TWI881162B - Colored curable resin composition, color filter, and display device - Google Patents

Abstract

The object of the present invention is to provide a coloring hardening resin composition capable of providing a color filter having an excellent dark color effect. A coloring hardening resin composition is characterized in that it comprises a coloring agent (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the resin (B) comprises a polymer whose constituent units include a (meth)acrylate unit (a1) containing a tertiary carbon and an unsaturated monomer unit (b1) having an acid group.

Description

Colored curable resin composition, color filter, and display device

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

In recent years, the development of display monitors to expand the color reproduction area that can be displayed has been promoted, and as part of this, color filters are also required to have darker colors. As a method for darkening color filters, there is a method of increasing the colorant concentration in the color filter, but when the colorant concentration increases, the pattern shape deteriorates, and the performance is insufficient. In addition, in order to have the target color characteristics, the color filter needs to be made into a thick film, but when applied to a liquid crystal display device, it will cause color mixing with the light of adjacent pixels, so thick film is also not ideal.

For example, Patent Document 1 describes a coloring curable resin composition containing a coloring agent, a resin, a predetermined polymerizable compound, a polymerization initiator, and a thiol compound, but further improvement in darkening (darkening effect) is desired. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2020-041154

[The problem that the invention wants to solve]

Therefore, the present invention discloses the following as a subject, namely, to provide a colored curable resin composition capable of providing a color filter having an excellent dark color effect. [Means for solving the subject]

That is, the coloring curable resin composition, color filter, and display device of the present invention have the following aspects. [1] A coloring curable resin composition characterized by comprising a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the resin (B) contains a polymer whose constituent units include a (meth)acrylate unit (a1) containing a tertiary carbon and an unsaturated monomer unit (b1) having an acid group. [2] The coloring curable resin composition as described in [1], wherein the unsaturated monomer having an acid group as the (b1) is at least one selected from acrylic acid and methacrylic acid. [3] The coloring curable resin composition as described in [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 coloring curable resin composition as described in any one of [1] to [3], wherein the coloring agent (A) contains at least a green coloring agent. [5] The coloring curable resin composition as described in [4], wherein the green coloring agent is at least one selected from C.I. Pigment Green 58 and C.I. Pigment Green 59. [6] A coloring curable resin composition as described in any one of [1] to [5], wherein the coloring agent (A) further includes a yellow coloring agent, and the yellow coloring agent 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 by the coloring curable resin composition as described in any one of [1] to [6]. [8] A display device comprising the color filter as described in [7]. [Effects of the invention]

According to the present invention, a colored curable resin composition for forming a color filter having an excellent deep color effect can be provided.

The colored curable resin composition of the present invention includes a colorant (hereinafter, sometimes referred to as a colorant (A)) and a resin (hereinafter, sometimes referred to as a resin (B)). The colored curable resin composition of the present invention may also include a polymerizable compound (hereinafter, sometimes referred to as a polymerizable compound (C)), a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)), a solvent (hereinafter, sometimes referred to as a solvent (E)), and a polymerization initiation aid (hereinafter, sometimes referred to as a polymerization initiation aid (D1)). The colored curable resin composition of the present invention may also include a leveling agent (hereinafter, sometimes referred to as a leveling agent (F)). In the present invention, the dark effect refers to the difference in color change between the coloring component layer after pre-baking and the color filter after post-baking, and the color becomes darker for every specified film thickness.

The coloring curable resin composition of the present invention is characterized in that it contains a coloring agent (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the resin (B) contains a polymer whose constituent units include a (meth)acrylate unit (a1) containing a tertiary carbon and an unsaturated monomer unit (b1) having an acid group. In addition, in this specification, the so-called "(meth)acrylate" means at least one selected from the group consisting of acrylate and methacrylate. Expressions such as "(meth)acryl" and "(meth)acrylic acid" also have the same meaning.

In the present specification, unless otherwise specified, the compounds exemplified as the components may be used alone or in combination of two or more.

<Colorant (A)> The colored curable resin composition of the present invention contains a colorant (A), and the colorant (A) preferably contains at least a green colorant. The green colorant may be any of a pigment and a dye, preferably a pigment, more preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine, more preferably polychlorinated zinc phthalocyanine, polybrominated zinc phthalocyanine, and particularly preferably selected from C.I. Pigment Green 58 and C.I. Pigment Green 59.

For the green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine), rosin treatment, surface treatment using a pigment derivative into which an acidic or alkaline group is introduced, grafting treatment of the pigment surface using a polymer compound, micronization treatment using a sulfuric acid micronization method, or cleaning treatment using an organic solvent or water to remove impurities, or treatment to remove ionic impurities using an ion exchange method, etc. may be performed as necessary.

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. The dispersant may also be mixed as needed.

The dispersant may be any of cationic, anionic and amphoteric dispersants, and polyester, polyamine and acrylic dispersants may be cited. These dispersants may be used alone or in combination of two or more. Dispersants may be cited by trade name: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-chemie Co., Ltd.), etc. As a dispersant, from the viewpoint of dispersibility of the colorant and compatibility with the resin (B), the resin (B) described later (preferably resin (B1)) can be used. When a dispersant is used, its usage amount is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the pigment. If the usage amount of the pigment dispersant is within the above range, there is a tendency to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solvent.

The solvent is not particularly limited, and the same solvents as the solvent (E) in the coloring curable resin composition of the present invention can be cited. Among them, preferred are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyethyl propionate, 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., and more preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxyethyl propionate, etc. The amount of solvent used is not particularly limited and can be adjusted to a concentration of 3% to 30% by mass, preferably 5% to 25% by mass, of solid components in the solvent and pigment dispersion.

Furthermore, the colorant (A) may contain a second colorant other than the green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine), i.e., a pigment or dye such as a yellow colorant or a blue colorant. The colorant (A) preferably further includes a yellow colorant.

As pigments, organic pigments and inorganic pigments can be listed, and compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists) can be listed. As organic pigments, they include: 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 and other yellow pigments; C.I. pigment blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. pigment violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. pigment green 1, 19, 23, 29, 32, 36, 38 and other purple pigments; Green) Green pigments other than polyhalogenated zinc phthalocyanine such as 7, 36, etc. etc.

Among them, as a pigment, it is preferred to contain at least one selected from the group consisting of green pigments, yellow pigments, and blue pigments other than zinc phthalocyanine. The green colorant (preferably a green pigment) and the blue colorant (preferably a blue pigment) are preferably C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:6, C.I Pigment Green 7, and C.I Pigment Green 36. The yellow colorant (preferably a yellow pigment) 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. Two or more of these pigments can be used.

The pigment may be treated with rosin, surface treated with pigment derivatives or pigment dispersants with acidic or alkaline groups, grafted with polymer compounds, micronized by sulfuric acid micronization, or cleaned with organic solvents or water to remove impurities, or removed by ion exchange methods. The pigment preferably has uniform particle size. By containing a pigment dispersant and dispersing the pigment, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric, polyester-based, polyamine-based, acrylic-based surfactants and the like. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, and the like. Trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (manufactured by BYK-Chemie Co., Ltd.). These may be used alone or in combination of two or more.

When a pigment dispersant is used, its usage amount is preferably 100 parts by mass or less, more preferably 1 to 50 parts by mass relative to the pigment. If the usage amount of the pigment dispersant is within the above range, there is a tendency to obtain a pigment dispersion in a uniform dispersed state.

The dye is not particularly limited, and known dyes can be used, for example, solvent dyes, acid dyes, direct dyes, mordant dyes, etc. As dyes, for example, compounds classified as having a hue other than a pigment in the Color Index (published by The Society of Dyers and Colourists) or known dyes described in the Dyeing Notes (Shikisensha Co., Ltd.) can be listed. In addition, based on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, oxyanthracene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes can be listed. Among these, organic solvent-soluble dyes are preferred.

From the viewpoint of the dark color effect, the content of all colorants relative to the solid content of the coloring curable resin composition is 45.5 mass % or more, preferably 46.0 mass % or more, further preferably 46.5 mass % or more, and is preferably 65 mass % or less, more preferably 63 mass % or less, and further preferably 61 mass % or less.

The content of the green colorant can be appropriately adjusted to obtain the desired chromaticity. From the perspective of the dark color effect, it is preferably 35% by mass or more and 99.9% by mass or less relative to the solid content of the entire colorant. The lower limit of the content of the green colorant is more preferably 40% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more. In addition, the upper limit of the content of the green colorant is more preferably 98% by mass or less, more preferably 95% by mass or less, and more preferably 90% by mass or less. From the perspective of the dark color effect, the content of the green colorant relative to the solid content of the coloring curable resin composition is preferably 5 mass % or more and 60 mass % or less, more preferably 10 mass % or more and 55 mass % or less, further preferably 15 mass % or more and 50 mass % or less, further preferably 20 mass % or more and 45 mass % or less.

When the coloring agent 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 by "content of C.I. Pigment Green 59: content of C.I. Pigment Green 58" may be in the range of 0.1 to 99.9:99.9 to 0.1, preferably 1 to 99:99 to 1. These content ratios can be appropriately adjusted according to the desired color.

When a green pigment other than zinc phthalocyanine is contained, the amount of the green pigment other than zinc phthalocyanine used is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 10 parts by mass or more, preferably 2000 parts by mass or less, more preferably 300 parts by mass or less, further preferably 100 parts by mass or less, relative to 100 parts by mass of zinc phthalocyanine.

The yellow coloring agent may be any of a yellow pigment and a yellow dye, preferably a yellow pigment. The content of all yellow pigments relative to the solid content of all coloring agents is preferably 5 mass % or more and 40 mass % or less, more preferably 10 mass % or more, further preferably 15 mass % or more, further preferably 20 mass % or more. The content of all yellow pigments relative to the solid content of all colored curable resin compositions is preferably 1 mass % or more and 30 mass % or less, more preferably 25 mass % or less, further preferably 20 mass % or less.

The blue coloring agent may be any of a blue pigment and a blue dye, preferably a blue pigment. The content of all blue pigments relative to the solid content of all coloring agents is preferably 0.1 mass % or more and 30 mass % or less, more preferably 1 mass % or more and 25 mass % or less, and further preferably 3 mass % or more and 20 mass % or less. The content of all blue pigments relative to the solid content of all coloring curable resin compositions is preferably 1 mass % or more and 30 mass % or less, more preferably 25 mass % or less, and further preferably 20 mass % or less. When the colorant (A) includes 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, further preferably 5 to 60 parts by mass, further preferably 8 to 40 parts by mass, relative to 100 parts by mass of the green colorant.

The total amount of the coloring agent (A) is preferably 25 to 65 mass %, more preferably 30 to 60 mass %, and even more preferably 35 to 55 mass %, based on 100 mass % of the solid content of the colored curable resin composition.

<Resin (B)> The resin (B) used in the present invention may be an alkali-soluble resin. The resin (B) contains a polymer (B1) whose constituent units include a (meth)acrylate unit (a1) containing a tertiary carbon and an unsaturated monomer unit (b1) having an acid group (hereinafter, sometimes referred to as resin (B1)).

The resin (B1) is a resin containing neither a monomer unit having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond nor a unit derived from the monomer unit.

The tertiary carbon-containing (meth)acrylate as the tertiary carbon-containing (meth)acrylate unit (a1) may be, for example, a compound represented by the following general formula (1): _CH2 =C(R)-C(=O)-OC( ^R1 )( ^R2 )( ^R3 ) (1) (R represents a hydrogen atom or a methyl group. ^R1 , ^R2 and ^R3 represent a monovalent organic group having a carbon atom at the bonding position to the carbon atom, and at least one of ^R1 , ^R2 and ^R3 has one or more hydrogen atoms on the carbon atom at the bonding position ^to the carbon atom. Among ^R1 , R2 and ^R3 , ^R1 and ^R2 , ^R2 and ^R3 , or ^R1 and ^R3 may form a ring together.)

The R ¹ , R ² and R ³ are the same or different, and are preferably a alkyl group having 1 to 30 carbon atoms, more preferably a saturated alkyl group having 1 to 15 carbon atoms, further preferably a saturated alkyl group having 1 to 10 carbon atoms, further preferably a saturated alkyl group having 1 to 5 carbon atoms, and particularly preferably a saturated alkyl group having 1 to 3 carbon atoms. The alkyl group may be a saturated alkyl group or an unsaturated alkyl group.

Examples of the alkyl group having 1 to 30 carbon atoms represented by R ¹ , R ² and R ³ include linear chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecanyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, hexadecanyl, heptadecanyl, twentidecyl, twenty-threedecyl, twenty-tetradecyl, pentadecyl, hexadecanyl, heptadecanyl, twenty-octadecanyl, nonadecyl and triacontanyl; Branched chain alkyl groups such as isopropyl, isobutyl, sec-butyl, t-butyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, neopentyl, 1,1-dimethylpropyl, 2-methylpentyl, 3-ethylpentyl, 2-propylpentyl, 1-methylpentyl, 4-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2-ethylhexyl, 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 3-ethylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1-methyloctyl, 1-ethylheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl and 1-butylhexyl; Cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl alicyclic alkyl groups such as cyclopentyl, cyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-dimethylcyclohexyl, cyclooctyl, 4-pentylcyclohexyl, 4-octylcyclohexyl and 4-cyclohexylcyclohexyl, decahydronaphthyl, norbornyl, adamantyl and bicyclo[2.2.2]octyl; Aromatic hydrocarbon groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, 4-butylphenyl, 4-pentylphenyl, 1-naphthyl, 2-naphthyl, 6-methyl-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl, fluorenyl, phenanthrenyl, anthracenyl, 2-dodecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl, perylenyl, chrysyl and pyrenyl. The alkyl group having 1 to 30 carbon atoms represented by ^R1 , ^R2 and ^R3 may be a combination of two selected from the above-mentioned linear alkyl groups, branched alkyl groups, alicyclic alkyl groups and aromatic alkyl groups. Among them, linear alkyl groups, branched alkyl groups and alicyclic alkyl groups are preferred, and branched alkyl groups and alicyclic alkyl groups are more preferred.

Examples of the ring that may be formed together ^by R1 and ^R2 , ^R2 and ^R3 , or ^R1 and ^R3 include the same groups as those exemplified as the alicyclic hydrocarbon group.

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

[In formula (a1-0), formula (a1-1) and formula (a1-2), ^La01 , ^La1 and ^La2 each independently represent an oxygen atom or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents any integer from 1 to 7, and * represents a bonding site with -CO-. ^Ra01 , ^Ra4 and ^Ra5 each independently represent a hydrogen atom or a methyl group. ^Ra02 , ^Ra03 and ^Ra04 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic alkyl group having 3 to 18 carbon atoms, or a group formed by combining these. ^Ra6 and ^Ra7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic alkyl group having 3 to 18 carbon atoms, or a group formed by combining these. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1' represents any integer from 0 to 3. ]

^Ra01 , ^Ra4 and ^Ra5 are preferably hydrogen atoms. ^La01 , ^Ra1 and ^Ra2 are preferably oxygen atoms or *-O-( _CH2 ) _k01 -CO-O- (wherein k01 is preferably any integer from 1 to 4, more preferably 1), and more preferably oxygen atoms. Examples of the alkyl group in ^Ra02 , ^Ra03 , ^Ra04 , ^Ra6 and ^Ra7 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and the like. The alicyclic alkyl group in ^Ra02 , ^Ra03 , ^Ra04 , ^Ra6 and ^Ra7 may be either monocyclic or polycyclic. Examples of monocyclic alicyclic alkyl groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic alkyl groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site).

Examples of the group formed by combining an alkyl group and an alicyclic alkyl group in ^Ra02 , ^Ra03 , ^Ra04 , ^Ra6 and ^Ra7 include methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, cyclohexylmethyl, adamantylmethyl, adamantyldimethyl and norbornylethyl.

The carbon number of the alkyl group in ^Ra02 , ^Ra03 and ^Ra04 is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 to 2. The carbon number of the alkyl group in ^Ra6 and ^Ra7 is preferably 1 to 6, more preferably 1 to 4, and further preferably 2 to 3. The carbon number of the alicyclic alkyl group in ^Ra02 , ^Ra03 and ^Ra04 is preferably 5 to 12, and further preferably 5 to 10. Regarding the group formed by combining an alkyl group and an alicyclic alkyl group, the total carbon number of the combination of the alkyl group and the alicyclic alkyl group is preferably 18 or less.

^Ra02 and ^Ra03 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably methyl or ethyl, and further preferably methyl. ^Ra04 is preferably alkyl groups having 1 to 6 carbon atoms or alicyclic alkyl groups having 5 to 12 carbon atoms, more preferably methyl, ethyl, cyclohexyl or adamantyl. ^Ra6 and ^Ra7 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably methyl, ethyl or isopropyl, and further preferably ethyl or isopropyl.

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.

As the structural unit (a1-0), for example, there can be mentioned a structural unit represented by any one of Formula (a1-0-1) to Formula (a1-0-12) and Formula (a1-0-13) to Formula (a1-0-24).

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

As the structural unit (a1-2), there can be exemplified a structural unit represented by any one of Formula (a2-2-1) to Formula (a1-2-6) and Formula (a1-2-7) to Formula (a1-2-12).

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 formulas (a1-0-1) to (a1-0-24), further preferably a structural unit represented by formulas (a1-0-13) to (a1-0-24), and further preferably a structural unit represented by formula (a1-0-13).

The content of the tertiary carbon-containing (meth)acrylate unit (a1) is preferably 1 mass % or more and less than 100 mass % in 100 mass % of the constituent units of the resin (B1). In addition, the resin (B1) may contain a polymer containing more than 80 mass % of the tertiary carbon-containing (meth)acrylate unit (a1) in 100 mass % of the constituent units of the resin (B1).

The unsaturated monomer having an acid group as 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.

The content of the unsaturated monomer units (b1) having an acid group is preferably more than 0 mass % and not more than 99 mass % in 100 mass % of the constituent units of the resin (B1).

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 not more than 9,000.

The acid value of the resin (B1) is preferably more than 80 mgKOH/g, more preferably more than 85 mgKOH/g, further preferably more than 95 mgKOH/g, further preferably more than 105 mgKOH/g, and preferably less than 300 mgKOH/g, further preferably less than 250 mgKOH/g, further preferably less than 200 mgKOH/g. 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 obtained, for example, by titration using an aqueous potassium hydroxide solution.

The polystyrene-equivalent weight average molecular weight of the resin (B1) is preferably 9,000 or less, more preferably 8,500 or less, further preferably 8,000 or less, further preferably 7,500 or less, preferably 1,000 or more, further preferably 1,500 or more, further preferably 2,000 or more, further preferably 2,500 or more.

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

The resin (B) may contain a resin (B2) different from the resin (B1) (hereinafter, sometimes referred to as the resin (B2)). Examples of the resin (B2) include the following resins [K1] to [K6], etc. Resin [K1]: A copolymer having a structural unit derived from a monomer (a2) (hereinafter referred to as "(a2)") selected from at least one of the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b2) (hereinafter referred to as "(b2)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond; 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) (which is different from (a2) and (b2)) (hereinafter referred to as "(c2)") copolymerizable with (a2; 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).

As (a2), specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid can be cited; unsaturated dicarboxylic acids such as cis-butenedioic acid, fumaric acid, citric 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, and 1,4-cyclohexenedicarboxylic acid can be cited; Bicyclic unsaturated compounds containing carboxyl 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, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Unsaturated dicarboxylic anhydrides such as maleic anhydride, conic 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)acryloxyalkyl] esters of divalent or higher polycarboxylic acids such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate; Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred in terms of copolymerization reactivity or solubility of the obtained resin in alkaline aqueous solution.

(b2) refers to a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxadiazine ring, an oxadiazine ring, and a tetrahydrofuran ring) and an ethylenic unsaturated bond. (b2) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

Examples of (b2) include a monomer (b2-1) having an oxycyclopropane group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b2-1)"), a monomer (b2-2) having an oxycyclobutane group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b2-2)"), and a monomer (b2-3) having a tetrahydrofuranyl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b2-3)").

Examples of (b2-1) include monomers having a structure in which a linear or branched chain aliphatic unsaturated hydrocarbon is epoxidized (b2-1-1) (hereinafter, sometimes referred to as "(b2-1-1)") and monomers having a structure in which alicyclic unsaturated hydrocarbon is epoxidized (b2-1-2) (hereinafter, sometimes referred to as "(b2-1-2)").

Examples of (b2-1-1) include: (meth) glycidyl acrylate, (meth) acrylate β-methyl glycidyl acrylate, (meth) acrylate β-ethyl glycidyl acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl 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-tri(glycidyloxymethyl)styrene, 2,3,5-tri(glycidyloxymethyl)styrene, 2,3,6-tri(glycidyloxymethyl)styrene, 3,4,5-tri(glycidyloxymethyl)styrene, 2,4,6-tri(glycidyloxymethyl)styrene, and the like.

Examples of (b2-1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Co., Ltd.), compounds represented by formula (I), and compounds represented by formula (II).

[In formula (I) and formula (II), ^Ra and ^Rb 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 by a hydroxyl group. Xa and Xb represent} a single bond, * ^-Rc- , * ^-Rc- O-, * ^-Rc- S- or *-Rc ^- NH-. ^Rc represents an alkanediyl group having 1 to 6 carbon atoms; * represents a bond with O]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. Examples of ^Ra and ^Rb include preferably a hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. Examples of ^Xa and ^Xb include preferably a single bond, methylene, ethylidene, * _-CH2- O-, and * _{-CH2CH2 -} O-, and more preferably a single bond _and * _-CH2CH2 -O- (* represents a bond with O).

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

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

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, the content ratio [compound represented by formula (I): compound represented by formula (II)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

As (b2-2), a monomer having an oxycyclobutane group and a (meth)acryloxy group is more preferred. Examples of (b2-2) include 3-methyl-3-methacryloxymethyloxycyclobutane, 3-methyl-3-acryloxymethyloxycyclobutane, 3-ethyl-3-methacryloxymethyloxycyclobutane, 3-ethyl-3-acryloxymethyloxycyclobutane, 3-methyl-3-methacryloxyethyloxycyclobutane, 3-methyl-3-acryloxyethyloxycyclobutane, 3-ethyl-3-methacryloxyethyloxycyclobutane, and 3-ethyl-3-acryloxyethyloxycyclobutane.

As (b2-3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b2-3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b2), (b2-1) is preferred in terms of further improving the reliability of the obtained color filter in terms of heat resistance, chemical resistance, etc. Furthermore, (b2-1-2) is more preferred in terms of excellent storage stability of the colored curable resin composition.

Examples of (c2) include 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 (usually referred to as "dicyclopentyl (meth)acrylate" in the art; in addition, sometimes referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ] (Meth)acrylates such as decen-8-yl ester (in the art, it is commonly referred to as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate; (meth)acrylates containing a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; Bicyclic 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 and 5,6-dihydroxybicyclo[2.2.1]hept-2-ene; Dicarbonyl imide derivatives such as N-phenyl cis-1-butenediamide, N-cyclohexyl cis-1-butenediamide, N-benzyl cis-1-butenediamide, N-succinimidyl-3-cis-1-butenediamide benzoate, N-succinimidyl-4-cis-1-butenediamide butyrate, N-succinimidyl-6-cis-1-butenediamide hexanoate, N-succinimidyl-3-cis-1-butenediamide propionate, and N-(9-acridinyl)cis-1-butenediamide; 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. Among them, 2-hydroxyethyl (meth)acrylate, styrene, vinyltoluene, N-phenyl cis-1-butylene diimide, N-cyclohexyl cis-1-butylene diimide, N-benzyl cis-1-butylene diimide, bicyclo[2.2.1]hept-2-ene, etc. are preferred in terms of copolymerization reactivity and heat resistance.

Among all the structural units constituting the resin [K1], the ratio of the structural units derived from each in the resin [K1] is preferably: Structural units derived from (a2): 2 mol% to 60 mol%; Structural units derived from (b2): 40 mol% to 98 mol%; More preferably, Structural units derived from (a2): 10 mol% to 50 mol%; Structural units derived from (b2): 50 mol% to 90 mol%; If 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 obtained color filter can be excellent.

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

Specifically, the following method can be cited: the specified amounts of (a2) and (b2), a polymerization initiator, and a solvent are placed in a reaction vessel, oxygen is replaced by nitrogen, for example, to create a deoxygenated environment, and the mixture is heated and kept warm while being stirred. The polymerization initiator and solvent used here are not particularly limited, and those commonly used in this field can be used. For example, as the polymerization initiator, there can be mentioned azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, etc.), and as the solvent, any solvent that can dissolve each monomer can be mentioned, and the solvents described later as the solvent (E) of the colored curable resin composition of the present invention can be mentioned.

Furthermore, the obtained copolymer may be used directly as a solution after the reaction, or as a concentrated or diluted solution, or as a solid (powder) obtained by reprecipitation or the like. In particular, by using the solvent contained in the coloring curable resin composition of the present invention as the solvent during the polymerization, the solution after the reaction can be directly used for the preparation of the coloring curable resin composition of the present invention, thereby simplifying the production steps of the coloring curable resin composition of the present invention.

Among all the structural units constituting the resin [K2], the ratio of the structural units derived from each in the resin [K2] is preferably: Structural units derived from (a2): 2 mol% to 45 mol%; Structural units derived from (b2): 2 mol% to 95 mol%; Structural units derived from (c2): 1 mol% to 65 mol%; More preferably, Structural units derived from (a2): 5 mol% to 40 mol%; Structural units derived from (b2): 5 mol% to 80 mol%; Structural units derived from (c2): 5 mol% to 60 mol%; If 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 obtained color filter can be excellent.

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

Among all the structural units constituting the resin [K3], the ratio of the structural units derived from each in the resin [K3] is preferably: Structural unit derived from (a2): 2 mol% to 60 mol%; Structural unit derived from (c2): 40 mol% to 98 mol%; More preferably Structural unit derived from (a2): 10 mol% to 50 mol%; Structural unit derived from (c2): 50 mol% to 90 mol%; Resin [K3] can be manufactured, for example, in the same manner as the method described as the manufacturing method of resin [K1].

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

Next, the cyclic ether having 2 to 4 carbon atoms in (b2) is reacted with a portion of the carboxylic acid and/or carboxylic anhydride derived from (a2) in the copolymer. After the copolymer of (a2) and (c2) is produced, the atmosphere in the flask is replaced from nitrogen to air, (b2), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in the flask, and the reaction is carried out at 60°C to 130°C for 1 hour to 10 hours, thereby producing resin [K4]. The amount of (b2) used is preferably 5 mol to 80 mol, more preferably 10 mol to 75 mol, relative to 100 mol of (a). By setting the range, the storage stability of the coloring 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 improved. In terms of the high reactivity of the cyclic ether and the difficulty in leaving unreacted (b2), the (b2) used in the resin [K4] is preferably (b2-1), and further preferably (b2-1-1). The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a2), (b2) and (c2). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a2), (b2) and (c2). The reaction conditions such as the loading method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization. In addition, the loading method or reaction temperature can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization, similar to the polymerization conditions.

Regarding resin [K5], as a first stage, a copolymer of (b2) and (c2) is obtained in the same manner as the production method of the above-mentioned resin [K1]. As described above, the obtained copolymer can be used directly as a solution after the reaction, or as a concentrated or diluted solution, or can be used as a solid (powder) obtained by a method such as reprecipitation. Relative to the total molar number of all structural units constituting the copolymer, the ratios of the structural units derived from (b2) and (c2) are preferably: Structural units derived from (b2): 5 mol% to 95 mol%; Structural units derived from (c2): 5 mol% to 95 mol%; More preferably Structural units derived from (b2): 10 mol% to 90 mol%; Structural units derived from (c2): 10 mol% to 90 mol%;

Furthermore, under the same conditions as the method for producing resin [K4], the carboxylic acid or carboxylic anhydride contained in (a2) and the cyclic ether derived from (b2) contained in the copolymer of (b2) and (c2) are reacted to obtain resin [K5]. The amount of (a2) reacted with the copolymer is preferably 5 mol to 80 mol relative to 100 mol of (b2). In terms of the high reactivity of the cyclic ether and the difficulty in leaving unreacted (b2), (b2-1) is preferably used as the (b2) used in resin [K5], and (b2-1-1) is more preferably used.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride and hydroxyl groups generated by the reaction of cyclic ether with carboxylic acid or carboxylic anhydride are reacted. Examples of carboxylic anhydride include maleic anhydride, conic 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, etc. The amount of carboxylic anhydride used is preferably 0.5 mol to 1 mol relative to 1 mol of (a2).

Specific examples of the resin (B2) include: 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid copolymer and the like resin [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-cyclohexyl butylene diimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] decyl ester/(meth)acrylic acid/N-cyclohexyl butylene diimide/2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxycyclobutane/(meth)acrylic acid/styrene copolymer and the like resins [K2]; (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer and the like resins [K3]; resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, [K4]; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate with (meth)acrylic acid; and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting the copolymer with tetrahydrophthalic anhydride. [K6] Among them, the resin (B2) is preferably resin [K1] or resin [K2], and particularly preferably resin [K1].

The weight average molecular weight of the resin (B2) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 30,000, further preferably 9500 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 rate or hardness of the obtained pattern tends to be high. The molecular weight distribution of the resin (B2) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1 to 6, more preferably 1.2 to 4.

The solid acid value of the resin (B2) is preferably 85 mgKOH/g or more, more preferably 100 mgKOH/g or more, and further preferably 110 mgKOH/g or more. In addition, the solid acid value is preferably 200 mgKOH/g or less, more preferably 180 mgKOH/g or less, and further preferably 160 mgKOH/g or less. When the solid acid value of the resin (B2) is within the above range, a well-shaped colored pattern tends to be obtained from the self-coloring 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 obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B2) in 100% by mass of the resin (B) is preferably 0% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, and even more preferably 10% by mass to 40% by mass. The content of the resin (B2) in 100% by mass of the solid content of the coloring curable resin composition is preferably 1% by mass to 40% by mass, more preferably 2% by mass to 35% by mass, and even more preferably 3% by mass to 30% by mass.

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

<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 polymerizable compounds having ethylenically unsaturated bonds and hydroxyl groups.

Specific examples of polymerizable compounds (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, trihydroxymethylpropane di(meth)acrylate, ethylene glycol-modified trihydroxymethylpropane di(meth)acrylate, ethylene glycol-modified glycerol di(meth)acrylate, propylene glycol-modified glycerol di(meth)acrylate, di-trihydroxymethylpropane tri(meth)acrylate, ethylene glycol-modified di-trihydroxymethylpropane tri(meth)acrylate, propylene glycol-modified di-trihydroxymethylpropane triacrylate, dipentaerythritol pentaacrylate, Trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tri(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.

The content of the polymerizable compound (C) relative to the total amount of the solid components of the colored curable resin composition is preferably 1 mass % or more, more preferably 2 mass % or more, further preferably 3 mass % or more, and is preferably 50 mass % or less, more preferably 40 mass % or less, further preferably 30 mass % or less.

<Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active free radicals, acids, etc. by the action of light or heat to start polymerization, and a known polymerization initiator can be used. Examples of polymerization initiators that generate active free radicals include phenylalkyl ketone compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds, and biimidazole compounds.

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

Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-( 3,3-dimethyl-2,4-dioxacyclopentylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02 (both manufactured by BASF), N-1919 (manufactured by ADEKA), and PBG-327 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) can also be used. Among them, the O-acyl oxime compound is preferably selected from N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, and N-acetyloxy- Preferably, the at least one selected from the group consisting of 1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine and 1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine is selected. More preferably, the at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine is selected. If the O-acyl oxime compounds are used, a color filter with high brightness can be obtained.

The phenylalkyl ketone 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.

Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) can also be used. Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-〔4-(2-hydroxyethoxy)phenyl〕propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzoyl dimethyl ketal. In terms of sensitivity, compounds having a partial structure represented by formula (d2) are preferred as phenylalkyl ketone compounds.

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-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

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, Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open No. 62-174204, etc.), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (for example, see Japanese Patent Laid-Open No. 7-10913, etc.).

Furthermore, the polymerization initiator (D) includes 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, benzoyl, methyl phenylglyoxylate, and titaniumocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) described later (especially amines).

Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylzincium p-toluenesulfonate, 4-hydroxyphenyldimethylzincium hexafluoroanticorate, 4-acetoxyphenyldimethylzincium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylzincium hexafluoroanticorate, triphenylzincium p-toluenesulfonate, triphenylzincium hexafluoroanticorate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroanticorate; nitrobenzyl toluenesulfonates; and benzoin toluenesulfonate.

The polymerization initiator (D) is preferably a polymerization initiator comprising at least one selected from the group consisting of an alkyl phenoxide compound, a triazine compound, an acyl phosphine oxide compound, an O-acyl oxime compound and a biimidazole compound, and more preferably a polymerization initiator comprising an O-acyl oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, relative to 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, high sensitivity can be achieved and the exposure time can be shortened, thereby improving the productivity of the color filter.

<Polymerization initiator (D1)> Polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound that starts polymerization by a polymerization initiator. When a polymerization initiator (D1) is included, it is used in combination with a polymerization initiator (D). As polymerization initiator (D1), amine compounds, alkoxyanthracene compounds, thioxanone compounds, and carboxylic acid compounds can be listed. Among them, thioxanone compounds are preferred. Two or more polymerization initiators (D1) may also be contained.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

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, and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thiothione compound include 2-isopropylthiothione, 4-isopropylthiothione, 2,4-diethylthiothione, 2,4-dichlorothiothione, and 1-chloro-4-propoxythiothione.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

The content of the polymerization initiator (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 initiator (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)> The colored 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.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, cyclohexanol acetate, and γ-butyrolactone.

Examples of the ether solvent 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, phenethyl ether and methyl anisole.

Examples of the ether ester solvent 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.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone.

As alcohol solvents, there are: methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerol. As aromatic hydrocarbon solvents, there are: benzene, toluene, xylene and mesitylene. As amide solvents, there are: N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

Two or more solvents (E) may be used in combination. In terms of coating properties and drying properties, organic solvents having a boiling point of 120°C or higher and 180°C or lower at 1 atm are preferred. Among them, preferred are 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, and more preferred are 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.

The content of the solvent (E) is preferably 70% by mass to 95% by mass, more preferably 75% by mass to 92% by mass, relative to the coloring curable resin composition. In other words, the solid content of the coloring curable resin composition is preferably 5% by mass to 30% by mass, more preferably 8% by mass to 25% by mass. When the content of the solvent (E) is within the above range, flatness during coating is improved, and when a color filter is formed, color concentration is not insufficient, and display characteristics tend to be improved.

<Leveling agent (F)> As the leveling agent (F), there can be listed: silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may also have polymerizable groups in the side chains.

Examples of silicone-based surfactants include surfactants having siloxane bonds in the molecule. Specifically, they include: Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (trade name; Toray Dow Corning) (manufactured by 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 Co., Ltd.), etc.

As fluorine-based surfactants, surfactants having fluorine-carbon chains in the molecule can be cited. Specifically, they include: Fluorad (registered trademark) FC430, Fluorad (registered trademark) FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-71 8-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC Corporation, formerly Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Laboratories Co., Ltd.), etc.

As silicone-based surfactants having fluorine atoms, surfactants having siloxane bonds and fluorocarbon chains in the molecule can be cited. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation) can be cited.

The content of the leveling agent (F) relative to the total amount of the coloring curable resin composition is, for example, 0.001 mass % or more and 0.2 mass % or less, preferably 0.002 mass % or more and 0.1 mass % or less, and more preferably 0.005 mass % or more and 0.05 mass % or less. In addition, this content does not include the content of the pigment dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

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

<Method for producing colored curable resin composition> The colored curable resin composition of the present invention can be prepared by containing a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and optionally a solvent (E), a leveling agent (F), a polymerization initiator aid (D1), and other components.

<Method for manufacturing color filter> As a method for manufacturing a color filter from the coloring curable resin composition of the present invention, photolithography, inkjet method, printing method, etc. can be listed. Among them, photolithography is preferred. Photolithography is a method of applying the coloring curable resin composition on a substrate, drying it to form a coloring composition layer, and exposing and developing the coloring composition layer through a photomask. In photolithography, a coloring coating film that is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or not performing development. The color filter of the present invention can be obtained by pre-baking the coloring curable resin composition (coloring composition layer), exposing the coloring composition layer (coloring coating), developing the coloring coating (coloring pattern), and post-baking the coloring pattern. It can also be obtained by post-baking the coloring coating without developing the coloring coating as needed.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, sodium calcium glass coated with silicon dioxide on the surface, or resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, or aluminum, silver, silver/copper/palladium alloy thin films, etc. can be used. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates. In addition, substrates subjected to surface treatment based on 1,1,1,3,3,3-hexamethyldisilazane, etc. can also be used.

The formation of each color pixel by photolithography can be performed by known or conventional devices or conditions. For example, it can be produced as follows. First, a coloring curable resin composition is applied to a substrate, and heat drying (pre-baking) and/or reduced pressure drying are performed to remove volatile components such as solvents and dry them, thereby obtaining a smooth coloring composition layer. As coating methods, spin coating, slit coating, slit and spin coating, etc. can be listed. The temperature during heat drying is preferably 30°C to 120°C, and more preferably 50°C to 110°C. In addition, the heating time is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. When performing reduced pressure drying, it is preferably performed at a pressure of 50 Pa to 150 Pa and a temperature range of 20°C to 25°C. The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected according to the film thickness of the target color filter.

Next, a colored coating film is obtained by exposing a photomask for forming a target colored pattern through a colored composition layer. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application is used. As a light source used in the exposure, a light source that generates light with a wavelength of 250 nm to 450 nm is preferred. For example, a filter that cuts off the wavelength range can be used to cut off light less than 350 nm, or a bandpass filter that takes out light in the wavelength range near 436 nm, 408 nm, and 365 nm can be used to selectively take out light in these wavelength ranges. Specifically, as a light source, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc. can be listed.

In order to irradiate the entire exposure surface with parallel light uniformly or to accurately align the mask with the substrate on which the coloring composition layer is formed, it is preferable to use an exposure device such as a mask aligner (proximity exposure machine) and a stepper (reduction projection exposure machine). The coloring coating film after exposure is brought into contact with a developer to form a coloring pattern on the substrate. By developing, the unexposed part of the coloring coating film is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 mass% to 10 mass%, and more preferably 0.03 mass% to 5 mass%. Furthermore, the developer may also contain a surfactant. The developing method may be any one of a coating method, an immersion method, and a spray method. Furthermore, the substrate may be tilted at any angle during development. After development, it is preferably washed with water. Furthermore, it is preferably to post-bake the obtained colored pattern. The post-bake temperature is preferably 80°C to 250°C, more preferably 100°C to 250°C, more preferably 150°C to 250°C, and more preferably 160°C to 235°C. The post-baking time is preferably 1 minute to 120 minutes, more preferably 2 minutes to 120 minutes, further preferably 10 minutes to 60 minutes, further preferably 10 minutes to 30 minutes.

The thickness of the resulting colored coating or colored pattern will affect adjacent pixels, so it is better to be as thin as possible. In particular, when a thick film is made, when making a liquid crystal panel, the light source light sometimes leaks through two or more pixels, and when the panel is observed from an oblique angle, there is a concern that the color vividness disappears. The thickness of the colored coating or colored pattern is preferably 4 μm or less or 3 μm or less, more preferably 2.8 μm or less, further preferably 2.5 μm or less, and further preferably 2.3 μm or less. The lower limit of the film thickness of the colored coating film or the 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.

The color filter is formed so that the film thickness after post-baking at a temperature of 230° C. for 30 minutes becomes 1 μm to 4 μm (preferably 1 μm to 3 μm, more preferably 2.8 μm or less, further preferably 2.5 μm or less, further preferably 2.3 μm or less).

By using the colored curable resin composition of the present invention, a color filter having an excellent deep color effect can be produced. The color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic electroluminescence (EL) device, an electronic paper, etc.) and a solid-state imaging element. [Example]

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples at all, and can be implemented with appropriate modifications within the scope of the subject matter described above and below, which are all included in the technical scope of the present invention. Furthermore, in the following, unless otherwise specified, "parts" means "parts by mass", and "%" means "% by mass".

Synthesis Example 1 Add 100 parts by mass of propylene glycol monomethyl ether acetate to a flask equipped with a stirring blade, a reflux cooling tube, a thermometer, and a dropping funnel and heat to 90°C. Mix 81 parts by mass of tert-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 and continuously drip into the flask using a dropping funnel. The temperature in the flask during the dripping of the mixed solution was maintained at 90±1°C, and the dripping was completed in 3 hours. After the addition was completed, the temperature in the flask was adjusted to 90±1°C and the reaction was carried out for 3 hours. Then, the temperature in the flask was raised to 105°C-110°C and the reaction was carried out for another 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 generated copolymer was 6100, and the solid content acid value was 131 mgKOH/g.

Synthesis Example 2 A suitable amount of nitrogen was passed through a flask equipped with a reflux cooler, a dropping funnel and a stirrer to replace the atmosphere with a nitrogen atmosphere, and 362 parts by mass of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. while stirring. Subsequently, 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 (containing ratio of 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 added dropwise 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 added dropwise over 6 hours. After the addition was completed, the mixture was kept 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 generated copolymer was 149 mgKOH/g, the weight average molecular weight Mw was 11220, and the dispersion degree was 2.25.

The polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn of the resin obtained in the above synthesis example were measured by GPC method under the following conditions. Apparatus: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: THF Flow rate: 1.0 mL/min Solid content concentration of test liquid: 0.001 mass% to 0.01 mass% Injection volume: 50 μL Detector: Refractive index (RI) Calibration standard substance: TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

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

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

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

[Preparation of dispersion (A-3)] C.I. Pigment Yellow 150                           12.0 parts Acrylic pigment dispersant                     5.4 parts Resin (B2) (solid content conversion)                4.2 parts Propylene glycol monomethyl ether acetate                    78.4 parts

Example 1 and Comparative Example 1 [Preparation of a coloring curable resin composition] The components listed in Table 1 were mixed to obtain a coloring curable resin composition.

[Table 1] (Mass) Embodiment 1 Comparison Example 1 Colorant (A) Dispersion liquid (A-1) 60.1 Dispersion liquid (A-2) 67.5 Dispersion liquid (A-3) 20.9 18.6 Resin (B) Resin (B1) 1.7 Resin (B2) 2.2 Polymerizable compound (C) 1.3 1.3 Polymerization initiator (D) 1.0 1.0 Solvent (E) 51.2 44.6 Leveling agent (F) 0.1 0.1 Color change after PoB when the film thickness is the same Δx -0.0113 -0.0035 Δy 0.0266 0.0083

The components in Table 1 are as follows. The amounts used in the table show the amounts used of the following components. Dispersion (A-1) to (A-3): Dispersion prepared as described above Resin (B1): Copolymer solution obtained in Synthesis Example 1 Resin (B2): Copolymer solution obtained in Synthesis Example 2 Polymerizable compound (C): Dipentaerythritol polyacrylate (A-9570W; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Polymerization initiator (D): IRGACURE (registered trademark) OXE-03: manufactured by BASF; compound represented by formula (d1-24)

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

<Production of color filter> A coloring curable resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) and pre-baked at 100°C for 3 minutes to form a coloring composition layer. After cooling, the substrate with the coloring composition layer formed thereon and a quartz glass mask were set at a distance of 100 μm, and light was irradiated in an atmospheric environment at an exposure dose of 150 mJ/ ^cm2 (365 nm reference) using an exposure machine (TME-150RSK; manufactured by Topcon). A mask with a 50 μm line and space pattern was used. The colored coating film after light irradiation was immersed in an aqueous developer containing 0.12% of a non-ionic surfactant and 0.04% of potassium hydroxide at 24° C. for 60 seconds, washed with water, and then baked in an oven at 230° C. for 20 minutes to obtain a color filter.

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

[Chromaticity measurement] The obtained color filter was measured for spectroscopy using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) in the XYZ color system of CIE were measured using the characteristic function of the C light source. The xy chromaticity coordinates were measured for the coloring composition layer after pre-baking and the color filter after post-baking, and Δx and Δy were calculated according to the following formula. When calculating Δx and Δy, the film thickness of Example 1 and Comparative Example 1 was the same. Δx = (x value of the color filter after post-baking) - (x value of the coloring composition layer after pre-baking) Δy = (y value of the color filter after post-baking) - (y value of the coloring composition layer after pre-baking) For example, in the green area, the larger the absolute values of Δx and Δy, the higher the dark effect from pre-baking to post-baking. [Industrial Availability]

The colored curable resin composition of the present invention can be preferably used in the manufacture of color filters, display devices, and solid-state imaging devices.

without

without

Claims (8)

A colored curable resin composition, characterized in that it comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the resin (B) comprises a polymer whose constituent units comprise a (meth)acrylate unit (a1) containing a tertiary carbon and an unsaturated monomer unit (b1) having an acid group, and the (meth)acrylate unit (a1) containing a tertiary carbon is any one of the following constituent units (a1-0) to (a1-2):

In formula (a1-0), formula (a1-1) and formula (a1-2), ^La01 , ^La1 and ^La2 each independently represent an oxygen atom or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents any integer of 1 to 7, * represents a bonding site with -CO-, ^Ra01 , ^Ra4 and ^Ra5 each independently represent a hydrogen atom or a methyl group, ^Ra02 , ^Ra03 and ^Ra04 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic alkyl group having 3 to 18 carbon atoms, or a group formed by combining these, ^Ra6 and ^Ra7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic alkyl group having 3 to 18 carbon atoms, or a group formed by combining these, m1 represents any integer of 0 to 14, n1 represents any integer of 0 to 10, n1' represents any integer from 0 to 3. The colored curable resin composition as described in claim 1, wherein the unsaturated monomer having an acid group as the (b1) is at least one selected from acrylic acid and methacrylic acid. A colored curable resin composition as described in claim 1 or claim 2, wherein the resin (B) has an acid value exceeding 80 mgKOH/g and a weight average molecular weight of 9000 or less. A colored curable resin composition as described in claim 1 or claim 2, wherein the colorant (A) contains at least a green colorant. A colored curable resin composition as described in claim 4, wherein the green colorant is at least one selected from C.I. Pigment Green 58 and C.I. Pigment Green 59. The colored curable resin composition as described in claim 1 or claim 2, wherein the colorant (A) further comprises 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. A color filter formed from a colored curable resin composition as described in any one of claims 1 to 6. A display device comprising a color filter as described in claim 7.