Color-curable resin composition, color filter, and display device

Abstract

A color-curable resin composition capable of forming a color filter with haze without the addition of inorganic fine particles can be provided. [Solution] The solution comprises a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the resin comprises structural unit A derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and formula (1): TIFF2026047239000016.tif1453[in the formula, R 1 This represents a hydrogen atom or a methyl group. R 2 [This represents a linear or branched alkyl group having 6 to 20 carbon atoms.] The copolymer α comprises a structural unit B derived from a monomer represented by the following: A colored curable resin composition wherein the content of structural unit B in the copolymer α is 50 to 90 mol% relative to the total amount of structural units constituting the copolymer α.

Description

[Technical Field]

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

[0002] A color filter substrate has a structure in which a black matrix layer and color filters, such as red (R), green (G), and blue (B) for forming each pixel are formed on a transparent substrate, and a protective film is sometimes laminated on top thereof. It is used in liquid crystal display devices and organic electroluminescent (EL) display devices. Such display devices require a sufficient field of view even when viewed from an oblique angle. For example, Patent Document 1 discloses a color-curable resin composition that contains inorganic fine particles and can form a color filter that provides a good field of view from an oblique angle. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-081304 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Conventional color-curable resin compositions use inorganic fine particles to scatter light transmitted through the display device in all directions, thereby averaging the light in the field of view and widening the viewing angle. However, in compositions capable of forming a color filter with haze using inorganic fine particles, the scattering effect may decrease due to the uneven dispersion state of the inorganic fine particles as they settle. Therefore, there is a need to further ensure the field of view when viewing the display device from an oblique angle in color filters formed from color-curable resin compositions.

[0005] Therefore, the object of the present invention is to provide a color-curable resin composition that can form a color filter having haze without the addition of inorganic fine particles. [Means for solving the problem]

[0006] The inventors have found that the above objective can be achieved by the colored curable resin composition of the present invention, as described below. That is, the present invention includes the following embodiments. [1] Contains a colorant, resin, polymerizable compound and polymerization initiator, The resin comprises structural unit A, which is derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and formula (1): [ka] [In the formula, R 1 This represents a hydrogen atom or a methyl group. R 2 [This represents a linear or branched alkyl group having 6 to 20 carbon atoms.] The copolymer α comprises a structural unit B derived from a monomer represented by the following: The content of structural unit B in the copolymer α is 50 to 90 mol% relative to the total amount of structural units constituting the copolymer α. Colored curable resin composition. [2] The colored curable resin composition according to [1], wherein the resin further comprises a copolymer β different from the copolymer α. [3] The colored curable resin composition according to [1] or [2], wherein copolymer α further comprises a structural unit C derived from an ethylenically unsaturated group-containing isocyanate compound or a monomer having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond. [4] The colored curable resin composition according to any one of [1] to [3], wherein the resin content is 20 to 60% by mass, based on the solid content of the colored curable resin composition. [5] The colored curable resin composition according to any one of [1] to [4], wherein the content of copolymer α is 5 to 80% by mass per 100 parts by mass of resin. The content of the overlapping compound is 50 to 85 parts by mass with respect to 100 parts by mass of the resin, and the colored curable resin composition according to any one of [1] to [5]. 〔7〕A color filter which is a cured film of the colored curable resin composition according to any one of [1] to [6]. 〔8〕The color filter according to [7], having a haze value of 1 to 50% in terms of a thickness of 2.5 μm. 〔9〕A display device including the color filter according to [7] or [8].

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a colored curable resin composition capable of forming a color filter having haze without adding inorganic fine particles.

Embodiments for Carrying Out the Invention

[0008] Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention. Also, when a plurality of upper limit values and lower limit values are described for specific parameters, any upper limit value and lower limit value among these can be combined to form a suitable numerical range.

[0009] <Colored Curable Resin Composition> The colored curable resin composition of the present invention contains a colorant, a resin, a polymerizable compound, and a polymerization initiator.

[0010] (Resin) The resin contained in the colored curable resin composition of the present invention includes a structural unit A derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and the formula (1):

Chemical formula

[0011] Conventionally, to impart haze to color filters, inorganic fine particles were used, for example, as described in Patent Document 1. However, problems can arise due to the sedimentation of the inorganic fine particles. In contrast, the color-curable resin composition of the present invention contains a copolymer α having structural unit A derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and structural unit B derived from a monomer represented by formula (1). This makes it possible to form a color filter with the desired haze without adding inorganic fine particles.

[0012] Examples of monomers that derive structural unit A from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides in copolymer α include: Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, p-vinylbenzoic acid; 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, and 1,4-cyclohexenedicarboxylic acid; Bicyclounsaturated 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, 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 valence of 2 or more, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl]; Unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid, etc. can be mentioned. Among these, from the viewpoints of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution, acrylic acid, methacrylic acid, etc. are preferable.

[0013] R in the monomer represented by formula (1) that gives structural unit B in copolymer α 2 has 6 to 20 carbon atoms, preferably 7 to 18 carbon atoms, more preferably 8 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms. R in the monomer represented by formula (1) 2 When the number of carbon atoms of is within the above range, a colored curable resin composition capable of forming a color filter having a desired haze can be obtained. When the number of carbon atoms of R in the monomer represented by formula (1) 2 is equal to or more than the lower limit value, sufficient haze can be obtained, which is advantageous. Further, when the number of carbon atoms of R in the monomer represented by formula (1) 2 is large, compared with the case where it is small, the haze of the film can be ensured with a smaller amount of copolymer α, which is advantageous for reliability such as chemical resistance. On the other hand, when the number of carbon atoms of R 2 is more than the above upper limit value, the surface state of the cured film tends to become rough.

[0014] R in the monomer represented by formula (1) 2 is preferably a branched-chain alkyl group. Also, in the monomer represented by formula (1), R 2Preferred branched alkyl groups in this compound are 2-ethylhexyl, 2-hexyldecyl, and 2-butyloctyl groups.

[0015] In one embodiment of the present invention, examples of monomers represented by formula (1) include heptyl acrylate, octyl acrylate, isononyl acrylate, dodecyl acrylate, isodecyl acrylate, hexadecyl acrylate, stearyl acrylate, isostearyl acrylate, docosyl acrylate, dodecyl methacrylate, and 2-ethylhexyl acrylate. When structural unit B in copolymer α is derived from the monomer represented by formula (1) as exemplified above, it is easier to secure the desired haze in the color filter, and furthermore, a good surface condition of the cured film is easily obtained, and it tends to have excellent chemical resistance, etc. The structural unit B in copolymer α may originate from one monomer represented by formula (1), or from two or more monomers represented by formula (1).

[0016] The content of structural unit B in copolymer α is 50 to 90 mol% relative to the total amount of structural units constituting copolymer α. When the content of structural unit B in copolymer α is within the above range, a color curable resin composition capable of forming a color filter having the desired haze can be obtained. If the content of structural unit B in copolymer α is above the lower limit, it may be advantageous in that sufficient haze can be secured. Furthermore, a high content of structural unit B in copolymer α is advantageous because haze can be secured in the film with a smaller amount of copolymer α compared to a low content. On the other hand, if the content of structural unit B in copolymer α is higher than the upper limit, development when forming a pattern may become difficult. Therefore, in one embodiment of the present invention, the content of structural unit B relative to the total amount of structural units constituting copolymer α is preferably 50 to 80 mol%, more preferably 50 to 70 mol%. Furthermore, in another embodiment, in order to more effectively increase the haze, the content of structural unit B relative to the total amount of structural units constituting copolymer α is preferably 55 to 85 mol%, more preferably 55 to 80 mol%, and even more preferably 55 to 75 mol%.

[0017] The copolymer α in the colored curable resin composition preferably further comprises a structural unit C derived from an ethylenically unsaturated group-containing isocyanate compound or a monomer having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond.

[0018] Structural unit C originates from, for example, an isocyanate compound (C0) having an isocyanate group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(C0)"). Examples of ethylenically unsaturated groups included in (C0) include vinyl groups and (meth)acryloyloxy groups. In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0019] Examples of (C0) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanates; and reaction products obtained by reacting 2-hydroxyalkyl (meth)acrylate with a diisocyanate compound in equimolar amounts (2-hydroxyalkyl (meth)acrylate:diisocyanate compound = 1 mole:1 mole).

[0020] In one embodiment of the present invention, from the viewpoint of storage stability of the colored curable resin composition, it is preferable that the isocyanate group in (C0) is a blocked isocyanate group (hereinafter sometimes referred to as "blocked isocyanate group"), and that the structural unit C is preferably derived from an isocyanate compound (C0-1) (hereinafter sometimes referred to as "(C0-1)") in which the isocyanate group in (C0) is blocked. The isocyanate group in (C0) may be blocked by a blocking agent.

[0021] Blocking agents for blocking the isocyanate group of (C0) include, for example, lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; methanol, ethanol, propanol, 1-methoxy-2-propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, malic acid esters, 2-methylmalic acid esters, 3-methylmalic acid esters, Alcohols such as 2,3-dimethylmalate, tartaric acid, and citrate; phenols, 2,6-dimethylphenol, cresol, 3,5-xylenol, ethylphenol, o-isopropylphenol, butylphenols such as p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrene-phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol Phenolic compounds such as methyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc.; Mercaptan compounds such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc.; Amine compounds such as diisopropylamine, diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.; Acid amide compounds such as acetanilide, acetanisidide, acetamide, benzamide, etc.; Acid imide compounds such as succinimide, maleimide, etc.; Imidazole, 2-methylimidazole, 2- Examples include imidazoles such as ethylimidazole; pyrazoles such as pyrazole and 3,5-dimethylpyrazole; ureas such as urea, thiourea, and ethyleneurea; carbamidates such as phenyl N-phenylcarbamate and 2-oxazolidone; imines such as ethyleneimine and polyethyleneimine; oximes such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; and bisulfites such as sodium bisulfite and potassium bisulfite.From the viewpoints of availability, cost, and neutrality after elimination, malonic acid diesters and malic acid esters are preferred as blocking agents, with dimethyl malonate, diethyl malonate, and diethyl malate being particularly preferred. These blocking agents may be used individually or in combination of two or more.

[0022] (C0-1) is preferably 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate, 2-[(diethyl malate)carbonylamino]ethyl acrylate, 2-[(diethyl malate)carbonylamino]methyl acrylate, 2-[(diethyl malate)carbonylamino]propyl acrylate, and 2-[(diethyl malate)carbonylamino]butyl acrylate.

[0023] (C0-1) is commercially available and includes, for example, AOI-DEM: Karenz® AOI-DEM (reaction product of 2-isocyanatoethyl acrylate and diethyl malonate, 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate, manufactured by Showa Denko K.K.) and AOI-MDE: Karenz® AOI-MDE (reaction product of 2-isocyanatoethyl acrylate and diethyl malate, 2-[(diethyl malate)carbonylamino]ethyl acrylate, manufactured by Showa Denko K.K.).

[0024] In one embodiment of the present invention, from the viewpoint of storage stability, availability, and neutrality after desorption of the colored curable resin composition, (C0-1) is particularly preferably 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate.

[0025] Structural unit C is derived from a monomer 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. As the monomer having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond, a monomer having a cyclic ether with 2 to 4 carbon atoms and a (meth)acryloyloxy group is preferred.

[0026] Examples of monomers having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond include monomers having an oxyranyl group and an ethylenically unsaturated bond (C1) (hereinafter sometimes referred to as "(C1)"), monomers having an oxetanyl group and an ethylenically unsaturated bond (C2) (hereinafter sometimes referred to as "(C2)"), and monomers having a tetrahydrofuryl group and an ethylenically unsaturated bond (C3) (hereinafter sometimes referred to as "(C3)").

[0027] Examples of (C1) include monomers having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized (C1-1) (hereinafter sometimes referred to as "(C1-1)") and monomers having a cyclic unsaturated hydrocarbon structure that has been epoxidized (C1-2) (hereinafter sometimes referred to as "(C1-2)").

[0028] (C1-1) includes glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyl Examples include oxymethylstyrene, 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, and 2,4,6-tris(glycidyloxymethyl)styrene.

[0029] Examples of (C1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celoxide 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), compounds represented by formula (CI), and compounds represented by formula (CII).

[0030] [ka] [In formulas (CI) and (CII), R a and R b This represents 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 hydroxyl group. X 1 and X 2 This is a single bond, *-R g -, *-R g-O-, *-R g -S- or *-R g Represents -NH- R g This represents an alkanediyl group with 1 to 6 carbon atoms. * represents a bond with O.

[0031] Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of alkyl groups in which a hydrogen atom is substituted with hydroxyl include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, and 4-hydroxybutyl group. R a and R b Preferably, the group can be a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

[0032] Examples of alkanediyl groups include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl. X 1 and X 2 Preferably, the bonds include single bonds, methylene groups, ethylene groups, *-CH2-O- and *-CH2CH2-O-, and more preferably, single bonds and *-CH2CH2-O- (* represents a bond with O).

[0033] Specific examples of compounds represented by formula (CI) include compounds represented by formulas (CI-1) to (CI-15), preferably compounds represented by formulas (CI-1), (CI-3), (CI-5), (CI-7), (CI-9), (CI-11) to (CI-15), and more preferably compounds represented by formulas (CI-1), (CI-7), (CI-9), and (CI-15).

[0034] [ka]

[0035] [ka]

[0036] Specific examples of compounds represented by formula (CII) include compounds represented by formulas (CII-1) to (CII-15), preferably compounds represented by formulas (CII-1), (CII-3), (CII-5), (CII-7), (CII-9), (CII-11) to (CII-15), and more preferably compounds represented by formulas (CII-1), (CII-7), (CII-9), and (CII-15).

[0037] [ka]

[0038] [ka]

[0039] The compound represented by formula (CI) and the compound represented by formula (CII) can each be used individually. They can also be used in combination in any ratio. When used in combination, the mixing ratio of formula (CI):formula (CII) [molar ratio] is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.

[0040] As (C2), monomers having an oxetanyl group and a (meth)acryloyloxy group are more preferred. Examples of (C2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

[0041] As (C3), monomers having a tetrahydrofurfuryl group and a (meth)acryloyloxy group are more preferred. Specifically, as (C3), examples include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0042] In terms of being advantageous for curing at low temperatures, the compound giving structural unit C is preferably an isocyanate compound containing an ethylenically unsaturated group and a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and more preferably a monomer having an isocyanate group or a glycidyl group and an ethylenically unsaturated group.

[0043] In one embodiment of the present invention, copolymer α may be composed of structural units other than the above-mentioned structural units A, B, and C. Examples of such structural units include structural units derived from monomer (B'), which are exemplified as structural units that can constitute copolymer β, as described later. In one embodiment of the present invention, the copolymer α can be, for example, the following resins [α1] to [α4].

[0044] Resin [α1]; a copolymer having structural unit A (hereinafter sometimes referred to as "(A)"), structural unit C (hereinafter sometimes referred to as "(C)"), and structural unit B (hereinafter sometimes referred to as "(B)"); Resin [α2]; a copolymer having a structural unit in which (C) is added to (A) and (B); Resin [α3]; a copolymer having a structural unit in which (A) is added to (C) and (B); A copolymer having a structural unit (B) obtained by adding (A) to resin [α4]; (C) and further adding a polycarboxylic acid and / or carboxylic acid anhydride.

[0045] The resin [α1] can be manufactured, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the cited literature.

[0046] Specifically, a method involves placing predetermined amounts of (A) and (C), a polymerization initiator, and a solvent into a reaction vessel, creating a deoxygenated atmosphere by, for example, replacing oxygen with nitrogen, and heating and maintaining the temperature while stirring. The polymerization initiator and solvent used here are not particularly limited and can be those commonly used in the field. For example, examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc.), and the solvent can be any solvent that dissolves each monomer. Examples of organic solvents that may be included in the colored curable resin composition of the present invention include those described later.

[0047] The resulting copolymer may be used as is after the reaction, or after being concentrated or diluted, or after being extracted as a solid (powder) by methods such as reprecipitation. In particular, by using a solvent as described later, which may be included in the composition contained in the colored curable resin composition of the present invention, as the solvent during polymerization, the solution after the reaction can be used directly in the preparation of the colored curable resin composition of the present invention, thereby simplifying the manufacturing process of the colored curable resin composition of the present invention.

[0048] In resin [α1], the ratio of each structural unit is, among all structural units constituting resin [α1], Structural unit A; 2-45 mol% Structural unit B; 50-90 mol% Structural unit C; 2-95 mol% It is preferable that this be the case. Structural unit A; 5-40 mol% Structural unit B; 50-80 mol% Structural unit C; 5-80 mol% It is preferable that it be so. When the ratio of structural units of resin [α1] is within the above range, it is considered that the desired haze in the color filter is more easily obtained. Furthermore, the colored curable resin composition tends to have excellent storage stability, developability when forming patterns, and the resulting cured film has excellent solvent resistance, heat resistance, and mechanical strength. From the viewpoint of easily improving curing at low temperatures, (C0) and (C1) are preferred as (C) used in resin [α1], and (C0-1) and (C1-1) are particularly preferred.

[0049] The resin [α2] can be produced by obtaining a copolymer of (A) and (B), and then adding the isocyanate group or carbon-2 to carbon-4 cyclic ether of (C) to the carboxylic acid and / or carboxylic acid anhydride of (A). First, a copolymer of (A) and (B) is produced in the same manner as described for the production of resin [α1]. In this case, the ratio of each structural unit is such that, among all structural units constituting resin [α2], Structural unit A; 10-50 mol% Structural unit B; 50-90 mol% It is preferable that this be the case. Structural unit A; 20-45 mol% Structural unit B; 55-80 mol% It is preferable that it be so.

[0050] Next, a portion of the carboxylic acid and / or carboxylic acid anhydride derived from (A) in the copolymer is reacted with an isocyanate group or a cyclic ether having 2 to 4 carbon atoms that (C) possesses. Following the production of the copolymer of (A) and (B), the atmosphere inside the flask is replaced from nitrogen to air, and (C), a reaction catalyst for the reaction between a carboxylic acid or carboxylic acid anhydride and an isocyanate compound or cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.) and a polymerization inhibitor (e.g., hydroquinone, methoquinone, etc.) are added to the flask and the mixture is reacted at, for example, 60 to 130°C for 1 to 10 hours to produce resin [α2]. The amount of (C) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (A). It is believed that when the ratio of structural units of resin [α2] is within the above range, the desired haze in the color filter is more easily obtained. Furthermore, the storage stability of the colored curable resin composition, developability when forming patterns, pattern shape, curability at low temperatures, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tend to be good. Since the isocyanate group has high reactivity and unreacted (C) is less likely to remain, (C0) is preferred as (C) to be used in resin [α2], and (C0-1) is even more preferred. Furthermore, since the cyclic ether has high reactivity and unreacted (C) is less likely to remain, (C1) is preferred as (C) to be used in resin [α2], and (C1-1) is even more preferred. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (A), (B), and (C). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (A), (B), and (C). The reaction conditions, such as the preparation method, reaction temperature, and time, can be adjusted as appropriate, taking into account the manufacturing equipment and the amount of heat generated by polymerization. Similarly, the preparation method and reaction temperature can be adjusted as appropriate, taking into account the manufacturing equipment and the amount of heat generated by polymerization.

[0051] As a first step, resin [α3] is produced in the same manner as the production method for resin [α1] described above to obtain a copolymer of (B) and (C). As described above, the obtained copolymer may be used as is after the reaction, or a concentrated or diluted solution may be used, or it may be used after being extracted as a solid (powder) by methods such as reprecipitation. The ratios of structural units derived from (B) and (C) are, in relation to the total number of moles of all structural units constituting the copolymer, respectively: Structural unit B; 50-90 mol% Structural unit C; 10-50 mol% It is preferable that this be the case. Structural unit B; 55-80 mol% Structural unit C; 20-45 mol% It is preferable that it be so. When the ratio of structural units of resin [α3] falls within the above range, it is considered easier to obtain the desired haze in the color filter. Furthermore, the storage stability of the colored curable resin composition, developability when forming patterns, pattern shape, curability at low temperatures, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tend to be good.

[0052] Furthermore, under the same conditions as for the production of resin [α2], resin [α3] can be obtained by reacting an isocyanate compound or cyclic ether derived from (C) in the copolymer of (B) and (C) with a carboxylic acid or carboxylic acid anhydride contained in (A). The amount of (A) used to react with the copolymer is preferably 5 to 100 moles per 100 moles of (C). Since the isocyanate group is highly reactive and unreacted (C) is less likely to remain, (C0) is preferred as (C) to be used in resin [α3], and (C0-1) is even more preferred. Furthermore, since the cyclic ether is highly reactive and unreacted (C) is less likely to remain, (C1) is preferred as (C) to be used in resin [α3], and (C1-1) is even more preferred.

[0053] Resin [α4] is a resin obtained by further reacting resin [α3] with a polycarboxylic acid and / or carboxylic acid anhydride. The hydroxyl group generated by the reaction of an isocyanate compound or cyclic ether derived from (C) with a carboxylic acid or carboxylic acid anhydride derived from (A) is further reacted with a polycarboxylic acid and / or carboxylic acid anhydride. Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and tricarbanilic acid. Examples of carboxylic acid anhydrides include succinic anhydride, 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, and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride. The amount of polycarboxylic acid and / or carboxylic acid anhydride used is preferably 0.05 to 1 mole, and more preferably 0.1 to 0.5 moles, per mole of (A).

[0054] In one embodiment of the present invention, the copolymer α is preferably a resin [α1] from the viewpoint of easily obtaining the desired haze in the color filter, good developability, and curability at low temperatures, and a resin [α1] using a monomer having an isocyanate group or a glycidyl group as (C) is particularly preferred. Among the resin [α1], glycidyl (meth)acrylate, AOI-DEM, and AOI-MDE are preferred as (C).

[0055] The color-curable resin composition of the present invention may contain one type of copolymer α, or it may contain a combination of two or more types of copolymer α.

[0056] The content of copolymer α may be 100% by mass per 100 parts by mass of resin, preferably 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 75% by mass, and even more preferably 15 to 75% by mass, and may be, for example, 5 to 50% by mass. It is believed that a color filter having haze can be obtained when the content of copolymer α is within the above range.

[0057] In one embodiment of the present invention, the content of copolymer α in the colored curable resin composition is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 1 to 30% by mass, even more preferably 5 to 25% by mass, and particularly preferably 7 to 20% by mass, based on the solid content of the colored curable resin composition. When the content of copolymer α is within the above range, the desired haze in the color filter is easily obtained. Furthermore, high reliability such as high chemical resistance is easily obtained.

[0058] The content of copolymer α in the colored curable resin composition is R in the monomer represented by formula (1) that gives structural unit B in copolymer α. 2 It tends to depend on the number of carbon atoms, for example, R 2 The larger the number of carbon atoms, the more likely it is that the desired haze can be obtained with a smaller content. It also tends to depend on the content of structural unit B in copolymer α. For example, if the content of structural unit B in copolymer α is high, the desired haze can be obtained with a smaller content compared to when it is low, or a higher haze can be obtained with the same content. When the content of copolymer α is small, it is possible to include more polymerizable compounds and resins such as copolymer β, which are different from copolymer α, if present. This can be advantageous in that it is easier to adjust the curability of the composition and easier to obtain a good cured film shape.

[0059] In a color-curable resin composition, the resin may further contain a (co)polymer different from copolymer α, and may further contain copolymer β different from copolymer α. The copolymer β is preferably one that can produce the desired haze when combined with copolymer α, and is preferably an alkali-soluble resin. In this specification, an alkali-soluble resin refers to a resin that dissolves in a developer solution, which is an aqueous solution of an alkaline compound. Specifically, examples include resins having carboxyl groups and / or phenolic hydroxyl groups, and preferably resins having carboxyl groups. The alkali-soluble resin can be appropriately selected from resins conventionally known in the art, and may be used alone or in combination of two or more. By further containing copolymer β different from copolymer α in the color-curable resin composition, developer solubility and solvent resistance are easily improved, and the cured film tends to have excellent shape and developability.

[0060] In one embodiment of the present invention, preferred alkali-soluble resins as copolymer β include, for example, the following resins [β1] to [β6].

[0061] Resin [β1]; copolymer having (A) and (C); A copolymer having resin [β2]; (A) and (C), and a monomer (B') copolymerizable with (A) [however different from (A) and (C)] (hereinafter sometimes referred to as "(B')"); Resin [β3]; a copolymer having structural units derived from (A) and (B'); Resin [β4]; a copolymer having a structural unit in which (C) is added to (A) and (B'); Resin [β5]; a copolymer having a structural unit in which (A) is added to (C) and (B'); A copolymer having a structural unit obtained by adding (A) to resin [β6] and further adding polycarboxylic acid and / or carboxylic acid anhydride, and (B').

[0062] Here, (A) and (C) are as described above for copolymer α. (B') is a monomer copolymerizable with (A) [however, different from (A) and (C)], and is also different from structural unit B derived from the monomer represented by formula (1) as described above for copolymer α. Note that copolymer β may further contain structural unit B. In the present invention, copolymers composed of both structural unit B and (B') are classified as copolymer α or copolymer β based on the content of structural unit (B) relative to the total structural units constituting the copolymer. (B') includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (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 relevant technical field, it is commonly called "dicyclopentanyl(meth)acrylate". It is also sometimes called "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.0 2,6 (Meth)acrylic acid esters such as decen-8-yl (meth)acrylate (commonly known as "dicyclopentenyl (meth)acrylate" in the relevant art), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; Hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Diethyl maleate, diethyl fumarate, diethyl itaconate, and other dicarboxylic acid diesters; 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-methoxybic Chlo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept -2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2- Bicyclounsaturated compounds such as ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide; Examples include 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, and the like. Of these, (meth)acrylic acid esters are preferred.

[0063] In resin [β1], the ratio of structural units derived from each is, among all structural units constituting resin [β1], Structural unit A; 2-60 mol% Structural unit C; 40-98 mol% It is preferable that this be the case. Structural unit A; 10-50 mol% Structural unit C; 50-90 mol% It is preferable that it be so. When the ratio of structural units of resin [β1] falls within the above range, it is considered that the desired haze in the color filter is more easily obtained when combined with copolymer α. Furthermore, the colored curable resin composition tends to have excellent storage stability, developability when forming patterns, and solvent resistance of the resulting cured film.

[0064] The resin [β1] can be manufactured, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the cited literature.

[0065] Specifically, a method involves placing predetermined amounts of (A) and (C), a polymerization initiator, and a solvent into a reaction vessel, creating a deoxygenated atmosphere by, for example, replacing oxygen with nitrogen, and heating and maintaining the temperature while stirring. The polymerization initiator and solvent used here are not particularly limited and can be those commonly used in the field. For example, examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc.), and the solvent can be any solvent that dissolves each monomer. Examples of organic solvents that may be included in the colored curable resin composition of the present invention include those described later.

[0066] The resulting copolymer may be used as is after the reaction, or after being concentrated or diluted, or after being extracted as a solid (powder) by methods such as reprecipitation. In particular, by using a solvent as described later, which may be included in the composition contained in the colored curable resin composition of the present invention, as the solvent during polymerization, the solution after the reaction can be used directly in the preparation of the colored curable resin composition of the present invention, thereby simplifying the manufacturing process of the colored curable resin composition of the present invention.

[0067] In resin [β2], the ratio of each structural unit is, among all structural units constituting resin [β2], Structural unit A; 2-45 mol% Structural unit B'; 1-65 mol% Structural unit C; 2-97 mol% It is preferable that this be the case. Structural unit A; 5-40 mol% Structural unit B'; 5-60 mol% Structural unit C; 5-90 mol% It is preferable that it be so. When the ratio of structural units of resin [β2] falls within the above range, it is considered that the desired haze in the color filter is more easily obtained when combined with copolymer α. Furthermore, the colored curable resin composition tends to have excellent storage stability, developability when forming patterns, and the resulting cured film exhibits excellent solvent resistance, heat resistance, and mechanical strength.

[0068] Resin [β2] can be manufactured, for example, in the same manner as described for the manufacturing method of resin [β1].

[0069] In resin [β3], the ratio of structural units derived from each is, among all structural units constituting resin [β3], Structural unit A; 2-60 mol% Structural unit B'; 40-98 mol% It is preferable that this be the case. Structural unit A; 10-50 mol% Structural unit B'; 50-90 mol% It is preferable that it be so. Resin [β3] can be manufactured, for example, in the same manner as described for the manufacturing method of resin [β1].

[0070] The resin [β4] can be produced by obtaining a copolymer of (A) and (B'), and then adding the isocyanate compound or carbon-2 to carbon-4 cyclic ether of (C) to the carboxylic acid and / or carboxylic acid anhydride of (A). First, a copolymer of (A) and (B') is produced in the same manner as described for the production of resin [β1]. In this case, it is preferable that the ratio of structural units derived from each is the same as that given for resin [β3].

[0071] Next, a portion of the carboxylic acid and / or carboxylic acid anhydride derived from (A) in the copolymer is reacted with an isocyanate group or a cyclic ether having 2 to 4 carbon atoms that (C) possesses. Following the production of the copolymer of (A) and (B'), the atmosphere inside the flask is replaced from nitrogen to air, and (C), a reaction catalyst for the reaction between a carboxylic acid or carboxylic acid anhydride and a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.) and a polymerization inhibitor (e.g., hydroquinone, methoquinone, etc.) are added to the flask and the reaction is carried out at, for example, 60 to 130°C for 1 to 10 hours to produce resin [β4]. The amount of (C) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (A). It is believed that this range makes it easier to obtain the desired haze in the color filter when combined with copolymer α. Furthermore, the storage stability of the colored curable resin composition, developability when forming patterns, pattern shape, curability at low temperatures, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tend to be good. Since the isocyanate group has high reactivity and unreacted (C) is less likely to remain, (C0) is preferred as (C) to be used in resin [β4], and (C0-1) is even more preferred. Since the cyclic ether has high reactivity and unreacted (C) is less likely to remain, (C1) is preferred as (C) to be used in resin [β4], and (C1-1) is even more preferred. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (A), (C), and (B'). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (A), (C), and (B'). The reaction conditions, such as the preparation method, reaction temperature, and time, can be adjusted as appropriate, taking into account the manufacturing equipment and the amount of heat generated by polymerization. Similarly, the preparation method and reaction temperature can be adjusted as appropriate, taking into account the manufacturing equipment and the amount of heat generated by polymerization.

[0072] As a first step, resin [β5] is produced in the same manner as the method for producing resin [β1] described above to obtain a copolymer of (C) and (B'). As described above, the obtained copolymer may be used as is after the reaction, or a concentrated or diluted solution may be used, or it may be used after being extracted as a solid (powder) by methods such as reprecipitation. The ratios of structural units derived from (C) and (B') are, respectively, with respect to the total number of moles of all structural units constituting the copolymer: Structural unit B'; 5-95 mol% Structural unit C; 5-95 mol% It is preferable that this be the case. Structural unit B'; 10-90 mol% Structural unit C; 10-90 mol% It is preferable that it be so. When the ratio of structural units of resin [β5] falls within the above range, it is considered easier to obtain the desired haze in the color filter when combined with copolymer α. Furthermore, the storage stability of the colored curable resin composition, developability when forming patterns, pattern shape, curability at low temperatures, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tend to be good.

[0073] Furthermore, under the same conditions as for the production of resin [β4], resin [β5] can be obtained by reacting an isocyanate compound or cyclic ether derived from (C) in the copolymer of (C) and (B') with a carboxylic acid or carboxylic acid anhydride from (A). The amount of (A) used to react with the copolymer is preferably 5 to 100 moles per 100 moles of (C). Since the isocyanate group is highly reactive and unreacted (C) is less likely to remain, (C0) is preferred as (C) to be used in resin [β4], and (C0-1) is even more preferred. Since the cyclic ether is highly reactive and unreacted (C) is less likely to remain, (C1) is preferred as (C) to be used in resin [β5], and (C1-1) is even more preferred.

[0074] Resin [β6] is a resin obtained by further reacting resin [β5] with a polycarboxylic acid and / or carboxylic acid anhydride. The hydroxyl group generated by the reaction of an isocyanate compound or cyclic ether derived from (C) with a carboxylic acid or carboxylic acid anhydride derived from (A) is further reacted with a polycarboxylic acid and / or carboxylic acid anhydride. Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and tricarbanilic acid. Examples of carboxylic acid anhydrides include succinic anhydride, 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, and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride. The amount of polycarboxylic acid and / or carboxylic acid anhydride used is preferably 0.05 to 1 mole, and more preferably 0.1 to 0.5 moles, per mole of (A).

[0075] In one embodiment of the present invention, the copolymer β is preferably a resin having structural units with ethylenically unsaturated bonds in the side chains (resin[β4], resin[β5], or resin[β6]), and more preferably a resin having structural units containing (meth)acryloyl groups in the side chains, from the viewpoint of good developability and curability at low temperatures. As resins having structural units containing a (meth)acryloyl group in the side chain, for example, resins [β4] using monomers having a (meth)acryloyl group such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-methyl-3-methacrylloyloxymethyl oxetane, and tetrahydrofurfuryl acrylate as (C), and resins [β5] and resins [β6] using monomers having a (meth)acryloyl group such as acrylic acid, methacrylic acid, and mono[2-(meth)acryloyloxyethyl] succinate as (A) are preferred. In resins [β4], [β5], and [β6], (B') is preferably (meth)acrylic acid esters. Furthermore, in one embodiment of the present invention, from the viewpoint of curability at low temperatures, a resin having a structural unit containing an isocyanate group or a glycidyl group is particularly preferred as copolymer β. Examples of resins having a structural unit containing an isocyanate group include resin [β4] using monomers having an isocyanate group such as (meth)acrylic acid (2-isocyanatoethyl), malonic acid-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, and 2-[(diethyl malate)carbonylamino]ethyl acrylate as (C), and resins [β4] and [β6] using monomers having a glycidyl group such as (meth)acrylic acid as (C).

[0076] The color-curable resin composition of the present invention may contain one type of copolymer β, or it may contain a combination of two or more types of copolymer β.

[0077] When the colored curable resin composition of the present invention contains copolymer β, its content is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 50% by mass, based on the solid content of the colored curable resin composition, and may be, for example, 25 to 45% by mass or 30 to 40% by mass. When the resin content is within the above range, it is easier to obtain the desired haze in the color filter, the curability of the colored curable resin composition is enhanced, a cured film is formed more easily, and the resolution of the pattern and the residual film rate tend to improve. In one embodiment of the present invention, the colored curable resin composition does not have to contain copolymer β. That is, the content of copolymer β may be 0% by mass based on the solid content of the colored curable resin composition.

[0078] When the color-curable resin composition of the present invention contains copolymer β, its content is preferably 10 to 500 parts by mass, more preferably 50 to 500 parts by mass, and even more preferably 100 to 500 parts by mass, relative to 100 parts by mass of copolymer α, and may be, for example, 200 to 500 parts by mass, 250 to 450 parts by mass, or 300 to 400 parts by mass. When the content of copolymer β is within the above range relative to 100 parts by mass of copolymer α, it is easier to obtain the desired haze in the color filter, the curability of the color-curable resin composition is easier to improve, a cured film is easier to form, and the resolution of the pattern and the residual film rate tend to improve.

[0079] The resin content is preferably 20-60% by mass, more preferably 30-55% by mass, and even more preferably 40-50% by mass, based on the solid content of the colored curable resin composition. When the resin content is within the above range, it is easier to obtain the desired haze in the color filter, the curability of the colored curable resin composition is enhanced, a cured film is formed more easily, and the pattern resolution and residual film rate tend to improve. In this specification, "solid content" refers to the amount obtained by subtracting the solvent content from the total amount of the colored curable resin composition. The solid content and the content of each component thereto can be measured by known analytical means such as liquid chromatography or gas chromatography. Furthermore, the resin content as used herein refers to the total amount of resin ((co)polymer) contained in the colored curable resin composition.

[0080] The weight-average molecular weight of the resin contained in the color-curable resin composition of the present invention, in terms of polystyrene equivalent, is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, even more preferably 5,000 to 30,000, and even more preferably 9,000 to 30,000, and may also be, for example, 10,000 to 30,000. When the weight-average molecular weight of the resin (particularly copolymer α) is within the above range, the hardness of the cured film of the composition of the present invention is improved, the residual film rate is high, the solubility of the unexposed areas in the developer is good, the pattern shape is improved, and the resolution of the pattern tends to be improved. It is also presumed that the desired haze in the color filter is easier to obtain.

[0081] The degree of dispersion of the resin [weight-average molecular weight (Mw) / number-average molecular weight (Mn)] is preferably 1.1 to 6, and more preferably 1.2 to 4.

[0082] The acid value of the resin is preferably 10 to 170 mg KOH / g, more preferably 15 to 150 mg KOH / g, and even more preferably 20 to 135 mg KOH / g, based on solid content. Here, the acid value is measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0083] (polymerizable compound) In this specification, polymerizable compounds are compounds that can be polymerized by active radicals and / or acids generated from polymerization initiators, and examples include compounds having polymerizable ethylenically unsaturated bonds.

[0084] As polymerizable compounds in the colored curable resin composition of the present invention, for example, those having two or more ethylenically unsaturated bonds can be used, and those having three or more ethylenically unsaturated bonds are preferred. Examples of such polymerizable compounds include glycerin triacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, and tetrapentaerythritol nona(meth)acrylate. Examples include rilate, 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, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. One polymerizable compound may be used alone or in combination of two or more.

[0085] From the viewpoint of easily obtaining the desired haze when combined with copolymer α, the polymerizable compound is preferably, for example, a chain-type aliphatic polymerizable compound. Furthermore, the polymerizable compound preferably has 3 to 6 ethylenically unsaturated bonds. When the polymerizable compound has 3 to 6 ethylenically unsaturated bonds, it is easier to obtain the desired haze in the color filter, and furthermore, high curability and a good cured film shape are easily obtained. Among the above polymerizable compounds, glycerin triacrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are particularly preferred.

[0086] The weight-average molecular weight of the polymerizable compound is preferably 150 to 2,900, more preferably 250 to 1,500, from the viewpoint of easily obtaining the desired haze when combined with copolymer α. Furthermore, when the weight-average molecular weight of the polymerizable compound is within the above range, it is easier to obtain a good cured film shape and to adjust the curability of the colored curable resin composition to an appropriate range. The weight-average molecular weight (Mw) can be measured, for example, using gel permeation chromatography (GPC). More specifically, it can be measured by the method described in the examples below.

[0087] The polymerizable compound content is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass, based on the solid content of the colored curable resin composition. When the polymerizable compound content is within the above range, the desired haze is easily obtained in the color filter. Furthermore, when the coating film of the colored curable resin composition is exposed and cured, variations in the degree of curing within the coating film are less likely to occur, and it becomes possible to cure the coating film thoroughly, especially to its depths, making it easier to obtain a good cured film.

[0088] The polymerizable compound content is preferably 50 to 85 parts by mass, more preferably 55 to 83 parts by mass, even more preferably 60 to 80 parts by mass, and particularly preferably 65 to 75 parts by mass, per 100 parts by mass of resin. When the polymerizable compound content is within the above range per 100 parts by mass of resin, a colored curable resin composition capable of forming a color filter having the desired haze can be obtained. When the polymerizable compound content is below the above upper limit per 100 parts by mass of resin, when the coating film of the colored curable resin composition is exposed and cured, variations in the degree of curing within the coating film are less likely to occur, and in particular, it becomes possible to sufficiently cure the coating film to its depths, making it easier to obtain a good cured film shape.

[0089] (Polymerization initiator) A polymerization initiator is a compound that generates active radicals, acids, etc., upon the action of light or heat, thereby initiating polymerization. While not particularly limited, examples of polymerization initiators include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds. Among these, O-acyloxime compounds are preferred. From the viewpoint of further improving the curability of the colored curable resin composition, the polymerization initiator preferably has a maximum absorption wavelength in the range of 365 to 390 nm, and more preferably in the range of 370 to 390 nm. The colored curable resin composition of the present invention may contain one type of polymerization initiator, or it may contain two or more types of polymerization initiators.

[0090] O-acyloxime compounds are preferred as polymerization initiators. Furthermore, it is also preferable that the polymerization initiator is a compound having a nitro group.

[0091] O-acyloxime compounds are given by formula (d1): [ka] This is a compound having the structure represented by . Hereafter, * represents a bond.

[0092] Examples of the O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N- Examples include acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, and 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one. Commercially available products such as Irgacure OXE01, OXE02, OXE03 (all manufactured by BASF), N-1919, NCI-730, NCI-831, NCI-930 (manufactured by ADEKA), PBG-314, PBG-317, PBG-326, PBG-327, PBG-329 (all manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) may also be used.In particular, the O-acyloxime compound is preferably at least one selected from the group consisting of N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine. These O-acyloxime compounds tend to yield high-brightness color filters.

[0093] Alkylphenone compounds are compounds having a substructure represented by formula (d2) or formula (d3). In these substructures, the benzene ring may have substituents.

[0094] [ka]

[0095] Compounds having the 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, and 379 (all manufactured by BASF) may also be used. Compounds having the 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-hydroxycyclohexylphenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. In terms of sensitivity, alkylphenone compounds having the structure represented by formula (d2) are preferred.

[0096] Examples of biimidazole compounds 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 Publication No. 6-75372, Japanese Patent Publication No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, and 2,2'-bis(2-chlorophenyl Examples include phenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), and biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Publication No. 7-10913, etc.). Among these, compounds represented by the following formula and mixtures thereof are preferred.

[0097] [ka]

[0098] Examples of triazine compounds 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, and 2,4-bis(trichloromethyl)-6-[2-( Examples include 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.

[0099] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0100] The polymerization initiator content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, even more preferably 1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass, based on 100 parts by mass of the total amount of resin and polymerizable compound contained in the colored curable resin composition. When the polymerization initiator content is within the above range, it is easier to form a pattern with a good shape by exposure and development, and it is easier to improve curability at low temperatures. In addition, since sensitivity tends to be increased and exposure time is shortened, the productivity of color filters and the like is improved.

[0101] (Coloring agent) The color-curable resin composition of the present invention contains at least one colorant. The color-curable resin composition of the present invention containing at least one colorant can be suitably used as a color-curable resin composition for creating a resist layer in a color filter. Furthermore, the color-curable resin composition of the present invention having the above composition can be darkened when used as a color resist composition, making it easier to achieve the desired color. The colorant may be either a dye or a pigment, but it is preferable to include a pigment. As the pigment, known pigments can be used, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0102] Specifically, yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231, 235, 236, etc. CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 272, 273, 291, 297, and other red pigments; CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, and other blue pigments; CI Pigment Violet 1, 19, 23, 29, 32, 36, 37, 38, and other violet color pigments; CI Pigment Green 7, 36, 58, 59, 62, 63, 64, 65, 66, 67 green pigments; CI Pigment Brown 23, 25, and other brown pigments; Examples include black pigments such as CI Pigment Black 1, 7, 31, and 32.

[0103] The pigment may be subjected to rosin treatment, surface treatment using pigment derivatives into which acidic or basic groups have been introduced, grafting treatment of the pigment surface with polymer compounds, atomization treatment by sulfuric acid atomization method, washing treatment with organic solvents or water to remove impurities, removal treatment of ionic impurities by ion exchange method, etc., as needed. It is preferable that the pigment has a uniform particle size. Furthermore, by dispersing the pigment with a pigment dispersant, a pigment dispersion can be obtained in which the pigment is uniformly dispersed in the solution.

[0104] Examples of pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used individually or in combination of two or more. Examples of pigment dispersants by trade name include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solspers (manufactured by Lubrizol), EFKA (manufactured by CIBA), Azisper (manufactured by Ajinomoto Fine Techno Co., Ltd.), and Disperbyk (manufactured by Bic Chemie).

[0105] When a pigment dispersant is used, the amount used is preferably 1% to 100% by mass, and more preferably 5% to 50% by mass, relative to the total amount of pigment. When the amount of pigment dispersant used is within the above range, a pigment dispersion liquid with a uniform dispersion state tends to be obtained.

[0106] The pigment content is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may also be 100% by mass.

[0107] The coloring agent may contain a dye. The dye is not particularly limited and any known dye can be used, such as solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as having hue other than pigments in the Color Index (published by The Society of Dyers and Colourists) and known dyes listed in the Dyeing Notes (Irozome Co., Ltd.). In addition, based on chemical structure, examples include 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, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

[0108] Specifically, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI solvent dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 1 82, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 1 23, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340; CI Acid Green dyes such as 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109, etc. CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. CI Direct dyes, CI Disperse Yellow 51, 54, 76; CI Disperse Violet 26, 27; CI Disperse Blue 1, 14, 56, 60 and other CI disperse dyes, CI Basic Red 1, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; CI Basic Violet 2; CI Basic Red 9; CI Basic Green 1 and other CI Basic dyes, CI Reactive Yellow 2,76,116; CI Reactive Orange 16; CI Reactive Dyes such as CI Reactive Red 36, CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI Modant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; CI Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI Modant Green dyes such as 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. Examples include CI bat dyes such as CI bat green 1.

[0109] The dye content is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less, particularly preferably 5% by mass or less, and may even be 0% by mass.

[0110] The colorant content is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by mass, based on the solid content of the colored curable resin composition. When the colorant content is within the above range, the color density when used as a color filter is sufficient, and the required amount of colored curable resin can be included in the composition, so that a cured film with sufficient mechanical strength can be formed.

[0111] In colored curable resin compositions where particularly deep coloring is required, the colorant content is preferably 15 to 60% by mass, more preferably 18 to 55% by mass, and even more preferably 20 to 50% by mass, based on the solid content of the colored curable resin composition. When the colorant content is within the above range, a particularly high color density can be achieved when used as a color filter, and the required amount of curable resin can be included in the composition, so that a cured film with sufficient mechanical strength can be formed.

[0112] (Potassium initiation aid) The colored curable resin composition of the present invention may further contain at least one polymerization initiator. A polymerization initiator is a compound or sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When a polymerization initiator is included, it is usually used in combination with a polymerization initiator. Examples of polymerization initiators include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michlaz's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, and N-phenylglycine.

[0113] When these polymerization initiators are used, their content is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the total amount of resin and polymerizable compound. When the amount of polymerization initiator is within this range, patterns can be formed with even higher sensitivity during exposure, and the productivity of color filters and the like tends to improve.

[0114] (solvent) The color-curable resin composition of the present invention may further contain at least one solvent. The solvent is not particularly limited, and solvents commonly used in the art can be used. Examples include ester solvents (solvents containing -COO- in the molecule but not -O-), ether solvents (solvents containing -O- in the molecule but not -COO-), ether ester solvents (solvents containing both -COO- and -O- in the molecule), ketone solvents (solvents containing both -CO- in the molecule but not -COO-), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxides, and the like.

[0115] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, 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.

[0116] 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, phenethole, and methylanisole.

[0117] 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, methyl 2-ethoxy-2-methylpropionate Examples include ethyl acetate, 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.

[0118] 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, diacetone alcohol, and isophorone.

[0119] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0120] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0121] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0122] The solvent preferably contains one or more selected from the group consisting of ether solvents, ether ester solvents, and ketone solvents, more preferably contains ether solvents and ether ester solvents, and even more preferably contains propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

[0123] The solvent content is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, relative to the total amount of the colored curable resin composition of the present invention. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the solvent content is within the above range, the flatness during application is good, and the display characteristics tend to be good because, for example, there is no shortage of color density when a color filter is formed.

[0124] (Leveling agent) The colored curable resin composition of the present invention may further contain at least one leveling agent. Examples of leveling agents include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have polymerizable groups in their side chains.

[0125] Examples of silicone-based surfactants include surfactants that have siloxane bonds in their molecules. Specifically, examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (product 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).

[0126] Examples of the aforementioned fluorine-based surfactants include surfactants having fluorocarbon chains in their molecules. Specifically, these include Florard® FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac® F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-Top® EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon® S381, S382, SC101, SC105 (manufactured by AGC Inc. (formerly Asahi Glass Co., Ltd.)), and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

[0127] Examples of silicone-based surfactants containing fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in their molecules. Specifically, examples include Megafac® R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0128] When a leveling agent is included, the leveling agent content is preferably 0.005 to 0.5% by mass, and more preferably 0.01 to 0.2% by mass, relative to the total amount of the colored curable resin composition. This content does not include the content of the pigment dispersant. When the leveling agent content is within the above range, the flatness of the cured film of the colored curable resin composition of the present invention, which is used as a color filter or the like, can be improved.

[0129] (Other ingredients) The colored curable resin composition of the present invention may optionally contain other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other additives known in the art.

[0130] <Method for producing a colored curable resin composition> The colored curable resin composition of the present invention can be prepared, for example, by mixing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent, as well as polymerization initiators, leveling agents, and other components as needed. The coloring agent may be prepared using the pigment dispersion described above. The desired curable resin composition can be prepared by mixing the remaining components with the pigment dispersion to a predetermined concentration. It is also preferable to filter the resulting curable resin composition through a filter with a pore size of approximately 0.01 to 10 μm.

[0131] According to the color-curable resin composition of the present invention, a color filter having haze can be formed without adding inorganic fine particles. Therefore, since the color-curable resin composition does not require a step of stirring inorganic fine particles and uniformly dispersing them in the composition, improved productivity can be expected, and it also has excellent storage stability. The content of inorganic fine particles in the color-curable resin composition of the present invention is, for example, 2% by mass or less, preferably 1.5% by mass or less, and more preferably 1% by mass or less, based on the solid content of the color-curable resin composition. In one embodiment of the present invention, the color-curable resin composition of the present invention substantially does not contain inorganic fine particles. In this specification, "substantially" means that the content of inorganic fine particles is 0.1% by mass or less based on the solid content of the color-curable resin composition. Similarly, the color-curable resin composition of the present invention substantially does not contain organic fine particles.

[0132] <How to manufacture color filters> Methods for producing a cured film, such as a colored pattern, from the colored curable resin composition of the present invention include photolithography, inkjet printing, and printing. Among these, photolithography is preferred. Photolithography is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and then exposed to light through a photomask for development. In photolithography, by not using a photomask during exposure and / or by not developing, a colored coating film, which is a cured film of the colored curable resin composition layer, can be formed. The cured film, such as a colored pattern or colored coating film formed in this way, can be used as a color filter.

[0133] As substrates, glass plates such as quartz glass, borosilicate glass, aluminasilate glass, and soda-lime glass with a silica coating on the surface are used; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used; silicon is used; and aluminum, silver, silver / copper / palladium alloy thin films are formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

[0134] The formation of each color pixel by photolithography can be carried out using known or conventional equipment and conditions. For example, it can be manufactured as follows. First, a colored resin composition is applied to a substrate, and volatile components such as solvents are removed by heat drying (pre-baking) and / or vacuum drying, and then dried to obtain a smooth colored composition layer. Coating methods include spin coating, slit coating, and slit and spin coating. The temperature for heat drying is preferably 30 to 120°C, and more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When performing vacuum drying, it is preferable to do so under a pressure of 50 to 150 Pa and at a temperature range of 20 to 25°C. The thickness of the colored composition layer is not particularly limited and can be appropriately selected according to the desired thickness of the color filter.

[0135] To form a pattern, the colored composition layer is exposed and developed through a photomask for forming the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern appropriate to the intended application is used. For exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferred. For example, light below 350 nm can be filtered out using a filter that cuts out this wavelength range, or light around 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specifically, examples of light sources include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps. Furthermore, the exposure dose based on a wavelength of 365 nm is 50 to 300 J / cm². 2 Preferably, the humidity is 60-200 J / cm². 2 It is more preferable that the temperature is between 65 and 180 J / cm². 2 It is even more preferable that this be the case. It is preferable to use an exposure apparatus such as a mask aligner and a stepper, as this allows for uniform irradiation of the entire exposure surface with parallel light rays and precise alignment between the photomask and the substrate on which the colored composition layer is formed.

[0136] A colored pattern is formed on the substrate by developing the colored composition layer after exposure by contacting it with a developer. During development, the unexposed parts of the colored composition layer are dissolved and removed by the developer. As the developer, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developer may also contain a surfactant. The development method can be any of the following: paddle method, dipping method, or spray method. Furthermore, the substrate may be tilted to any angle during development. After developing, it is preferable to wash the film with water.

[0137] Furthermore, it is preferable to perform post-baking on the obtained coloring pattern. The post-baking temperature may be 200°C or lower, but is preferably 170°C or lower, and more preferably 150°C or lower, in order to form a color filter used in an organic EL display device. In the present invention, it is preferable to perform post-baking at an even lower temperature, for example, 130°C or lower. The lower limit of the post-baking temperature is preferably 70°C or higher, and more preferably 75°C or higher. The post-baking time is preferably 1 to 120 minutes, and more preferably 5 to 60 minutes.

[0138] <Color Filter> The present invention also provides a color filter, which is a cured film of the color-curable resin composition of the present invention. The color filter of the present invention may be a cured film in which a pattern is formed on the color-curable resin composition of the present invention as described above.

[0139] The thickness of the cured film is not particularly limited and can be adjusted as appropriate depending on the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.3 to 6 μm, and even more preferably 0.5 to 3 μm.

[0140] The color filter, which is the cured film of the colored curable resin composition of the present invention, has a haze value of preferably 1-50%, more preferably 3-45%, even more preferably 5-40%, and even more preferably 7-38% when calculated to a thickness of 2.5 μm. The haze value of the cured film can be measured by a haze meter. The present invention also provides the cured film of the colored curable resin composition of the present invention.

[0141] Furthermore, according to the present invention, a display device including the color filter can also be provided. A display device of the present invention that includes at least one color filter of the present invention as a component is useful as a display device with fewer display defects. Moreover, since the color-curable resin composition of the present invention can form a color filter having haze, it is particularly suitable as a color filter for an organic EL display device. [Examples]

[0142] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing content or usage are by mass unless otherwise specified.

[0143] <Weight average molecular weight> The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured using the GPC method under the following conditions. Equipment: HLC-8120GPC (manufactured by Tosoh Corporation) Column; TSK-GELG2000HXL Column temperature: 40°C Solvent: Tetrahydrofuran [THF] Flow rate: 1.0mL / min Test liquid solid content concentration: 0.001~0.01% by mass Injection volume: 50μL Detector; RI Calibration standard material;TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (Manufactured by Tosoh Corporation)

[0144] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing content or usage are by mass unless otherwise specified.

[0145] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing content or usage are by mass unless otherwise specified.

[0146] <Synthesis Example 1: Preparation of Pigment Dispersion 1> CI Pigment Blue 15:6 14.1 parts CI Pigment Violet 23 0.5 part Acrylic pigment dispersant 4.0 parts Propylene glycol monomethyl ether acetate 81.4 parts A pigment dispersion 1 was obtained by mixing the ingredients and thoroughly dispersing the pigment using a bead mill.

[0147] <Synthesis Example 2: Preparation of Pigment Dispersion 2> CI Pigment Red 291 12.3 bu CI Pigment Yellow 139 1.4 parts Acrylic pigment dispersant 4.3 parts Propylene glycol monomethyl ether acetate 82 parts By mixing the ingredients and thoroughly dispersing the pigment using a bead mill, a pigment dispersion 2 was obtained.

[0148] <Synthesis Example 3: Preparation of Pigment Dispersion 3> CI Pigment Green 36 5.6 bu CI Pigment Yellow 150 6.8 parts Acrylic pigment dispersant 4.4 parts Propylene glycol monomethyl ether acetate 83.2 parts A pigment dispersion 3 was obtained by mixing the ingredients and thoroughly dispersing the pigment using a bead mill.

[0149] <Synthesis Example 4: Preparation of Resin (Resin 1)> 349 parts of propylene glycol monomethyl ether acetate were added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen, and the temperature was raised to 120°C. Next, 23.4 parts of T-butyl peroxy-2-ethylhexanoate were added to a monomer mixture consisting of 169.2 parts benzyl methacrylate, 103.3 parts methacrylic acid, and 52.9 parts dicyclopentanyl methacrylate, and this mixture was added dropwise to the flask from a dropping funnel over a period of 2 hours. After the addition was complete, the mixture was stirred for another 30 minutes to carry out the copolymerization reaction. Subsequently, the flask was purged with air, and 51.2 parts of glycidyl methacrylate, 1.1 parts of triphenylphosphine, and 1.1 parts of methoquinone were added. The reaction was continued at 120°C for 10 hours to obtain a polymer. Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to achieve a polymer solid content concentration of 40%, yielding a resin (resin 1) solution with a weight-average molecular weight of 10300. The acid value per solid content of resin (resin 1) was 20.9 mg KOH / g. The content of structural unit B relative to the total structural units constituting resin 1 is 0 mol%.

[0150] <Synthesis Example 5: Preparation of Resin (Resin 2)> 439 parts of propylene glycol monomethyl ether were added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 90°C. Next, 53.1 parts of dimethyl 2,2'-azobis(2-methylpropionate) were added to a monomer mixture consisting of 140 parts of 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate, 77 parts of 2-[(diethyl malate)carbonylamino]ethyl acrylate, 57 parts of 2-ethylhexyl acrylate, 30 parts of 2-hydroxyethyl methacrylate, 27 parts of methacrylic acid, 100 parts of propylene glycol monomethyl ether, and 153 parts of propylene glycol monomethyl ether acetate, and this mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the dropwise addition was complete, the mixture was stirred for a further 2 hours to carry out the copolymerization reaction and obtain the polymer. Subsequently, to a solution containing the resin precursor and solvent in a flask at atmospheric pressure under a nitrogen gas atmosphere, 0.8 parts of hydroxymonomethyl ether as a polymerization inhibitor and 10.0 parts of 1,8-diazabicyclo[5.4.0]-7-undecene as a basic catalyst were added to obtain a resin precursor composition. The resin precursor composition was held at 98°C for 30 minutes with stirring in a flask at atmospheric pressure under a nitrogen gas atmosphere to obtain a reaction solution containing the copolymer and solvent. To this solution, propylene glycol monomethyl ether acetate was added as a solvent so that the non-solvent components accounted for 35% by mass, to obtain a resin (resin 2) solution with a weight-average molecular weight of 6800. The acid value per solid content of resin (resin 2) was 50.2 mgKOH / g. The content of structural unit B relative to all structural units constituting resin 2 is 19.6 mol%.

[0151] <Synthesis Example 6: Preparation of Resin (Resin 3)> 261 g of propylene glycol monomethyl ether was added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen, and the temperature was raised to 90°C. Next, 41.6 parts of dimethyl 2,2'-azobis(2-methylpropionate) were added to a monomer mixture consisting of 100 parts of 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate, 175 parts of 2-ethylhexyl acrylate, 34 parts of 2-hydroxyethyl methacrylate, 17 parts of methacrylic acid, 18 parts of allyl methacrylate, 124 parts of propylene glycol monomethyl ether, and 158 parts of propylene glycol monoethyl ether acetate, and this mixture was added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the mixture was stirred for a further 2 hours to carry out the copolymerization reaction and obtain the polymer. Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to achieve a polymer solids concentration of 35%, yielding a resin (resin 3) solution with a weight-average molecular weight of 16,000. The acid value per solids of resin (resin 3) was 29.5 mg KOH / g. The content of structural unit B relative to all structural units constituting resin 3 is 50.5 mol%.

[0152] <Synthesis Example 7: Preparation of Resin (Resin 4)> 386 parts of propylene glycol monomethyl ether were added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 90°C. Next, 61.5 parts of dimethyl 2,2'-azobis(2-methylpropionate) were added to a monomer mixture consisting of 147 parts of 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate, 285 parts of 2-ethylhexyl acrylate, 50 parts of 2-hydroxyethyl methacrylate, 26 parts of methacrylic acid, 183 parts of propylene glycol monomethyl ether, and 234 parts of propylene glycol monoethyl ether acetate. This mixture was then added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the mixture was stirred for a further 2 hours to carry out the copolymerization reaction and obtain the polymer. Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to achieve a polymer solids concentration of 35%, yielding a resin (resin 4) solution with a weight-average molecular weight of 9000. The acid value per solids of resin (resin 4) was 32.7 mgKOH / g. The content of structural unit B relative to all structural units constituting resin 4 is 56.9 mol%.

[0153] <Synthesis Example 8: Preparation of Resin (Resin 5)> 1176 parts of propylene glycol monomethyl ether were added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 90°C. Next, 93.1 parts of dimethyl 2,2'-azobis(2-methylpropionate) were added to a monomer mixture consisting of 491 parts of 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate, 950 parts of 2-ethylhexyl acrylate, 165 parts of 2-hydroxyethyl methacrylate, 86 parts of methacrylic acid, 609 parts of propylene glycol monomethyl ether, and 778 parts of propylene glycol monoethyl ether acetate. This mixture was then added dropwise to the flask from a dropping funnel over a period of 1 hour. After the addition was complete, the mixture was stirred for a further 2 hours to carry out the copolymerization reaction and obtain the polymer. Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to achieve a polymer solids concentration of 35%, yielding a resin (resin 5) solution with a weight-average molecular weight of 16,300. The acid value per solids of resin (resin 5) was 37.4 mg KOH / g. The content of structural unit B relative to all structural units constituting resin 5 is 56.9 mol%.

[0154] <Synthesis Example 9: Preparation of Resin (Resin 6)> In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 124.3 parts of propylene glycol monomethyl ether acetate were added as a solvent, and the mixture was stirred while purging with nitrogen, and the temperature was raised to 100°C. Next, a monomer mixture consisting of 158.5 parts 2-ethylhexyl acrylate, 32.7 parts acrylic acid, and 179.7 parts propylene glycol monomethyl ether acetate was mixed with 11.5 parts 2,2'-azobis(isobutyronitrile) and then added dropwise to the flask from a dropping funnel over a period of 1 hour. After the dropwise addition was complete, the solution in the flask was stirred and polymerized at 100°C for 2 hours to obtain a liquid containing the copolymer precursor and solvent. In a flask at atmospheric pressure under a 6% oxygen gas atmosphere, a liquid containing a copolymer precursor and a solvent was added. 0.69 parts hydroquinone monomethyl ether was added as a polymerization inhibitor, 0.69 parts triphenylphosphine as a catalyst, and 37.4 parts glycidyl methacrylate were added, and the mixture was held at 120°C for 720 minutes with stirring. To the reaction solution containing the copolymer obtained in this manner and the solvent, propylene glycol monomethyl ether acetate was added as the solvent so that the non-solvent components accounted for 35% by mass, yielding a resin (resin 6) solution with a weight-average molecular weight of 14300. The acid value per solid content of resin (resin 6) was 60.8 mgKOH / g. The content of structural unit B relative to all structural units constituting resin 5 is 65.5 mol%.

[0155] <Examples 1-7 and Reference Example 1> (1) Preparation of a colored curable resin composition A colored curable resin composition was obtained by mixing each component listed in Table 1 in the amounts specified in Table 1. In preparing the colored curable resin composition, propylene glycol monomethyl ether acetate was mixed in so that the solid content of the colored curable resin composition was 18% by weight. The units for the amounts of each component in Table 1 are "parts by mass," and the amounts of colorants and dispersants, resins (Resin 1) to (Resin 6), polymerizable compounds, polymerization initiators, and leveling agents in the pigment dispersion are expressed on a solid content basis. The polymerizable compounds, polymerization initiators, and leveling agents are as follows: Polymerizable compound: Glycerin triacrylate (Arronix® M-930; manufactured by Toagosei Co., Ltd.) Polymerization initiator: ADEKA ARCULUS (registered trademark) NCI-831E (manufactured by ADEKA Corporation) Leveling agent: Polyether-modified silicone oil (product name "Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.).

[0156] [Table 1]

[0157] (2) Hayes' evaluation A colored curable resin composition was applied by spin coating onto a 5cm square glass substrate (Eagle 2000; Corning Corporation) to a post-baking thickness of 2.5 μm. The substrate was then pre-baked at 85°C for 2 minutes to form a colored composition layer. After cooling, the colored composition layer formed on the substrate was exposed to 100 mJ / cm² of air using an exposure unit (TME-150RSK; Topcon Corporation) in an atmospheric environment. 2 The sample was irradiated with light at the specified exposure level (based on 365 nm). After light irradiation, post-bake was performed in an oven at 85°C for 30 minutes to obtain a colored coating. The haze of the obtained colored coating film was measured using a haze meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.).

[0158] [Table 2]

[0159] As shown in Table 2, Reference Example 1 had low haze and insufficient scattering performance. In contrast, the colored coatings obtained in Examples 1 to 7 had high haze and showed good scattering performance.

[0160] <Examples 8-10> In the same manner as in Examples 1 to 7, a colored curable resin composition was prepared using pigment dispersion 2 or pigment dispersion 3 instead of pigment dispersion 1, in the proportions shown in Table 3, to obtain a colored coating film.

[0161] [Table 3]

[0162] For each colored coating obtained from the colored curable resin compositions listed in Table 3, the haze was measured using a haze meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.) in the same evaluation method as in Examples 1 to 7.

[0163] [Table 4]

[0164] As shown in Table 4, the colored coatings obtained in Examples 8-10 exhibited high haze and good scattering performance.

Claims

1. It contains a colorant, resin, polymerizable compound and polymerization initiator, The resin comprises structural unit A, which is derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and formula (1): 【Chemistry 1】 [In the formula, R １ This represents a hydrogen atom or a methyl group. R ２ [This represents a linear or branched alkyl group having 6 to 20 carbon atoms.] The copolymer α comprises a structural unit B derived from a monomer represented by the following: The content of structural unit B in the copolymer α is 50 to 90 mol% relative to the total amount of structural units constituting the copolymer α. Colored curable resin composition.

2. The colored curable resin composition according to claim 1, wherein the resin further comprises a copolymer β different from the copolymer α.

3. The colored curable resin composition according to claim 1, wherein copolymer α further comprises a structural unit C derived from an ethylenically unsaturated group-containing isocyanate compound or a monomer having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond.

4. The colored curable resin composition according to claim 1, wherein the resin content is 20 to 60% by mass, based on the solid content of the colored curable resin composition.

5. The colored curable resin composition according to claim 1, wherein the content of copolymer α is 5 to 80% by mass with respect to 100 parts by mass of resin.

6. The colored curable resin composition according to claim 1, wherein the polymerizable compound content is 50 to 85 parts by mass per 100 parts by mass of the resin.

7. A color filter, which is a cured film of the colored curable resin composition according to claim 1 or 2.

8. The color filter according to claim 7, having a haze value of 1 to 50% when converted to a thickness of 2.5 μm.

9. A display device comprising the color filter described in claim 7.

Images