polymerization initiators can be used. Examples of the polymerization initiator that generates active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds, and biimidazole compounds.

[0104] The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

[0105]

Chemical formula

[0106] Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF), N-1919 (manufactured by ADEKA), PBG-327 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) may be used. Among them, the O-acyl oxime compound is preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, and N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, and more preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine.With these O-acyl oxime compounds, a highly bright color filter can be obtained.

[0107] The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

[0108]

Chemical formula

[0109] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, 379 (manufactured by BASF) etc. may also be used. Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, an oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. In terms of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by formula (d2) is preferred.

[0110] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0111] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

[0112] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboxyalkoxy groups (see, for example, JP-A-7-10913).

[0113] Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation aid (D1) (particularly amines) described later.

[0114] Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, etc., nitrobenzyl tosylates, benzoin tosylate, and the like.

[0115] As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound is preferable, and a polymerization initiator containing an O-acyl oxime compound is more preferable.

[0116] The content of the polymerization initiator (D) is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity can be increased and the exposure time can be shortened, so that the productivity of the color filter is improved.

[0117] <Polymerization initiation aid (D1)> The polymerization initiation aid (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiation aid (D1) is included, it is used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, etc. Among them, thioxanthone compounds are preferable. Two or more kinds of the polymerization initiation aid (D1) may be contained.

[0118] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. Among them, 4,4'-bis(diethylamino)benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

[0119] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

[0120] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0121] Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

[0122] The content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C1). When the amount of the polymerization initiation aid (D1) is within this range, a more sensitive coloring pattern can be formed, and the productivity of the color filter tends to be improved.

[0123] <Solvent (E)> The color-curable resin composition of the present invention preferably contains a solvent (E). Examples of the solvent (E) include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0124] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0125] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

[0126] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate, and the like.

[0127] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.

[0128] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like. Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

[0129] Two or more of the solvents (E) may be used in combination. From the viewpoints of coatability and drying property, an organic solvent having a boiling point of 120°C or higher and 180°C or lower at 1 atm is preferred. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and ethyl 3-ethoxypropionate are more preferred.

[0130] The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness during coating becomes good, and the display characteristics tend to be good because the color density is sufficient when forming a color filter.

[0131] <Leveling agent (F)> Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

[0132] Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) and the like.

[0133] Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by AGC Inc., former Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories Co., Ltd.) etc. are included.

[0134] Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation) etc. are included.

[0135] The content of the leveling agent (F) is, for example, 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.05% by mass or less with respect to the total amount of the colored curable resin composition. Note that the content of the pigment dispersant is not included in this content. When the content ratio of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0136] <Method for producing the dispersion liquid> The colorant (A) may be dispersed in a dispersant and a solvent (E) to form a dispersion liquid. The dispersant is preferably one or both of an acrylic dispersant and a resin (B1), and more preferably both an acrylic dispersant and a resin (B1). The content ratio of the colorant (A) is preferably 1 to 25% by mass, more preferably 2 to 20% by mass in 100% by mass of the dispersion liquid. The content rate of the resin (B1) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass in 100% by mass of the dispersion liquid. The content rate of the acrylic dispersant is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass in 100% by mass of the dispersion liquid.

[0137] <Method for producing a colored curable resin composition> The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and can be prepared by mixing a solvent (E), a leveling agent (F), a polymerization initiation assistant (D1), and other components as required. The colorant (A) can be mixed as the dispersion liquid.

[0138] <Method for producing a color filter> Examples of the method for producing a color filter from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method, etc. Among them, the photolithography method is preferable. The photolithography method is a method of applying the colored curable resin composition to a substrate, drying it to form a colored composition layer, exposing the colored composition layer through a photomask, and developing it. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The color filter of the present invention may be obtained by pre-baking (colored composition layer) of the colored curable resin composition, exposure of the colored composition layer (colored coating film), development of the colored coating film (colored pattern), and post-baking of the colored pattern, or the development of the colored coating film may be omitted as required and obtained by post-baking of the colored coating film.

[0139] As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda-lime glass with a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or a substrate with an aluminum, silver, silver / copper / palladium alloy thin film or the like formed on the substrate is used. Another color filter layer, resin layer, transistor, circuit, etc. may be formed on these substrates. Further, a substrate subjected to surface treatment with 1,1,1,3,3,3-hexamethyldisilazane or the like may be used for the above substrate.

[0140] The formation of each color pixel by photolithography can be performed with known or conventional devices and conditions. For example, it can be produced as follows. First, a colored curable resin composition is applied onto a substrate, and volatile components such as solvents are removed by heating and drying (pre-baking) and / or drying under reduced pressure to obtain a smooth colored composition layer. Examples of the coating method include spin coating, slit coating, slit and spin coating, etc. When performing heating and drying, the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. Also, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When performing drying under reduced pressure, it is preferably performed in a temperature range of 20 to 25°C under a pressure of 50 to 150 Pa. The film thickness of the colored composition layer is not particularly limited and may be appropriately selected according to the film thickness of the target color filter.

[0141] Next, the colored composition layer is exposed through a photomask for forming a target colored pattern to obtain a colored coating film. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application is used. As the light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferred. For example, light with a wavelength of less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, near 408 nm, or near 365 nm can be selectively extracted using a band-pass filter that extracts these wavelength ranges. Specifically, examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, and the like.

[0142] Since it is possible to irradiate the entire exposure surface with parallel light rays uniformly or to perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner (proximity exposure machine) and a stepper (reduction projection exposure machine). By bringing the exposed colored coating film into contact with a developer and developing it, a colored pattern is formed on the substrate. By development, the unexposed portion of the colored coating film is dissolved and removed by the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant. The development method may be any of a paddle method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to perform water washing. Furthermore, it is preferable to perform post-baking on the obtained colored pattern. The post-baking temperature is preferably 80 to 250°C, more preferably 100 to 250°C, still more preferably 150 to 250°C, and even more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 2 to 120 minutes, still more preferably 10 to 60 minutes, and even more preferably 10 to 30 minutes.

[0143] Since the film thickness of the obtained colored coating film and colored pattern affects adjacent pixels, it is preferably as thin as possible. Particularly when it becomes a thick film, when manufacturing a liquid crystal panel, the light of the light source may pass through two or more colors of pixels and leak out. When viewing the panel obliquely, the vividness of the color may be lost. The film thickness of the colored coating film and colored pattern is preferably, for example, 4 μm or less or 3 μm or less, more preferably 2.8 μm or less, still more preferably 2.5 μm or less, and even more preferably 2.3 μm or less. The lower limit of the film thickness of the colored coating film and colored pattern is not particularly limited, but is usually 0.1 μm or more, preferably 0.2 μm or more, 0.5 μm or more, or 1 μm or more, and may be 1.5 μm or more.

[0144] The color filter is formed such that the film thickness after post-baking at a temperature of 230° C. for 30 minutes is 1 to 4 μm (preferably 1 to 3 μm, more preferably 2.8 μm or less, still more preferably 2.5 μm or less, and even more preferably 2.3 μm or less).

[0145] By using the colored curable resin composition of the present invention, a color filter having an excellent dark color effect can be manufactured. The color filter is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging device.

Examples

[0146] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and it is of course possible to appropriately modify and implement it within the range that can conform to the gist of the foregoing and following descriptions, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0147] Synthesis Example 1 A flask equipped with a stirring blade, a reflux cooling tube, a thermometer, and a dropping funnel was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and heated to 90°C. A solution prepared by mixing 81 parts by mass of t-butyl acrylate, 19 parts by mass of acrylic acid, 15 parts by mass of azobis(isobutyronitrile), and 54 parts by mass of propylene glycol monomethyl ether acetate was continuously dropped into the flask from the dropping funnel. The temperature inside the flask during the dropping of the mixed solution was maintained at 90 ± 1°C, and the dropping was completed in 3 hours. After the completion of the dropping, the temperature inside the flask was set to 90 ± 1°C and the reaction was carried out for 3 hours. Then, the temperature inside the flask was raised to 105 - 110°C and the reaction was further carried out for 1.5 hours to obtain a copolymer (resin B1) solution with a solid content of 40.3% by mass (hereinafter sometimes referred to as resin solution (B1)). The weight average molecular weight Mw of the produced copolymer was 6100, and the solid content acid value was 131 mgKOH / g.

[0148] Synthesis Example 2 An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer and replaced with a nitrogen atmosphere. 362 parts by mass of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C with stirring. Next, a mixed solution of 58 parts by mass of acrylic acid, 167 parts by mass of a mixture of 3,4-epoxytricyclo[5.2.1.0 2,6 decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 decane-9-yl acrylate (the content ratio is 1:1 in molar ratio), 65 parts by mass of 2-ethylhexyl acrylate, and 111 parts by mass of propylene glycol monomethyl ether acetate was dropped over 5 hours. On the other hand, a mixed solution prepared by dissolving 27 parts by mass of 2,2-azobis(2,4-dimethylvaleronitrile) in 210 parts by mass of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the completion of the dropping, the mixture was held at 80°C for 5.5 hours and then cooled to room temperature to obtain a copolymer (resin B2) solution having a B-type viscosity (23°C) of 43 mPa·s and a solid content of 29.8% by mass (hereinafter sometimes referred to as resin solution (B2)). The solid content acid value of the produced copolymer was 149 mgKOH / g, the weight average molecular weight Mw was 11220, and the dispersity was 2.25.

[0149] Regarding the measurement of the polystyrene-reduced weight-average molecular weight Mw and number-average molecular weight Mn of the resin obtained in the above synthesis example, the measurement was carried out under the following conditions using the GPC method. Apparatus; HLC-8120GPC (manufactured by Tosoh Corporation) Column; TSK-GEL G2000HXL Column temperature; 40 °C Solvent; THF Flow rate; 1.0 mL / min Concentration of the test solution solid content; 0.001 to 0.01 mass% Injection volume; 50 μL Detector; RI Standard substance for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0150] [Preparation of dispersion liquid] Dispersion liquids (A-1) to (A-3) were prepared by mixing the following components respectively and sufficiently dispersing the pigment using a bead mill. As resins (B1) to (B2), the above resin solutions (B1) to (B2) were used.

[0151] [Preparation of dispersion liquid (A-1)] C.I. Pigment Green 58 14.0 parts Acrylic pigment dispersant 1.9 parts Resin (B2) (in terms of solid content) 6.5 parts Propylene glycol monomethyl ether acetate 77.6 parts

[0152] [Preparation of dispersion liquid (A-2)] C.I. Pigment Green 58 14.0 parts Acrylic pigment dispersant 3.3 parts Resin (B1) (in terms of solid content) 5.6 parts Propylene glycol monomethyl ether acetate 77.1 parts

[0153] [Preparation of dispersion liquid (A-3)] 12.0 parts of C.I. Pigment Yellow 150 5.4 parts of an acrylic pigment dispersant 4.2 parts of resin (B2) (in terms of solid content) 78.4 parts of propylene glycol monomethyl ether acetate

[0154] Example 1 and Comparative Example 1 [Preparation of Colored Curable Resin Composition] The components shown in Table 1 were mixed to obtain a colored curable resin composition.

[0155] [Table 1]

[0156] In Table 1, each component is as follows. The amounts used in the table indicate the amounts of the following components. Dispersion liquids (A-1) to (A-3): The dispersion liquids prepared above Resin (B1): The copolymer solution obtained in Synthesis Example 1 Resin (B2): The copolymer solution obtained in Synthesis Example 2 Polymerizable compound (C): Dipentaerythritol polyacrylate (A-9570W; manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerization initiator (D): Irgacure (registered trademark) OXE-03; manufactured by BASF; a compound represented by formula (d1-24)

[0157] [Chemical Formula] Solvent (E): Propylene glycol monomethyl ether acetate Leveling agent (F): Polyether-modified silicone oil (SH8400; manufactured by Toray Dow Corning Co., Ltd., a propylene glycol monomethyl ether acetate solution with a solid content of 10%)

[0158] [Fabrication of Color Filter] The colored curable resin composition was spin-coated on a 2-inch square glass substrate (Eagle XG; manufactured by Corning Incorporated), and then pre-baked at 100 °C for 3 minutes to form a colored composition layer. After cooling to room temperature, with the distance between the substrate with the colored composition layer formed thereon and a quartz glass photomask set at 100 μm, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), light was irradiated in an air atmosphere at an exposure dose of 150 mJ / cm 2 (standard for 365 nm). As the photomask, one with a 50-μm line and space pattern formed thereon was used. After the light irradiation, the colored coating film was immersed and developed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 24 °C for 60 seconds. After washing with water, post-baking was carried out in an oven at 230 °C for 20 minutes to obtain a color filter.

[0159] [Film Thickness Measurement] For the obtained color filter, the film thickness FT (μm) was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

[0160] [Chromaticity Measurement] For the obtained color filter, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) in the CIE XYZ color system were measured using the characteristic function of the C light source. The xy chromaticity coordinates were measured for the colored composition layer after pre-baking and the color filter after post-baking, and Δx and Δy were calculated using the following equations. When calculating Δx and Δy, the film thicknesses of Example 1 and Comparative Example 1 were the same. Δx = (x value of the color filter after post-baking) - (x value of the colored composition layer after pre-baking) Δy = (y value of the color filter after post-baking) - (y value of the colored composition layer after pre-baking) For example, in the green region, it can be said that the darker color effect from after pre-baking to after post-baking is higher as the absolute values of Δx and Δy are larger. [Industrial Applicability]

[0161] The colored curable resin composition of the present invention can be suitably used in the production of color filters, display devices, and solid-state imaging devices.

Claims

1. It contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), As the resin (B), the constituent units include a polymer composed only of a tertiary carbon-containing (meth)acrylate unit (a1) and an unsaturated monomer unit (b1) having an acid group, The tertiary carbon-containing (meth)acrylate that becomes the tertiary carbon-containing (meth)acrylate unit (a1) is a compound represented by the following general formula (1), A colored curable resin composition for a color filter, characterized in that the resin (B) has an acid value of more than 80 mgKOH / g and 300 mgKOH / g or less, and a weight average molecular weight of 1000 or more and 9000 or less. CH2=C(R)-C(=O)-O-C(R1)(R2)(R3) (1) (R represents a hydrogen atom or a methyl group. R1, R2, and R3 represent monovalent organic groups having a carbon atom at the bonding position with a carbon atom, and at least one of R1, R2, and R3 has one or more hydrogen atoms at the carbon atom at the bonding position with a carbon atom. Among R1, R2, and R3, R1 and R2, R2 and R3, or R1 and R3 may form a ring together.)

2. The colored curable resin composition for a color filter according to claim 1, wherein the unsaturated monomer having an acid group that becomes the (b1) is at least one selected from acrylic acid and methacrylic acid.

3. The content of the colorant (A) is 45.5% by mass or more and 65% by mass or less based on the solid content of the colored curable resin composition for a color filter, The colored curable resin composition for a color filter further contains a dispersant, the colorant (A) contains a pigment, and the content of the dispersant is 1 to 50% by mass based on the pigment. The colored curable resin composition for a color filter according to claim 1 or 2.

4. The colored curable resin composition for a color filter according to any one of claims 1 to 3, wherein the colorant (A) contains at least a green colorant.

5. The color filter coloring curable resin composition according to claim 4, wherein the green colorant is at least one selected from C.I. Pigment Green 58 and C.I. Pigment Green 59.

6. The color filter coloring curable resin composition according to any one of claims 1 to 5, wherein the colorant (A) further includes a yellow colorant, and the yellow colorant is at least one selected from C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185.

7. A color filter formed from the color filter coloring curable resin composition according to any one of claims 1 to 6.

8. A display device including the color filter according to claim 7.

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