Colored curable resin composition, color filter and display device

Abstract

The invention relates to a colored curable resin composition, a color filter and a display device. The present invention addresses the problem of providing a colored curable resin composition capable of forming a color filter having haze even without the addition of inorganic fine particles. [Solution] The colored curable resin composition contains a colorant, a resin, a polymerizable compound and a polymerization initiator, and the resin contains a copolymer [alpha] having: a structural unit A derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a structural unit B derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit C derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides; and a structural unit B derived from a monomer represented by formula (1), the content of the structural unit B in the copolymer [alpha] being 50-90 mol% with respect to the total amount of the structural units constituting the copolymer [alpha]. In formula (1), R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group having 6-20 carbon atoms.

Description

Technical Field

[0001] This invention relates to color-curing resin compositions, color filters, and display devices. Background Technology

[0002] A color filter substrate has the following structure: a black matrix layer is formed on a transparent substrate, and color filters for forming pixels, such as red (R), green (G), and blue (B), are formed thereon. A protective film is laminated on top of the substrate as needed. This color filter substrate is used in liquid crystal display devices and organic electroluminescent (EL) display devices. In such display devices, it is required to obtain a sufficient field of view even when viewed at an angle. For example, Patent Document 1 discloses a color-curable resin composition that, by containing inorganic microparticles, can form a color filter that provides a good field of view when viewed at an angle.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2023-081304 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] Conventional color-curing resin compositions widen the viewing angle by using inorganic microparticles to scatter light passing through the display device in all directions, thereby averaging the light within the field of view. However, in compositions that can form color filters with haziness by using inorganic microparticles, there is a possibility that the dispersion of the inorganic microparticles becomes uneven due to sedimentation, thus reducing the scattering effect. Therefore, for color filters formed from color-curing resin compositions, it is necessary to further ensure the viewing angle when viewing the display device from an oblique angle.

[0008] Therefore, the objective of this invention is to provide a color-curing resin composition that can form a color filter with haze even without the addition of inorganic particles.

[0009] Methods for solving problems

[0010] The inventors of this application have discovered that the above-mentioned objectives can be achieved through the coloring and curing resin composition of the present invention, as described below. That is, the present invention includes the following embodiments.

[0011] [1] A coloring and curing resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator.

[0012] The aforementioned resin comprises copolymer α, wherein copolymer α has:

[0013] Structural unit A derived from at least one of the groups consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides; and

[0014] Derived from the structural unit B of the single entity represented by equation (1),

[0015]

[0016] [In the formula,

[0017] R 1 Indicates a hydrogen atom or a methyl group.

[0018] R 2 [Refers to straight-chain or branched alkyl groups with 6 to 20 carbon atoms]

[0019] The content of structural unit B in the aforementioned copolymer α is 50 to 90 mol% relative to the total amount of structural units constituting the copolymer α.

[0020] [2] The coloring curable resin composition as described in [1], wherein the resin further comprises a copolymer β that is different from the aforementioned copolymer α.

[0021] [3] The coloring curable resin composition as described in [1] or [2], wherein the copolymer α further comprises the following structural unit C, said structural unit C being derived from an isocyanate compound containing an olefinic unsaturated group or a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an olefinic unsaturated bond.

[0022] [4] The coloring curable resin composition as described in any one of [1] to [3], wherein the resin content is 20 to 60% by mass based on the amount of solid components in the coloring curable resin composition.

[0023] [5] The coloring and curing resin composition as described in any one of [1] to [4], wherein the content of copolymer α is 5 to 80 parts by mass relative to 100 parts by mass of resin.

[0024] [6] The coloring and curing resin composition according to any one of [1] to [5], wherein the content of the polymeric compound is 50 to 85 parts by mass relative to 100 parts by mass of the resin.

[0025] [7] A color filter, which is a cured film of the color curable resin composition described in any one of [1] to [6].

[0026] [8] The color filter described in [7] has a haze value of 1 to 50% when its thickness is converted to 2.5 μm.

[0027] [9] A display device comprising the color filter described in [7] or [8].

[0028] Invention Effects

[0029] According to the present invention, a color-curing resin composition is provided that can form a color filter with haze even without the addition of inorganic particles. Detailed Implementation

[0030] The embodiments of the present invention will now be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the invention. Furthermore, when multiple upper and lower limits are specified for a particular parameter, any combination of these upper and lower limits can be used as a suitable numerical range.

[0031] <Coloring and Curing Resin Composition>

[0032] The coloring and curing resin composition of the present invention comprises a colorant, a resin, a polymerizable compound, and a polymerization initiator.

[0033] (resin)

[0034] The coloring and curing resin composition of the present invention comprises a copolymer α having the following characteristics:

[0035] Structural unit A derived from at least one of the groups consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides; and

[0036] Derived from the structural unit B of the single entity represented by equation (1),

[0037]

[0038] [In the formula,

[0039] R 1 Indicates a hydrogen atom or a methyl group.

[0040] R 2 [Refers to straight-chain or branched alkyl groups with 6 to 20 carbon atoms]

[0041] The content of structural unit B in the aforementioned copolymer α is 50 to 90 mol% relative to the total amount of structural units constituting the copolymer α.

[0042] Conventionally, inorganic particles have been used to impart haze to color filters, as described in Patent Document 1, but this has resulted in problems due to the sedimentation of these particles. In contrast, the color-curing resin composition according to the present invention, by comprising copolymer α, enables the formation of a color filter with the desired haze even without the addition of inorganic particles, wherein copolymer α has structural unit A derived from at least one of the groups selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and structural unit B derived from a monomer represented by formula (1).

[0043] As a monomer introduced into copolymer α, derived from at least one structural unit A selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, examples include:

[0044] Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinylbenzoic acid;

[0045] Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, zeaxanthin, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid.

[0046] Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc., are bicyclic unsaturated compounds containing carboxyl groups;

[0047] Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxylic acid bicyclic [2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic acid anhydrides;

[0048] Unsaturated mono[(meth)acryloyloxyethyl] esters of polycarboxylic acids with two or more members, such as mono[2-(meth)acryloyloxyethyl] ester of succinate and mono[2-(meth)acryloyloxyethyl] ester of phthalate.

[0049] Unsaturated acrylates such as α-(hydroxymethyl)acrylic acid, which contain both hydroxyl and carboxyl groups in the same molecule.

[0050] Among them, acrylic acid and methacrylic acid are preferred from the perspective of copolymerization reactivity and the solubility of the resulting resin in alkaline aqueous solution.

[0051] The monomer represented by formula (1) (which provides the structural unit B in copolymer α) contains R 2 The number of carbon atoms is 6 to 20, preferably 7 to 18, more preferably 8 to 12, and even more preferably 8 to 10. R in the monomer represented by formula (1) 2 When the number of carbon atoms is within the above range, a color-curable resin composition capable of forming a color filter with the desired haze can be obtained. If R in the monomer represented by formula (1) 2 If the number of carbon atoms is above the aforementioned lower limit, sufficient haze can be obtained, which is therefore advantageous. Furthermore, R in the monomer represented by formula (1) 2 With a higher number of carbon atoms, compared to a lower number, a smaller amount of copolymer α can ensure film haze, thus offering advantages in reliability such as chemical resistance. On the other hand, R 2 When the number of carbon atoms is greater than the upper limit mentioned above, the surface of the cured film tends to become rougher.

[0052] R in the monomer represented by equation (1) 2 Branched alkyl groups are preferred. Additionally, in the monomer represented by formula (1), R... 2 Preferred branched alkyl groups are 2-ethylhexyl, 2-hexyldecyl, and 2-butyloctyl.

[0053] In one embodiment of the present invention, examples of monomers represented by formula (1) include heptyl acrylate, octyl acrylate, isononyl acrylate, dodecyl acrylate, isodecanyl acrylate, hexadecyl acrylate, stearyl acrylate, isostearyl acrylate, dodecyl methacrylate, and 2-ethylhexyl acrylate. When the structural unit B in copolymer α is derived from the monomer represented by formula (1) in the above examples, there is a tendency to ensure the desired haze of the color filter, thereby easily obtaining a good surface condition of the cured film, and excellent chemical resistance, etc.

[0054] The structural unit B in copolymer α can be derived from one monomer represented by formula (1) or from two or more monomers represented by formula (1).

[0055] The content of structural unit B in copolymer α is 50-90 mol%, preferably 55-85 mol%, more preferably 55-80 mol%, and even more preferably 55-75 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 with the desired haze can be obtained. If the content of structural unit B in copolymer α is above the aforementioned lower limit, it is advantageous in ensuring sufficient haze. In addition, if the content of structural unit B in copolymer α is high, compared with the low case, the haze of the film can be ensured with a smaller amount of copolymer α, which is therefore advantageous. On the other hand, if the content of structural unit B in copolymer α is higher than the aforementioned upper limit, it becomes difficult to develop the pattern. Therefore, the content of structural unit B relative to the total amount of structural units constituting copolymer α is preferably 50-80 mol%, more preferably 50-70 mol%.

[0056] The copolymer α in the coloring and curing resin composition preferably further comprises the following structural unit C, which is derived from an isocyanate compound containing an olefinic unsaturated group or a monomer having a cyclic ether structure with 2 to 4 carbon atoms and an olefinic unsaturated bond.

[0057] Structural unit C is derived, for example, from isocyanate compounds (C0) having an isocyanate group and an olefinic unsaturated bond (hereinafter, sometimes referred to as "(C0)"). Examples of olefinic unsaturated groups included in (C0) include vinyl groups, (meth)acryloyloxy groups, etc.

[0058] It should be noted that in this specification, "(meth)acrylic acid" means 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.

[0059] Specifically, examples of (C0) include: ethyl 2-isocyanate of (meth)acrylate, propyl 2-isocyanate of (meth)acrylate, propyl 3-isocyanate of (meth)acrylate, 1-methyl ethyl 2-isocyanate of (meth)acrylate, 1,1-dimethyl ethyl 2-isocyanate of (meth)acrylate, cyclohexyl 4-isocyanate of (meth)acrylate, and methacryloyl isocyanate; and reaction products formed by reacting 2-hydroxyalkyl methacrylate with a diisocyanate compound in equimolar amounts (2-hydroxyalkyl methacrylate: diisocyanate compound = 1 mole: 1 mole).

[0060] In one embodiment of the present invention, from the viewpoint of the storage stability of the coloring and curing resin composition, the isocyanate group in (C0) is preferably a capped isocyanate group (hereinafter, sometimes referred to as "capped isocyanate group"), and the structural unit C is preferably derived from an isocyanate compound (C0-1) (hereinafter, sometimes referred to as "(C0-1)") whose isocyanate group in (C0) has been capped. The isocyanate group in (C0) can be capped by a capping agent.

[0061] Examples of end-capping agents for capping the isocyanate group of (C0) include: β-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, and other lactams; methanol, ethanol, propanol, 1-methoxy-2-propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, malate, 2-methyl malate, 3-methyl malate, 2,3-dimethyl malate, tartrate esters, and citrate esters; phenol, 2,6-dimethylphenol, cresol, 3,5-dimethylphenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, etc., butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrene-modified phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol, etc. Phenolic compounds such as phenol; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; thiol compounds such as butyl thiol, thiophenol, and tert-dodecyl thiol; amine compounds such as diisopropylamine, diphenylamine, phenylnaphthylamine, aniline, and carbazole; amide compounds such as acetanilide, methoxyacetanilide, acetamide, and benzamide; imide compounds such as succinimide and maleimide; and imidazole, 2... Imidazole-based compounds such as methylimidazole and 2-ethylimidazole; pyrazole-based compounds such as pyrazole and 3,5-dimethylpyrazole; urea-based compounds such as urea, thiourea, and vinylurea; carbamate-based compounds such as N-phenylcarbamate and 2-oxazolidinone; imine-based compounds such as ethyleneimine and polyethyleneimine; oxime-based compounds such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, and cyclohexanone oxime; and bisulfite-based compounds such as sodium bisulfite and potassium bisulfite. As capping agents, from the viewpoints of ease of acquisition, cost, and neutrality after removal, dimalonate and malate are preferred, especially dimethyl malonate, diethyl malonate, and diethyl malate. These capping agents can be used alone or in combination of two or more.

[0062] (C0-1) is preferably 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl acrylate, 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.

[0063] (C0-1) Commercially available, for example, AOI-DEM: Karenz (registered trademark) AOI-DEM (reaction product of 2-isocyanate ethyl acrylate and diethyl malonate, 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl acrylate, manufactured by Showa Denko Co., Ltd.), and AOI-MDE: Karenz (registered trademark) AOI-MDE (reaction product of 2-isocyanate ethyl acrylate and diethyl malate, 2-[(diethyl malate)carbonylamino]ethyl acrylate, manufactured by Showa Denko Co., Ltd.).

[0064]

[0065] In one embodiment of the present invention, from the viewpoints of the preservation stability, ease of acquisition, and neutrality after removal of the coloring and curing resin composition, (CO-1) is particularly preferred to be 2-malonic acid-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester.

[0066] Structural unit C is derived, for example, from a monomer having a cyclic ether structure having 2 to 4 carbon atoms (e.g., selected from at least one of the groups consisting of ethylene oxide ring, oxobutane ring, and tetrahydrofuran ring) and an olefinic unsaturated bond. Preferably, the monomer having a cyclic ether structure having 2 to 4 carbon atoms and an olefinic unsaturated bond is a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0067] Examples of monomers having a cyclic ether structure with 2 to 4 carbon atoms and an olefinic unsaturated bond include monomers having an ethylene oxide group and an olefinic unsaturated bond (C1) (hereinafter sometimes referred to as "(C1)"), monomers having an oxocyclobutyl group and an olefinic unsaturated bond (C2) (hereinafter sometimes referred to as "(C2)"), and monomers having a tetrahydrofuran group and an olefinic unsaturated bond (C3) (hereinafter sometimes referred to as "(C3)").

[0068] As (C1), examples include monomers having an epoxidized structure of a straight-chain or branched aliphatic unsaturated hydrocarbon (C1-1) (hereinafter sometimes referred to as "(C1-1)") and monomers having an epoxidized structure of an alicyclic unsaturated hydrocarbon (C1-2) (hereinafter sometimes referred to as "(C1-2)").

[0069] Examples of (C1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, and 2,3-bis(glycidyloxymethyl) 2,4-Bis(glycidyloxymethyl)styrene, 2,5-Bis(glycidyloxymethyl)styrene, 2,6-Bis(glycidyloxymethyl)styrene, 2,3,4-Tris(glycidyloxymethyl)styrene, 2,3,5-Tris(glycidyloxymethyl)styrene, 2,3,6-Tris(glycidyloxymethyl)styrene, 3,4,5-Tris(glycidyloxymethyl)styrene, 2,4,6-Tris(glycidyloxymethyl)styrene, etc.

[0070] Examples of compounds represented by (C1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Co., Ltd.), methyl 3,4-epoxycyclohexyl methacrylate (e.g., Cyclomer A400; manufactured by Daicel Co., Ltd.), methyl 3,4-epoxycyclohexyl methacrylate (e.g., Cyclomer M100; manufactured by Daicel Co., Ltd.), compounds represented by formula (CI), and compounds represented by formula (CII).

[0071]

[0072] In formulas (CI) and (CII), R a and R b It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the hydrogen atom contained in the alkyl group may be replaced by a hydroxyl group.

[0073] X 1 and X 2 Indicates a single bond, *-R g -、*-R g -O-、*-R g -S- or *-R g -NH-.

[0074] R g It represents the dimethyl groups of alkanes with 1 to 6 carbon atoms.

[0075] * indicates a connection to 'O'.

[0076] Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.

[0077] Examples of alkyl groups in which hydrogen atoms are replaced by hydroxyl groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.

[0078] As R a and R b Preferably, hydrogen atoms, methyl groups, hydroxymethyl groups, 1-hydroxyethyl groups, and 2-hydroxyethyl groups are included; more preferably, hydrogen atoms and methyl groups are included.

[0079] Examples of alkane dimethyl groups include methylene, ethylene, propane-1,2-dimethyl, propane-1,3-dimethyl, butane-1,4-dimethyl, pentane-1,5-dimethyl, and hexane-1,6-dimethyl.

[0080] As X 1 and X 2 Preferred examples include single bonds, methylene, ethylene, *-CH2-O- and *-CH2CH2-O-, and more preferably single bonds and *-CH2CH2-O- (* indicates a bond with O).

[0081] 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), and (CI-11) to (CI-15), and more preferably compounds represented by formulas (CI-1), (CI-7), (CI-9), and (CI-15).

[0082]

[0083] 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), and (CII-11) to (CII-15), and more preferably compounds represented by formulas (CII-1), (CII-7), (CII-9), and (CII-15).

[0084]

[0085] The compounds represented by formula (CI) and formula (CII) can each be used alone. They can be used together in any ratio. When used together, the mixing ratio is preferably 5:95 to 95:5 in molar ratio of formula (CI): formula (CII), more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.

[0086] As (C2), a monomer having an oxetyl group and a (meth)acryloyloxy group is more preferably preferred. Examples of (C2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc.

[0087] As (C3), a monomer having a tetrahydrofuran group and a (meth)acryloyloxy group is more preferred. Specifically, examples of (C3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemicals Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0088] From the perspective of its advantage in curing at low temperatures, the compound providing structural unit C is preferably an isocyanate compound containing an olefinic unsaturated group and a monomer having a linear or branched aliphatic unsaturated hydrocarbon structure after epoxidation, more preferably a monomer having an isocyanate group or a glycidyl group and an olefinic unsaturated group.

[0089] In one embodiment of the present invention, the copolymer α can be exemplified by resins [α1] to [α4].

[0090] 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)");

[0091] Resin [α2]: A copolymer having a structural unit obtained by adding (C) to (A) and (B);

[0092] Resin [α3]: A copolymer having a structural unit obtained by adding (A) to (C) and (B);

[0093] Resin [α4]: A copolymer having a structural unit (B) obtained by adding (A) to (C), further adding to a polycarboxylic acid and / or a carboxylic anhydride.

[0094] The resin [α1] can be manufactured, for example, by referring to the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Dojin 1st Edition 1st Printing, March 1, 1972) and the references cited in that document.

[0095] Specifically, the following method can be used: A predetermined amount of (A) and (C), the polymerization initiator, and the solvent are placed in a reaction vessel. For example, nitrogen is used to replace oxygen, thereby creating a deoxygenated atmosphere. The mixture is then heated and kept at a constant temperature while stirring. It should be noted that the polymerization initiator and solvent used herein are not particularly limited, and substances commonly used in the art can be used. For example, as polymerization initiators, examples include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile) etc.) and organic peroxides (benzoyl peroxide, tert-butyl peroxide, etc.). As solvents, any solvent that dissolves the monomers is acceptable; examples include organic solvents that may be included in the coloring and curing resin composition of the present invention, as described below.

[0096] It should be noted that, regarding the obtained copolymer, the solution after the reaction can be used directly, or a concentrated or diluted solution can be used, or a substance extracted in solid (powder) form by methods such as reprecipitation can be used. In particular, during this polymerization, by using a solvent, as described below, which may be included in the composition of the color-curing resin composition of the present invention, the solution after the reaction can be directly used in the preparation of the color-curing resin composition of the present invention, thus simplifying the manufacturing process of the color-curing resin composition of the present invention.

[0097] In resin [α1], the preferred ratio of each structural unit among all the structural units constituting resin [α1] is:

[0098] Structural unit A: 2-45 mol%

[0099] Structural Unit B: 50–90 mol%

[0100] Structural unit C: 2–95 mol%

[0101] More preferably:

[0102] Structural unit A: 5–40 mol%

[0103] Structural unit B: 50-80 mol%

[0104] Structural unit C: 5–80 mol%.

[0105] It is believed that if the ratio of the structural units of the resin [α1] is within the above-mentioned range, the desired haze of the color filter can be easily obtained. Furthermore, the color-curing resin composition exhibits excellent storage stability, developability during pattern formation, and solvent resistance, heat resistance, and mechanical strength of the resulting cured film. From the viewpoint of easily improving curing at low temperatures, (C) used as resin [α1] is preferably (C0) and (C1), especially (C0-1) and (C1-1).

[0106] The resin [α2] can be manufactured by obtaining a copolymer of (A) and (B), and then adding the isocyanate group or cyclic ether having 2 to 4 carbon atoms of (C) to the carboxylic acid and / or carboxylic anhydride of (A).

[0107] First, the copolymer of (A) and (B) is manufactured in the same manner as described in the method for manufacturing resin [α1]. In this case, the preferred ratio of each structural unit in all structural units constituting resin [α2] is:

[0108] Structural unit A: 10-50 mol%

[0109] Structural Unit B: 50–90 mol%

[0110] More preferably:

[0111] Structural Unit A: 20–45 mol%

[0112] Structural unit B: 55-80 mol%.

[0113] Next, the isocyanate group or cyclic ether having 2 to 4 carbon atoms in (C) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (A) in the aforementioned copolymer.

[0114] After manufacturing the copolymer of (A) and (B), the atmosphere inside the flask is replaced with air instead of nitrogen, and (C), a reaction catalyst (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.) and a polymerization inhibitor (e.g., hydroquinone, p-hydroxyanisole, etc.) are added to the flask, for example, and reacted at 60 to 130°C for 1 to 10 hours, thereby manufacturing resin [α2].

[0115] The amount of (C) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (A). It is believed that if the ratio of the structural units of the resin [α2] is within the above range, the desired haze of the color filter can be easily obtained. Furthermore, there is a tendency for the color-curing resin composition to exhibit good storage stability, developability when forming a pattern, pattern shape, low-temperature curability, and a good balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern. Considering the high reactivity of the isocyanate group and the low likelihood of unreacted (C) residue, (C0) is preferred as (C0) as the (C) used in the resin [α2], and more preferably (C0-1). Furthermore, considering the high reactivity of the cyclic ether and the low likelihood of unreacted (C) residue, (C1) is preferred as (C1) as the (C) used in the resin [α2], and more preferably (C1-1).

[0116] The amount of the aforementioned reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the combined amount of (A), (B), and (C). The amount of the aforementioned polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the combined amount of (A), (B), and (C).

[0117] The charging method, reaction temperature, and time, among other reaction conditions, can be appropriately adjusted by taking into account the manufacturing equipment and the heat generated by polymerization. It should be noted that the charging method and reaction temperature can be appropriately adjusted by considering the manufacturing equipment and the heat generated by polymerization, similar to the polymerization conditions.

[0118] Regarding resin [α3], as a first stage, copolymers of (B) and (C) are obtained in the same manner as those for resin [α1] described above. Similarly, regarding the obtained copolymer, the solution after the reaction can be used directly, or a concentrated or diluted solution can be used, or a substance extracted in solid (powder) form by methods such as reprecipitation can be used.

[0119] The preferred ratios of structural units derived from (B) and (C) are respectively, relative to the total molar number of all structural units constituting the aforementioned copolymer.

[0120] Structural Unit B: 50–90 mol%

[0121] Structural unit C: 10–50 mol%

[0122] More preferably:

[0123] Structural Unit B: 55-80 mol%

[0124] Structural unit C: 20–45 mol%.

[0125] It is believed that if the ratio of the structural units of the resin [α3] is within the above range, the desired haze of the color filter can be easily obtained. In addition, there is a tendency for the color curable resin composition to have good storage stability, developability when forming a pattern, pattern shape, curability at low temperature, and a good balance of solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern.

[0126] Furthermore, under the same conditions as the manufacturing method of resin [α2], resin [α3] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (A) with the isocyanate compound or cyclic ether derived from (C) in the copolymer of (B) and (C).

[0127] The amount of (A) used in reaction with the aforementioned copolymer is preferably 5 to 100 moles relative to 100 moles of (C). Considering the high reactivity of the isocyanate group and the low likelihood of unreacted (C) residue, (C0) is preferred as (C0) and more preferably (C0-1) as (C0) used in the resin [α3]. Furthermore, considering the high reactivity of the cyclic ether and the low likelihood of unreacted (C) residue, (C1) is preferred as (C1) used in the resin [α3] and more preferably (C1-1).

[0128] Resin [α4] is a resin obtained by further reacting a polycarboxylic acid and / or a carboxylic anhydride with resin [α3]. The hydroxyl groups generated by reacting an isocyanate compound or cyclic ether derived from (C) with a carboxylic acid or carboxylic anhydride derived from (A) are further reacted with the polycarboxylic acid and / or a carboxylic anhydride.

[0129] Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and trimalic acid. Examples of carboxylic 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-dicarboxylic bicyclo[2.2.1]hept-2-ene anhydride. The amount of polycarboxylic acid and / or carboxylic anhydride used is preferably 0.05 to 1 mole, more preferably 0.1 to 0.5 moles, relative to 1 mole of (A).

[0130] In one embodiment of the present invention, from the viewpoint of easily obtaining the desired haze, good developability, and low-temperature curability of the color filter, the copolymer α is preferably a resin [α1], and more preferably a resin [α1] using a monomer having an isocyanate group or a glycidyl group as (C). Among the resin [α1], glycidyl (meth)acrylate, AOI-DEM, and AOI-MDE are preferred as (C).

[0131] The coloring and curing resin composition of the present invention may contain one copolymer α, or may contain two or more copolymers α in combination.

[0132] Based on the amount of solid components in the color-curing resin composition, the resin content is preferably 20-60% by mass, more preferably 30-55% by mass, and even more preferably 40-50% by mass. If the resin content is within the above range, the following tendencies are observed: it is easier to obtain the desired haze of the color filter; it is easier to improve the curability of the color-curing resin composition; it is easier to form a cured film; and the resolution of the pattern and the residual film rate are improved. It should be noted that, in this specification, the term "amount of solid components" refers to the amount remaining after subtracting the solvent content from the total amount of the color-curing resin composition. The amount of solid components and the content of each component relative to it can be determined, for example, using known analytical methods such as liquid chromatography or gas chromatography.

[0133] The content of copolymer α relative to 100 parts by mass of resin can be 100% by mass, preferably 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 75% by mass, even more preferably 15 to 75% by mass, and can be 5 to 50% by mass. It is believed that when the content of copolymer α is within the above range, a color filter with haze can be obtained.

[0134] In one embodiment of the present invention, based on the amount of solid components in the color-curing resin composition, the content of copolymer α in the color-curing resin composition is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 7 to 20% by mass. When the content of copolymer α is within the above range, the desired haze of the color filter can be easily obtained. Furthermore, high reliability, such as high chemical resistance, is easily obtained.

[0135] The content of copolymer α in the coloring curable resin composition depends on the R in the monomer represented by formula (1) that provides the structural unit B in copolymer α. 2 The tendency of the number of carbon atoms, for example, has R 2The higher the number of carbon atoms, the more likely the desired haze can be obtained with a lower content. Additionally, there is a tendency to depend on the content of structural unit B in copolymer α. For example, a higher content of structural unit B in copolymer α results in a lower desired haze or a higher haze with the same content compared to a lower content. When the content of copolymer α is small, it becomes advantageous because more polymerizable compounds and (if present) resins such as copolymer β, which are different from copolymer α, can be included. This makes it easier to adjust the curability of the composition and obtain a good cured film shape.

[0136] The color-curing resin composition may further include a copolymer β, which is different from copolymer α. Copolymer β is preferably a substance that, when combined with copolymer α, can obtain the desired haze, and is preferably an alkali-soluble resin. In this specification, an alkali-soluble resin refers to a resin that has the property of dissolving in a developer solution that is an aqueous solution of an alkali compound. Specifically, examples include resins having carboxyl groups and / or phenolic hydroxyl groups, with resins having carboxyl groups being preferred. As an alkali-soluble resin, it can be appropriately selected from resins conventionally known in the art; only one type may be used, or two or more types may be used in combination. By including copolymer β, which is different from copolymer α, in the color-curing resin composition, there is a tendency to easily improve the solubility and solvent resistance of the developer solution, and to achieve excellent shape and developability of the cured film.

[0137] In one embodiment of the present invention, the preferred alkali-soluble resin as copolymer β includes, for example, the following resins [β1] to [β6].

[0138] Resin [β1]: A copolymer having (A) and (C);

[0139] Resin [β2]: A copolymer having (A), (C) and a monomer (B') capable of copolymerizing with (A) [However, it is different from (A) and (C).] (Hereinafter sometimes referred to as "(B')");

[0140] Resin [β3]: A copolymer having structural units (A) and (B') derived from it;

[0141] Resin [β4]: A copolymer having a structural unit obtained by adding (C) to (A) and (B');

[0142] Resin [β5]: A copolymer having a structural unit obtained by adding (A) to (C) and (B');

[0143] Resin [β6]: A copolymer having a structural unit (B') obtained by adding (A) to (C), further adding to a polycarboxylic acid and / or a carboxylic anhydride.

[0144] Here, (A) and (C) are as described with respect to the copolymer α above. (B') is a monomer capable of copolymerizing with (A) [however, it is different from (A) and (C)], and is also different from the structural unit B of the monomer represented by formula (1) described with respect to the copolymer α above. As (B'), for example, the following can be cited:

[0145] 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(meth)acrylate [5.2.1.0] 2,6 ] Decane-8-yl ester (commonly known in this technical field as "(meth)acrylate dicyclopentyl ester". Additionally, it is sometimes referred to as "(meth)acrylate tricyclodecyl ester"), (meth)acrylate tricyclo[5.2.1.0] 2,6 Decen-8-yl ester (commonly referred to as "(meth)acrylate dicyclopentenyl ester"), (meth)acrylate dicyclopentyloxyethyl ester, (meth)acrylate isobornyl ester, (meth)acrylate adamantane ester, (meth)acrylate allyl ester, (meth)acrylate propargyl ester, (meth)acrylate phenyl ester, (meth)acrylate naphthyl ester, (meth)acrylate benzyl ester, and other (meth)acrylate esters;

[0146] Hydroxyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate;

[0147] Diethyl maleate, diethyl fumarate, diethyl itaconic acid, and other dicarboxylic acid diesters;

[0148] Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 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-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, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]Hept-2-ene, etc., are bicyclic unsaturated compounds;

[0149] Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, and N-(9-acridyl)maleimide;

[0150] Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0151] Among them, (meth)acrylates are preferred.

[0152] In resin [β1], the preferred ratio of structural units from each of the various structural units constituting resin [β1] is:

[0153] Structural unit A: 2-60 mol%

[0154] Structural unit C: 40–98 mol%

[0155] More preferably:

[0156] Structural unit A: 10-50 mol%

[0157] Structural unit C: 50–90 mol%.

[0158] It is believed that if the ratio of the structural units of the resin [β1] is within the above-mentioned range, the desired haze of the color filter can be easily obtained when combined with copolymer α. In addition, the color-curing resin composition tends to have excellent storage stability, developability when forming patterns, and solvent resistance of the obtained cured film.

[0159] The resin [β1] can be manufactured, for example, by referring to the method described in the literature "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Dojin 1st Edition 1st Printing, March 1, 1972) and the references cited in that literature.

[0160] Specifically, the following method can be used: A predetermined amount of (A) and (C), the polymerization initiator, and the solvent are added to a reaction vessel. For example, nitrogen is used to replace oxygen, thereby creating a deoxygenated atmosphere. The mixture is then heated and kept at a constant temperature while stirring. It should be noted that the polymerization initiator and solvent used herein are not particularly limited, and substances commonly used in the art can be used. For example, as polymerization initiators, examples include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile) etc.) and organic peroxides (benzoyl peroxide, tert-butyl peroxide, etc.). As solvents, any solvent that dissolves the monomers is acceptable; examples include organic solvents that may be included in the coloring and curing resin composition of the present invention, as described below.

[0161] It should be noted that, regarding the obtained copolymer, the solution after the reaction can be used directly, or a concentrated or diluted solution can be used, or a substance extracted in solid (powder) form by methods such as reprecipitation can be used. In particular, during this polymerization, by using a solvent, as described below, which may be included in the composition of the color-curing resin composition of the present invention, the solution after the reaction can be directly used in the preparation of the color-curing resin composition of the present invention, thus simplifying the manufacturing process of the color-curing resin composition of the present invention.

[0162] In resin [β2], the preferred ratio of each structural unit among all the structural units constituting resin [β2] is:

[0163] Structural unit A: 2-45 mol%

[0164] Structural unit B': 1–65 mol%

[0165] Structural unit C: 2–97 mol%

[0166] More preferably:

[0167] Structural unit A: 5–40 mol%

[0168] Structural unit B': 5-60 mol%

[0169] Structural unit C: 5–90 mol%.

[0170] It is believed that if the ratio of the structural units of the resin [β2] is within the above-mentioned range, the desired haze of the color filter can be easily obtained when combined with copolymer α. In addition, the color-curing resin composition tends to have excellent storage stability, developability when forming patterns, and solvent resistance, heat resistance and mechanical strength of the obtained cured film.

[0171] Resin [β2] can be manufactured, for example, in the same manner as the method described for manufacturing resin [β1].

[0172] In resin [β3], the preferred ratio of structural units from each of the various structural units constituting resin [β3] is:

[0173] Structural unit A: 2-60 mol%

[0174] Structural unit B': 40–98 mol%

[0175] More preferably:

[0176] Structural unit A: 10-50 mol%

[0177] Structural unit B': 50–90 mol%.

[0178] Resin [β3] can be manufactured, for example, in the same manner as the method described for manufacturing resin [β1].

[0179] The resin [β4] can be manufactured by obtaining a copolymer of (A) and (B'), and then adding the isocyanate compound or cyclic ether having 2 to 4 carbon atoms contained in (C) to the carboxylic acid and / or carboxylic anhydride contained in (A).

[0180] First, the copolymer of (A) and (B') is manufactured in the same manner as described in the method for manufacturing resin [β1]. In this case, the ratio of the structural units from each is preferably the same as the ratio given for resin [β3].

[0181] Next, the isocyanate group or cyclic ether having 2 to 4 carbon atoms in (C) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (A) in the aforementioned copolymer.

[0182] After producing the copolymer of (A) and (B'), the atmosphere inside the flask is replaced with air instead of nitrogen, and (C), a reaction catalyst for carboxylic acid or carboxylic anhydride with cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.) and a polymerization inhibitor (e.g., hydroquinone, p-hydroxyanisole, etc.) are added to the flask, and the reaction is carried out at 60 to 130°C for 1 to 10 hours, thereby producing resin [β4].

[0183] The amount of (C) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (A). It is believed that by setting this range, the desired haze of the color filter can be easily obtained when combined with copolymer α. Furthermore, there is a tendency for the color-curing resin composition to exhibit good storage stability, developability when forming a pattern, pattern shape, low-temperature curability, and a good balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern. Considering the high reactivity of the isocyanate group and the low likelihood of unreacted (C) residue, (C0) is preferred as (C0) in the resin [β4], and more preferably (C0-1). Considering the high reactivity of the cyclic ether and the low likelihood of unreacted (C) residue, (C1) is preferred as (C1) in the resin [β4], and more preferably (C1-1).

[0184] The amount of the aforementioned reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the combined amount of (A), (C), and (B'). The amount of the aforementioned polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the combined amount of (A), (C), and (B').

[0185] The charging method, reaction temperature, and time, among other reaction conditions, can be appropriately adjusted by taking into account the manufacturing equipment and the heat generated by polymerization. It should be noted that the charging method and reaction temperature can be appropriately adjusted by considering the manufacturing equipment and the heat generated by polymerization, similar to the polymerization conditions.

[0186] Regarding resin [β5], as a first stage, a copolymer of (C) and (B') is obtained in the same manner as that used for resin [β1] described above. Similarly, regarding the obtained copolymer, the solution after the reaction can be used directly, or a concentrated or diluted solution can be used, or a substance extracted in solid (powder) form by methods such as reprecipitation can be used.

[0187] The preferred ratios of structural units derived from (C) and (B') are respectively, relative to the total molar number of all structural units constituting the aforementioned copolymer.

[0188] Structural unit B': 5–95 mol%

[0189] Structural unit C: 5–95 mol%

[0190] More preferably:

[0191] Structural unit B': 10–90 mol%

[0192] Structural unit C: 10–90 mol%.

[0193] It is believed that if the ratio of the structural units of the resin [β5] is within the above-mentioned range, the desired haze of the color filter can be easily obtained when combined with copolymer α. In addition, there is a tendency for the color curable resin composition to have good storage stability, developability when forming a pattern, pattern shape, curability at low temperature, and a good balance of solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern.

[0194] Furthermore, under the same conditions as the manufacturing method of resin [β4], the carboxylic acid or carboxylic anhydride contained in (A) is reacted with the isocyanate compound or cyclic ether derived from (C) in the copolymer of (C) and (B'), thereby obtaining resin [β5].

[0195] The amount of (A) used in reaction with the aforementioned copolymer is preferably 5 to 100 moles relative to 100 moles of (C). Considering the high reactivity of the isocyanate group and the low likelihood of unreacted (C) residue, (C0) is preferred as (C0) and more preferably (C0-1) as (C0) is used as (C0) as (C0) as (C0) is preferred, and more preferably (C1-1) as (C1) is used as (C1) ...

[0196] Resin [β6] is a resin obtained by further reacting a polycarboxylic acid and / or a carboxylic anhydride with resin [β5]. A hydroxyl group generated by reacting an isocyanate compound or cyclic ether derived from (C) with a carboxylic acid or carboxylic anhydride derived from (A) is further reacted with a polycarboxylic acid and / or a carboxylic anhydride.

[0197] Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and trimalic acid. Examples of carboxylic 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-dicarboxylic bicyclo[2.2.1]hept-2-ene anhydride. The amount of polycarboxylic acid and / or carboxylic anhydride used is preferably 0.05 to 1 mole, more preferably 0.1 to 0.5 moles, relative to 1 mole of (A).

[0198] In one embodiment of the present invention, from the viewpoint of good developability and curability at low temperature, the copolymer β is preferably a resin having structural units containing olefinic unsaturated bonds in the side chain (resin [β4], resin [β5], or resin [β6]), and more preferably a resin having structural units containing (meth)acryloyl groups in the side chain.

[0199] As resins having structural units containing (meth)acryloyl groups in their side chains, for example, resins using monomers containing (meth)acryloyl groups such as glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 3-methyl-3-methacryloyloxymethyloxetane, and tetrahydrofurfuryl acrylate as (C) are preferred [β4], as are resins using monomers containing (meth)acryloyl groups such as acrylic acid, methacrylic acid, and mono[2-(meth)acryloyloxyethyl] succinate as (A) [β5] and resin [β6].

[0200] Among resins [β4], [β5] and [β6], (meth)acrylates are preferred as (B).

[0201] In another embodiment of the present invention, from the viewpoint of curability at low temperatures, a resin having structural units comprising isocyanate groups or glycidyl groups is particularly preferred as copolymer β. For example, resins using monomers having isocyanate groups such as (meth)acrylate (2-isocyanate ethyl) ester, 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) [β4], and resins using monomers having isocyanate groups such as (meth)acrylate glycidyl ester as (C) [β4] and [β6].

[0202] The coloring and curing resin composition of the present invention may contain one copolymer β, or may contain two or more copolymers β in combination.

[0203] In one embodiment of the present invention, based on the amount of solid components in the color-curing resin composition, the content of copolymer β is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, and even more preferably 30 to 40% by mass. If the resin content is within the above range, there is a tendency to: easily obtain the desired haze of the color filter, easily improve the curability of the color-curing resin composition, easily form a cured film, and improve the resolution of the pattern and the residual film rate.

[0204] In one embodiment of the present invention, the content of copolymer β is preferably 200 to 500 parts by weight relative to 100 parts by weight of copolymer α, more preferably 250 to 450 parts by weight, and even more preferably 300 to 400 parts by weight. When the content of copolymer β is within the above range relative to 100 parts by weight of copolymer α, it tends to: easily obtain the desired haze of the color filter, easily improve the curability of the color curable resin composition, easily form a cured film, and improve the resolution of the pattern and the residual film rate.

[0205] The weight-average molecular weight of the resin included in the coloring and curing resin composition of the present invention, converted to polystyrene, is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, further preferably 5,000 to 30,000, and even more preferably 10,000 to 30,000. If the weight-average molecular weight of the resin is within the aforementioned range, there is a tendency for the cured film of the composition of the present invention to have increased hardness, high residual film rate, good solubility of the unexposed portion in the developer, improved pattern shape, and improved pattern resolution. Furthermore, it is expected that the desired haze of the color filter can be easily obtained.

[0206] The dispersion of the resin [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1 to 6, more preferably 1.2 to 4.

[0207] The acid value of the resin, converted from solid content, 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. Here, the acid value is a value determined as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, and can be obtained, for example, by titration using an aqueous solution of potassium hydroxide.

[0208] (polymeric compounds)

[0209] In this specification, a polymerizable compound is a compound that can be polymerized by active free radicals and / or acids generated by a polymerization initiator. Examples include compounds with polymerizable olefinic unsaturated bonds.

[0210] As the polymerizable compound in the coloring and curing resin composition of the present invention, for example, a compound having two or more olefinic unsaturated bonds can be used, preferably a compound having three or more olefinic unsaturated bonds. Examples of such polymeric compounds include, for example, triglyceride, 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, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. As a polymerizable compound, it can be used with only one type or in combination with two or more types.

[0211] From the viewpoint that the desired haze can be easily obtained when combined with copolymer α, the polymerizable compound is preferably a chain-type aliphatic polymerizable compound. Furthermore, the polymerizable compound preferably has 3 to 6 olefinic unsaturated bonds. If the polymerizable compound has 3 to 6 olefinic unsaturated bonds, the desired haze of the color filter is easily obtained, and high curability and good cured film shape are also easily achieved. Among the above-mentioned polymerizable compounds, triglyceride, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are particularly preferred.

[0212] From the viewpoint of easily obtaining the desired haze when combined with copolymer α, the weight-average molecular weight of the polymeric compound is preferably 150 to 2,900, more preferably 250 to 1,500. Furthermore, if the weight-average molecular weight of the polymeric compound is within the above range, it is easier to obtain a good cured film shape and to easily adjust the curability of the colored curable resin composition to a suitable range. The weight-average molecular weight (Mw) can be determined, for example, by gel permeation chromatography (GPC). More specifically, it can be determined using the method described in the examples below.

[0213] Based on the solid content of the color-curing resin composition, the content of the polymeric compound is preferably 10-50% by mass, more preferably 15-45% by mass, and even more preferably 20-40% by mass. When the content of the polymeric compound is within the above range, the desired haze can be easily obtained in the color filter. Furthermore, when the coating film of the color-curing resin composition is exposed to light to cure, the degree of curing within the coating film is less likely to deviate, and in particular, it can be fully cured to the depth of the coating film, making it easy to obtain a good cured film.

[0214] The content of the polymeric compound relative to 100 parts by weight of resin is preferably 50 to 85 parts by weight, more preferably 55 to 83 parts by weight, even more preferably 60 to 80 parts by weight, and particularly preferably 65 to 75 parts by weight. When the content of the polymeric compound relative to 100 parts by weight of resin is within the above range, a color-curing resin composition capable of forming a color filter with the desired haze can be obtained. When the content of the polymeric compound relative to 100 parts by weight of resin is below the above upper limit, when the coating film of the color-curing resin composition is exposed to light and cured, the degree of curing within the coating film is less likely to deviate, and in particular, it can be fully cured to the depth of the coating film, making it easier to obtain a good cured film shape.

[0215] (Polymerization initiator)

[0216] Polymerization initiators are compounds that can generate active free radicals, acids, etc., under the influence of light and heat, thereby initiating polymerization. There are no particular limitations on polymerization initiators; examples include O-acyl oxime compounds, alkyl phenyl ketone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds. O-acyl oxime compounds are preferred. From the viewpoint of easily further improving the curability of the coloring and curing resin composition, the polymerization initiator preferably has a maximum absorption wavelength in the range of 365–390 nm, and more preferably in the range of 370–390 nm. The coloring and curing resin composition of the present invention may contain one polymerization initiator or two or more polymerization initiators.

[0217] O-acyl oxime compounds are preferred as polymerization initiators. Additionally, compounds with nitro groups are also preferred as polymerization initiators.

[0218] O-acyloxime compounds are compounds having the structure represented by formula (d1).

[0219]

[0220] In the following text, * indicates a connection key.

[0221] Examples of the aforementioned O-acyl oxime compounds include, for instance, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine. Alkyl-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[4-(2-hydroxyethyloxy)phenylthiophenyl]propane-1-one-2-imine, N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, 2-[(acetoxy)imino]-3-cyclohexyl-1-[4-(phenylthiophenyl)phenyl]propane-1-one, etc. Commercially available products such as IRGACURE OXE01, OXE02, OXE03 (manufactured by BASF), N-1919, NCI-730, NCI-831, NCI-930 (manufactured by ADEKA), PBG-314, PBG-317, PBG-326, PBG-327, and PBG-329 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) can also be used. The O-acyl oxime compound is preferably selected from at least one of the following groups: N-acetoxy-1-[4-(2-hydroxyethyloxy)phenylthiophenyl]propane-1-one-2-imine, N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, 2-[(acetoxy)imino]-3-cyclohexyl-1-[4-(phenylthiophenyl)propane-1-one, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine. When these O-acyl oxime compounds are used, there is a tendency to obtain color filters with high brightness.

[0222] Alkyl phenyl ketone compounds are compounds having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have substituents.

[0223]

[0224] Examples of compounds having the structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one. Commercially available products such as IRGACURE 369, 907, and 379 (manufactured by BASF) can be used.

[0225] Examples of compounds having the structure represented by formula (d3) include oligomers of 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzoyladimethyl ketal.

[0226] From a sensitivity perspective, compounds having the structure represented by formula (d2) are preferred as alkyl phenyl ketone compounds.

[0227] 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 Application Publication No. 6-75372, Japanese Patent Application Publication No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, and 2,2'-bis(2-chlorophenyl)biimidazole. Biimidazole compounds obtained by substituting the phenyl group at the 4,4',5,5'-position with an alkoxycarbonyl group (e.g., see Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.) and bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g., see Japanese Patent Application Publication No. 7-10913, etc.). Among these, compounds represented by the following formulas and mixtures thereof are preferred.

[0228]

[0229] 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-piperyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2- [5-Methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0230] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0231] Relative to 100 parts by mass of the total amount of resin and polymerizable compound contained in the coloring and curing resin composition, the content of the polymerization initiator 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. If the content of the polymerization initiator is within the aforementioned range, it is easier to form a well-shaped pattern through exposure and development, and it is also easier to improve curability at low temperatures. Furthermore, there is a tendency to increase sensitivity and shorten exposure time, thus improving the productivity of color filters, etc.

[0232] (Coloring agent)

[0233] The coloring-curing resin composition of the present invention comprises at least one colorant. With regard to the coloring-curing resin composition of the present invention comprising at least one colorant, the composition can be suitably used as a coloring-curing resin composition for making a resist layer in a color filter. Furthermore, the coloring-curing resin composition of the present invention having the above composition can achieve color concentration when used as a colored resist composition, easily achieving the desired color. The colorant can be any of dyes and pigments, preferably including pigments. As pigments, known pigments can be used; for example, pigments classified as pigments in the Dye Index (published by The Society of Dyers and Colourists) can be cited.

[0234] Specifically, examples include:

[0235] 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.

[0236] CI pigments include orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, and other orange pigments;

[0237] CI pigments include 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, etc.

[0238] CI pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments;

[0239] CI pigments include purple 1, 19, 23, 29, 32, 36, 37, 38, and other purple pigments;

[0240] The green pigments in CI pigments 7, 36, 58, 59, 62, 63, 64, 65, 66, and 67;

[0241] CI pigments, such as brown 23 and 25;

[0242] CI pigments include black 1, 7, 31, 32, and other black pigments.

[0243] Pigments can be treated as needed with: rosin treatment; surface treatment using pigment derivatives with introduced acidic or basic groups; grafting treatment to the pigment surface using polymers; micronization treatment using sulfuric acid micronization; cleaning treatment using organic solvents, water, etc. to remove impurities; and removal treatment of ionic impurities using ion exchange, etc.

[0244] The pigment is preferably of uniform particle size. Furthermore, by dispersing it with a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

[0245] Examples of pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants can be used alone 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.), Solsperse (manufactured by Lubrizol Corporation), EFKA (manufactured by CIBA Corporation), AJISPER (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (manufactured by BYK-Chemie Corporation).

[0246] When using a pigment dispersant, the amount used is preferably 1% to 100% by mass relative to the total amount of pigment, more preferably 5% to 50% by mass. If the amount of pigment dispersant used is within the aforementioned range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

[0247] The pigment content in the colorant 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.

[0248] Coloring agents may contain dyes. Known dyes can be used without particular limitation, including solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as hues (excluding pigments) in the Dye Index (published by The Society of Dyers and Colourists) and known dyes listed in dyeing guides (for dyeing companies). Furthermore, based on their chemical structure, examples include azo dyes, cyanide dyes, triphenylmethane dyes, xanthannaphthalene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methyl methacrylate dyes, methyl imine dyes, squaric acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

[0249] Specifically, examples include:

[0250] CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189;

[0251] 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;

[0252] CI Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;

[0253] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

[0254] 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;

[0255] CI solvent green dyes 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.

[0256] 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, 15 7, 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;

[0257] 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, 182 183, 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;

[0258] CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

[0259] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

[0260] Acid Blue (CI) 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, 123 126, 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;

[0261] CI Acid Green 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 acid dyes

[0262] 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;

[0263] 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;

[0264] CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0265] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

[0266] 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, 16 7, 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;

[0267] CI Direct Green includes CI direct dyes such as 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82.

[0268] CI Disperse Yellow 51, 54, 76;

[0269] CI Disperse Violet 26, 27;

[0270] CI disperse blue 1, 14, 56, 60 and other CI disperse dyes,

[0271] CI Basic Red 1, 10;

[0272] 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;

[0273] CI Basic Violet 2;

[0274] CI Basic Red 9;

[0275] CI Basic Green 1 and other CI basic dyes

[0276] CI Active Yellow 2, 76, 116;

[0277] CI Active Orange 16;

[0278] CI reactive dyes such as CI Reactive Red 36

[0279] CI mediator yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0280] CI-mediated redness 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;

[0281] CI-mediated orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

[0282] CI Mordant Purple 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;

[0283] CI Mordant 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;

[0284] CI mordant green dyes 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc.

[0285] CI vat green 1 and other CI vat dyes, etc.

[0286] The dye content in the colorant 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 also be 0% by mass.

[0287] Based on the amount of solid components in the color-curing resin composition, the content of the colorant is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by mass. If the content of the colorant is within the aforementioned range, the color concentration when the filter is made is sufficient, and the composition contains the required amount of color-curing resin, thus enabling the formation of a cured film with sufficient mechanical strength.

[0288] Especially in color-curing resin compositions requiring high color intensity, the colorant content is preferably 15-60% by mass, more preferably 18-55% by mass, and even more preferably 20-50% by mass, based on the amount of solid components in the color-curing resin composition. If the colorant content is within the aforementioned range, a particularly high color concentration can be achieved when manufacturing a color filter, and the composition can contain the required amount of curing resin, thus forming a cured film with sufficient mechanical strength.

[0289] (Polymerization initiator)

[0290] The coloring and curing resin composition of the present invention may further contain at least one polymerization initiator. The polymerization initiator is a compound used to promote the polymerization of a polymerizable compound initiated by a polymerization initiator, or a sensitizer. When a polymerization initiator is included, it is usually used in combination with the polymerization initiator.

[0291] Examples of polymerization initiators include 4,4'-bis(dimethylamino)benzophenone (commonly known as michalcone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, and N-phenylglycine.

[0292] When using these polymerization initiators, the content is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the total amount of resin and polymerizable compound. If the amount of polymerization initiator is within this range, patterns can be formed with higher sensitivity during exposure, tending to increase the productivity of color filters, etc.

[0293] (solvent)

[0294] The coloring and curing 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- and not -O-), ether solvents (solvents containing -O- and not -COO-), ether ester solvents (solvents containing both -COO- and -O-), ketone solvents (solvents containing -CO- and not -COO-), alcohol solvents (solvents containing OH and not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

[0295] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0296] 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, phenethyl ether, and methyl anisole.

[0297] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

[0298] 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.

[0299] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

[0300] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0301] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0302] As a solvent, it is preferred to include one or more solvents selected from the group consisting of ether solvents, ether ester solvents and ketone solvents, more preferably including ether solvents and ether ester solvents, and even more preferably including propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

[0303] The solvent content is preferably 70-95% by mass, more preferably 75-92% by mass, relative to the total amount of the color-curing resin composition of the present invention. In other words, the solid component of the color-curing resin composition is preferably 5-30% by mass, more preferably 8-25% by mass. If the solvent content is within the aforementioned range, there is a tendency for the flatness during coating to be good, and for example, the color concentration will not be insufficient when forming a color filter, thus resulting in good display properties.

[0304] (Leveling agent)

[0305] The coloring and curing resin composition of the present invention may further contain at least one leveling agent. Examples of leveling agents include silicone surfactants, fluorinated surfactants, and silicone surfactants having fluorine atoms. They may have polymerizable groups on their side chains.

[0306] Examples of organosilicon surfactants include surfactants that have intramolecular siloxane bonds. Specifically, examples include TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (trade name, manufactured by Toray D. 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 Advanced Materials Japan Contract Co., Ltd.).

[0307] As examples of the aforementioned fluorinated surfactants, surfactants with intramolecular fluorocarbon chains can be cited. Specifically, examples include FLOURAD (registered trademark) FC430, FLOURAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F183, MEGAFACE F554, MEGAFACE R30, MEGAFACE RS-718-K (manufactured by DIC Co., Ltd.), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Materials Electronics & Chemicals Co., Ltd.), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, and SURFLON... SC105 (manufactured by AGC Corporation (formerly Asahi Glass Corporation)) and E5844 (manufactured by Daikin Fine Chemicals Research Institute Co., Ltd.), etc.

[0308] As examples of organosilicon surfactants containing fluorine atoms, surfactants with siloxane bonds and fluorocarbon chains within the molecule can be cited. Specifically, examples include MEGAFACE (registered trademark) R08, MEGAFACE BL20, MEGAFACE F475, MEGAFACE F477, and MEGAFACE F443 (manufactured by DIC Co., Ltd.).

[0309] When a leveling agent is included, the leveling agent content is preferably 0.005 to 0.5% by mass, more preferably 0.01 to 0.2% by mass, relative to the total amount of the color-curing resin composition. It should be noted that this content does not include the aforementioned pigment dispersant content. If the leveling agent content is within the aforementioned range, the cured film of the color-curing resin composition of the present invention, used as a color filter or the like, can have good flatness.

[0310] (Other ingredients)

[0311] The coloring and curing resin composition of the present invention may contain other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and other additives known in the art as needed.

[0312] <Method for manufacturing coloring and curing resin compositions>

[0313] The coloring and curing 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, and, as needed, a polymerization initiation aid, a leveling agent and other components.

[0314] The colorant can also be prepared using the pigment dispersion described above. The remaining components can be mixed into the pigment dispersion to achieve a predetermined concentration, thereby preparing the target curable resin composition. Furthermore, the mixed curable resin composition is preferably filtered using a filter with a pore size of 0.01 to 10 μm.

[0315] According to the color-curing resin composition of the present invention, a color filter with haze can be formed even without the addition of inorganic particles. Therefore, for the color-curing resin composition, there is no need for a stirring process to uniformly disperse the inorganic particles in the composition, thus improving productivity and providing excellent storage stability. Based on the solid content of the color-curing resin composition, the content of inorganic particles in the color-curing resin composition of the present invention is, for example, 2% by mass or less, preferably 1.5% by mass or less, more preferably 1% by mass or less. In one embodiment of the present invention, the color-curing resin composition of the present invention substantially does not contain inorganic particles. It should be noted that, in this specification, "substantially" means that, based on the solid content of the color-curing resin composition, the content of inorganic particles is 0.1% by mass or less. Similarly, the color-curing resin composition of the present invention also substantially does not contain organic particles.

[0316] <Method for Manufacturing Color Filters>

[0317] Methods for manufacturing cured films containing colored patterns, etc., from the color-curable resin composition of the present invention include photolithography, inkjet printing, and printing. Photolithography is preferred. The photolithography method involves coating the aforementioned color-curable resin composition onto a substrate, drying it to form a color composition layer, exposing the color composition layer through a photomask, and developing it. In the photolithography method, by not using a photomask during exposure and / or not developing, a colored coating film, which is the cured film of the aforementioned color-curable resin composition layer, can be formed. Cured films such as colored patterns and colored coatings formed in this manner can be used as color filters.

[0318] As substrates, the following can be used: glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass with a silica coating; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and substrates on which aluminum, silver, or silver / copper / palladium alloy thin films are formed. Other color filter layers, resin layers, transistors, circuits, etc., can also be formed on these substrates.

[0319] The formation of pixels of various colors using photolithography can be carried out using known or conventional apparatus and conditions. For example, it can be fabricated in the following manner.

[0320] First, the coloring resin composition is coated onto a substrate, and then removed by heating and drying (pre-baking) and / or vacuum drying to remove volatile components such as solvents and dry the substrate, resulting in a smooth coloring composition layer.

[0321] Examples of coating methods include spin coating, slot coating, and a combination of slot and spin coating.

[0322] The preferred temperature for heating and drying is 30–120°C, more preferably 50–110°C. The preferred heating time is 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

[0323] When performing vacuum drying, it is preferable to carry out the process at a pressure of 50–150 Pa and a temperature range of 20–25 °C.

[0324] There is no particular limitation on the film thickness of the coloring composition layer; it can be appropriately selected according to the film thickness of the target color filter.

[0325] In the case of pattern formation, the coloring composition layer is exposed and developed through a photomask used to form the target coloring pattern, thereby forming the pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application can be used.

[0326] The light source used for exposure is preferably a light source that generates light with wavelengths of 250–450 nm. For example, a filter that cuts off wavelengths less than 350 nm can be used to cut off this wavelength region; or a bandpass filter that extracts wavelengths around 436 nm, 408 nm, and 365 nm can be used to selectively extract light. 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 preferably 50–300 J / cm². 2 More preferably 60–200 J / cm 2 Further preferred is 65–180 J / cm 2 .

[0327] In order to uniformly irradiate the entire exposure surface with parallel light, or to accurately align the photomask with the substrate on which the colored composition layer is formed, it is preferable to use exposure devices such as a mask aligner and a stepper.

[0328] A colored pattern is formed on a substrate by contacting the exposed coloring composition layer with a developing solution. During development, the unexposed portions of the coloring composition layer dissolve in the developing solution and are removed. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developing solution may also contain a surfactant.

[0329] The development method can be any of the following: spin-dip, immersion, or spray. Furthermore, the substrate can be tilted at any angle during development.

[0330] After development, it is preferable to wash with water.

[0331] Furthermore, it is preferable to perform a post-baking process on the obtained colored pattern. Regarding the post-baking temperature, in order to form a color filter used in an organic EL display device, it can be below 200°C, preferably below 170°C, and more preferably below 150°C. In this invention, it is preferable to perform the post-baking at a lower temperature, for example, below 130°C. The lower limit of the post-baking temperature is preferably above 70°C, more preferably above 75°C. The post-baking time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes.

[0332] <Color Filter>

[0333] The present invention also provides a color filter as a cured film of the color-curing resin composition of the present invention. As described above, the color filter of the present invention can be a cured film obtained by forming a pattern on the color-curing resin composition of the present invention.

[0334] The thickness of the cured film is not particularly limited and can be appropriately adjusted according to the purpose and application. For example, it is 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.

[0335] Regarding the color filter used as the cured film of the color-curing resin composition of the present invention, when the thickness is converted to 2.5 μm, it preferably has a haze value of 1 to 50%, more preferably 3 to 45%, further preferably 5 to 40%, and even more preferably 7 to 38%. The haze value of the cured film can be measured using a haze meter. The present invention also provides a cured film of the color-curing resin composition of the present invention.

[0336] Furthermore, according to the present invention, a display device incorporating the color filter can also be provided. The display device of the present invention, incorporating the color filter as at least one component, is useful as a display device with fewer display defects. Moreover, the color-curing resin composition according to the present invention can form a color filter with haze, and is therefore particularly suitable as a color filter for organic EL display devices.

[0337] Example

[0338] The present invention is illustrated below with examples and comparative examples to further illustrate the invention, but the invention is not limited to these examples. In the examples, unless otherwise specified, the percentages and parts of content or usage are based on mass.

[0339] <Weight-average molecular weight>

[0340] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined using the GPC method under the following conditions.

[0341]

[0342] F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0343] <Synthetic Example 1: Preparation of Pigment Dispersion 1>

[0344]

[0345] The above components are mixed and the pigment is fully dispersed using a bead mill to obtain pigment dispersion 1.

[0346] <Synthesis Example 2: Preparation of Pigment Dispersion 2>

[0347]

[0348] The above components are mixed and the pigment is fully dispersed using a bead mill to obtain pigment dispersion 2.

[0349] <Synthesis Example 3: Preparation of Pigment Dispersion 3>

[0350]

[0351] The above components are mixed and the pigment is fully dispersed using a bead mill to obtain pigment dispersion 3.

[0352] <Synthesis Example 4: Preparation of Resin (Resin 1)>

[0353] Add 349 parts of propylene glycol monomethyl ether acetate to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While performing nitrogen replacement, stir and heat to 120°C.

[0354] Next, the product obtained by adding 23.4 parts of tert-butyl 2-ethylhexanoate to a monomer mixture comprising 169.2 parts of benzyl methacrylate, 103.3 parts of methacrylic acid, and 52.9 parts of dicyclopentyl methacrylate was added dropwise from a dropping funnel to the aforementioned flask over 2 hours. After the addition was complete, the mixture was stirred for an additional 30 minutes to carry out the copolymerization reaction.

[0355] Then, the flask was purged with air, and 51.2 parts of glycidyl methacrylate, 1.1 parts of triphenylphosphine, and 1.1 parts of p-hydroxyanisole were added. The reaction was carried out at 120°C for 10 hours to obtain the polymer. Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to achieve a polymer solids concentration of 40%, resulting in a resin solution (resin 1) with a weight average molecular weight of 10300. The acid value of resin (resin 1) based on solids was 20.9 mg KOH / g.

[0356] <Synthesis Example 5: Preparation of Resin (Resin 2)>

[0357] Add 439 parts of propylene glycol monomethyl ether to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While performing nitrogen replacement, stir and heat to 90°C.

[0358] Next, 53.1 parts of 2,2'-azobis(2-methylpropionic acid) dimethyl ester were added to a monomer mixture comprising 140 parts of 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, 77 parts of 2-[(diethyl malate)carbonylamino]ethyl ester, 57 parts of 2-ethylhexyl acrylate, 30 parts of 2-hydroxyethyl methacrylate, 27 parts of methacrylate, 100 parts of propylene glycol monomethyl ether, and 153 parts of propylene glycol monomethyl ether acetate. This product was then added dropwise from a dropping funnel to the aforementioned flask over 1 hour. After the addition was complete, the mixture was stirred for another 2 hours to carry out the copolymerization reaction, yielding the polymer.

[0359] Then, 0.8 parts of hydroxy monomethyl ether as a polymerization inhibitor and 10.0 parts of 1,8-diazabicyclo[5.4.0]-undec-7-ene as a basic catalyst were added to a solution containing the resin precursor and solvent in a flask under a nitrogen atmosphere at atmospheric pressure to obtain a resin precursor composition. While stirring the resin precursor composition in a flask under a nitrogen atmosphere at atmospheric pressure, the temperature was maintained at 98°C for 30 minutes. Propylene glycol monomethyl ether acetate, as a solvent, was added to the resulting reaction solution containing the copolymer and solvent in a manner where the components other than the solvent constituted 35% by mass, to obtain a resin (resin 2) solution with a weight-average molecular weight of 6800. The acid value of resin (resin 2) based on the solid component was 50.2 mg KOH / g.

[0360] <Synthesis Example 6: Preparation of Resin (Resin 3)>

[0361] Add 261g of propylene glycol monomethyl ether to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While performing nitrogen replacement, stir and heat to 90°C.

[0362] Next, 41.6 parts of 2,2'-azobis(2-methylpropionic acid) dimethyl ester were added to a monomer mixture comprising 100 parts of 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, 175 parts of 2-ethylhexyl acrylate, 34 parts of 2-hydroxyethyl methacrylate, 17 parts of methacrylate, 18 parts of allyl methacrylate, 124 parts of propylene glycol monomethyl ether, and 158 parts of propylene glycol monoethyl ether acetate. This product was then added dropwise from a dropping funnel to the aforementioned flask over 1 hour. After the addition was complete, the mixture was stirred for another 2 hours to carry out the copolymerization reaction, yielding the polymer.

[0363] Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to achieve a polymer solids concentration of 35%, yielding a resin solution (resin 3) with a weight-average molecular weight of 16,000. The acid value of resin (resin 3) based on solids content was 29.5 mg KOH / g.

[0364] <Synthesis Example 7: Preparation of Resin (Resin 4)>

[0365] Add 386 parts of propylene glycol monomethyl ether to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While performing nitrogen replacement, stir and heat to 90°C.

[0366] Next, 61.5 parts of 2,2'-azobis(2-methylpropionic acid) dimethyl ester were added to a monomer mixture comprising 147 parts of 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, 285 parts of 2-ethylhexyl acrylate, 50 parts of 2-hydroxyethyl methacrylate, 26 parts of methacrylate, 183 parts of propylene glycol monomethyl ether, and 234 parts of propylene glycol monoethyl ether acetate. This product was then added dropwise from a dropping funnel to the aforementioned flask over 1 hour. After the addition was complete, the mixture was stirred for another 2 hours to carry out the copolymerization reaction, yielding the polymer.

[0367] Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to achieve a polymer solids concentration of 35%, yielding a resin solution (resin 4) with a weight-average molecular weight of 9000. The acid value of resin (resin 4) based on solids content was 32.7 mg KOH / g.

[0368] <Synthesis Example 8: Preparation of Resin (Resin 5)>

[0369] Add 1176 parts of propylene glycol monomethyl ether to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. While performing nitrogen replacement, stir and heat to 90°C.

[0370] Next, 93.1 parts of 2,2'-azobis(2-methylpropionic acid) dimethyl ester were added to a monomer mixture comprising 491 parts of 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, 950 parts of 2-ethylhexyl acrylate, 165 parts of 2-hydroxyethyl methacrylate, 86 parts of methacrylate, 609 parts of propylene glycol monomethyl ether, and 778 parts of propylene glycol monoethyl ether acetate. This product was then added dropwise from a dropping funnel to the aforementioned flask over 1 hour. After the addition was complete, the mixture was stirred for another 2 hours to carry out the copolymerization reaction, yielding the polymer.

[0371] Finally, propylene glycol monomethyl ether acetate was added to the reaction solution to achieve a polymer solids concentration of 35%, yielding a resin solution (resin 5) with a weight-average molecular weight of 16300. The acid value of resin (resin 5) based on solids content was 37.4 mg KOH / g.

[0372] <Synthesis Example 9: Preparation of Resin (Resin 6)>

[0373] Add 124.3 parts of propylene glycol monomethyl ether acetate as a solvent to a flask equipped with a stirring device, dropping funnel, condenser, thermometer and gas inlet tube, and stir while performing nitrogen replacement, and heat to 100°C.

[0374] Next, the product obtained by adding 11.5 parts of 2,2'-azobis(isobutyronitrile) to a monomer mixture containing 158.5 parts of 2-ethylhexyl acrylate, 32.7 parts of acrylic acid, and 179.7 parts of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel to the aforementioned flask over 1 hour.

[0375] After the addition was completed, the solution in the flask was stirred while the polymerization reaction was carried out at 100°C for 2 hours to obtain a liquid containing copolymer precursor and solvent.

[0376] 0.69 parts of hydroquinone monomethyl ether as a polymerization inhibitor, 0.69 parts of triphenylphosphine as a catalyst, and 37.4 parts of glycidyl methacrylate were added to a liquid containing copolymer precursor and solvent in a flask containing an atmosphere of 6% oxygen at atmospheric pressure. The mixture was stirred and kept at 120°C for 720 minutes.

[0377] Propylene glycol monomethyl ether acetate, used as a solvent, was added to the reaction solution containing the copolymer and solvent obtained in this manner, with the components other than the solvent accounting for 35% by mass, to obtain a resin (resin 6) solution with a weight average molecular weight of 14300. The acid value of resin (resin 6) based on solid components is 60.8 mg KOH / g.

[0378] <Examples 1-7 and Reference Example 1>

[0379] (1) Preparation of coloring and curing resin composition

[0380] The components listed in Table 1 are mixed in the amounts specified in Table 1 to obtain a color-curing resin composition. It should be noted that propylene glycol monomethyl ether acetate is mixed such that the solid component of the color-curing resin composition is 18% by weight when preparing the color-curing resin composition. The units for the amounts of each component in Table 1 are "parts by mass". The amounts of colorant and dispersant, resins (resin 1) to (resin 6), polymerizable compounds, polymerization initiators, and leveling agents in the pigment dispersion are converted according to the solid component.

[0381] Polymerizable compounds, polymerization initiators, and leveling agents are described below.

[0382] Polymerizable compound: Glyceryl triacrylate (Aronix (registered trademark) M-930; manufactured by Toa Synthetic Co., Ltd.)

[0383] Polymerization initiator: ADEKA ARKLS (registered trademark) NCI-831E (manufactured by ADEKA Co., Ltd.)

[0384] Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.).

[0385] [Table 1]

[0386]

[0387] (2) Evaluation of fog

[0388] Using spin coating, a colored and curable resin composition was coated onto a 5cm square glass substrate (Eagle 2000; Corning Corporation) to a thickness of 2.5μm after baking. It was then pre-baked at 85°C for 2 minutes to form the colored composition layer. After cooling, an exposure machine (TME-150RSK; TOPCON Corporation) was used to expose the substrate at 100mJ / cm² under atmospheric conditions. 2 The coloring composition layer formed on the substrate was irradiated with light at an exposure level (based on 365 nm). After irradiation, it was baked in an oven at 85°C for 30 minutes to obtain the colored coating film.

[0389] The haze of the obtained colored coating was measured using a haze meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.).

[0390] [Table 2]

[0391] Haze Reference Example 1 0.3％ Example 1 8％ Example 2 10％ Example 3 16％ Example 4 4％ Example 5 7％ Example 6 15％ Example 7 17％

[0392] As shown in Table 2, Reference Example 1 exhibits low haze and insufficient scattering performance. In contrast, the colored coatings obtained in Examples 1-7 exhibit high haze and good scattering performance.

[0393] Similar to Examples 1-7, pigment dispersion 2 or pigment dispersion 3 was used instead of pigment dispersion 1 to prepare a coloring curable resin composition in the manner described in Table 3, thereby obtaining a colored coating film.

[0394] [Table 3]

[0395]

[0396] Similar to Examples 1-7, the haze of each colored coating obtained from the coloring curable resin compositions described in Table 3 was measured using a haze meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.).

[0397] [Table 4]

[0398]

[0399] As shown in Table 4, the colored coatings obtained in Examples 8 to 10 have high haze and exhibit good scattering properties.

Claims

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, the resin comprising a copolymer α having: a structural unit A derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride; and a structural unit B derived from a monomer represented by formula (1), in the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a linear or branched alkyl group having 6 to 20 carbon atoms, the content ratio of the structural unit B in the copolymer α is 50 to 90 mol% relative to the total amount of the structural units constituting the copolymer α.

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 the copolymer α further comprises a structural unit C derived from an isocyanate compound containing an ethylenic unsaturated group or a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond.

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

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

6. The colored curable resin composition according to claim 1, wherein the content of the polymerizable compound is 50 to 85 mass parts relative to 100 mass parts 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, which has a haze value of 1 to 50% when converted to a thickness of 2.5 μm.

9. A display device comprising the color filter according to claim 7.

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