Color-curable resin composition, cured film of color-curable resin composition, and display device

Abstract

This invention provides a color-curable resin composition that provides a color filter and has sufficient curability, wherein the color filter provides an organic EL display device that can provide a sufficiently good field of view even when viewed from an oblique angle. A color-curable resin composition comprises a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic microparticles. In the color-curable resin composition, when the scattering intensity in Mie scattering of the inorganic microparticles is set as X, and the content of the inorganic microparticles relative to the solid component of the color-curable resin composition is set as Y (mass%), X is 4 or more, Y is 15 or less, and the value a calculated by equation (1): a = X × Y (1) is 10 or more.

Description

Technical Field

[0001] This invention relates to a color-curable resin composition, a cured film of the color-curable resin composition, and a display device. Prior Technology

[0002] Organic electroluminescence (EL) display devices include, for example, organic EL films formed on a substrate. The organic EL film includes: a hole transport layer, a light-emitting layer for forming individual pixels, emitting light in colors such as red (R), green (G), and blue (B), and an electron transport layer. The device utilizes the following mechanism: by applying a voltage to the electrodes at both ends of the organic EL film, electrons flow from the cathode into the organic EL film, and holes flow from the anode into the organic EL film. Electrons and holes recombine with light-emitting molecules in the light-emitting layer, causing the light-emitting molecules to emit light. To increase the intensity of the emitted light of each color, a macrocavity structure is used, designed so that the optical path length between the upper and lower electrodes matches the wavelength of each color of light. By using a microcavity structure, the resonant effect of light between the electrodes can be utilized to make the spectrum of the light extracted to the outside steeper and higher intensity, improving the brightness and color purity of each color in the RGB spectrum. [Existing Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2007-33963 Summary of the Invention

[0004] [The problem that the invention aims to solve] Especially in organic EL display devices with organic EL films having microcavity structures, as described above, the spectrum of light extracted to the outside becomes steep and becomes high-intensity, thus enabling good color intensity or color rendering. However, when viewing the display device from an oblique angle, a sufficient field of view is sometimes not obtained. In addition, as in Patent Document 1, in order to achieve a sufficient field of view, it has been studied to manufacture color filters using resin compositions containing organic microparticles. However, if organic microparticles are added, sufficient curing properties are sometimes not obtained when manufacturing color filters from resin compositions, or it is sometimes difficult to form patterns with the required resolution.

[0005] Therefore, the object of the present invention is to provide a color curable resin composition that provides a color filter and has sufficient curability, wherein the color filter provides an organic EL display device that can provide a sufficiently good field of view even when viewed from an oblique angle. [Methods for solving problems]

[0006] The inventors have discovered that the aforementioned objective can be achieved by the curable resin composition of the present invention, as described below. That is, the present invention comprises the following components. [1] A coloring-curing resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic microparticles, wherein, in the coloring-curing resin composition, when the scattering intensity in the Mie scattering of the inorganic microparticles is set as X, and the content of the inorganic microparticles relative to the solid content of the coloring-curing resin composition is set as Y (mass%), X is 4 or more, Y is 15 or less, and according to formula (1): a = X × Y (1) The calculated value 'a' is 10 or higher. [2] The coloring curable resin composition as described in [1], wherein the inorganic microparticles are metal oxides. [3] A coloring curable resin composition as described in [1] or [2], wherein the inorganic microparticles have a refractive index of 1.3 or higher. [4] A coloring curable resin composition as described in any one of [1] to [3], wherein the inorganic microparticles have an average particle size of 0.05 μm to 0.70 μm. [5] The coloring curing resin composition as described in any one of [1] to [4], wherein the content of the polymeric compound is 0% to 50% by mass relative to the solid content of the coloring curing resin composition. [6] The coloring curable resin composition as described in any one of [1] to [5], wherein the haze value of the cured film of the curable resin composition is 8% to 40% when converted to a thickness of 2 μm. [7] A curing film, which is a curing film of a colored curing resin composition as described in any one of [1] to [6]. [8] The hardened film as described in [7], wherein it has a haze value of 8% to 40% when converted to a thickness of 2 μm. [9] The hardened film as described in [7] or [8] constitutes the color filter contained in the color filter substrate.

[10] A display device comprising a hardened film as described in any one of [7] to [9]. [The effects of the invention]

[0007] The present invention provides a color curable resin composition that can provide a color filter and has sufficient curability, wherein the color filter can provide an organic EL display device with a sufficiently good field of view even when viewed from an oblique angle. Implementation

[0008] The embodiments of the present invention will now be described in detail. Furthermore, 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. Additionally, when multiple upper and lower limits are specified for a particular parameter, any combination of these upper and lower limits can be used to define a preferred numerical range.

[0009] <Coloring and curing resin composition> The color-curing resin composition of the present invention is as follows: it comprises a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic microparticles, wherein when the scattering intensity in Mie scattering of the inorganic microparticles is set as X, and the content of the inorganic microparticles relative to the solid content of the color-curing resin composition is set as Y (mass%), X is 4 or more, Y is 15 or less, and according to formula (1): a = X × Y (1) The calculated value 'a' is 10 or higher. Furthermore, the color-curing resin composition of the present invention will also be referred to below as the composition of the present invention.

[0010] (Inorganic microparticles) The color-curing resin composition of the present invention contains at least one inorganic microparticle. In this specification, the inorganic microparticle is generally an inorganic particle with an average particle size of 10 μm or less. The average particle size of the inorganic microparticle is not particularly limited to 10 μm or less; it can be a micrometer-scale average particle size or a nanometer-scale average particle size. The average particle size of the inorganic microparticle is preferably 1 μm or less, more preferably 0.70 μm or less. The composition of the present invention may contain one inorganic microparticle or two or more inorganic microparticles. Here, when the scattering intensity in the Mie scattering of the inorganic microparticle is set as X, and the content of the inorganic microparticle relative to the solid component of the color-curing resin composition is set as Y (mass%), X is 4 or more, Y is 15 or less, and according to formula (1): a = X × Y (1) The calculated value 'a' is 10 or higher.

[0011] The scattering intensity X in Mie scattering by inorganic microparticles is a value calculated using unpolarized light, a light source wavelength of 550 nm, and a scattering angle of 0 degrees. For example, it can be calculated using Mieplot (see http: / / www.philiplaven.com / mieplot.htm), a program for calculating scattering intensity in Mie scattering. A higher scattering intensity X indicates a higher light scattering effect. When the scattering intensity X is less than 4, the light scattering effect from the inorganic microparticles becomes insufficient, making it difficult to adequately ensure the field of view when viewing an organic EL display device from an oblique angle. From the viewpoint of ensuring visibility when viewing an organic EL display device from an oblique angle, the scattering intensity of the inorganic microparticles contained in the composition of the present invention is 4 or higher. From the viewpoint of easily improving the visibility of the organic EL display device, a value of scattering intensity X of 4 or higher is preferred, 5 or higher, more preferably 6 or higher, and even more preferably 7 or higher. Furthermore, when the value of X is large, the visibility when viewing an organic EL display device from an oblique angle and the hardening properties when forming a color filter from the composition of the present invention are also easily improved. There is no particular upper limit to the scattering intensity X, but from the point of view of interface reflection control, it is preferably below 10,000, more preferably below 1,000, even more preferably below 300, and even more preferably below 100.

[0012] The content of the inorganic microparticles relative to the solid content of the color-curing resin composition (Y mass%) is 15% or less. When the content of inorganic microparticles exceeds 15% by mass, it is difficult to improve the curability when forming a color filter from the color-curing resin composition, and the color intensity in the obtained color filter is also prone to decrease. From the viewpoint of curability during color filter formation and color rendering properties of the color filter, the content of the inorganic microparticles relative to the solid content of the color-curing resin composition (Y mass%) is preferably 15% or less, more preferably 10% or less, more preferably 8% or less, and more preferably 6% or less.

[0013] Based on the scattering intensity (X) of inorganic microparticles in Mie scattering and the content (Y mass%) of inorganic microparticles relative to the solid component of the color-curing resin composition, from equation (1): a = X × Y (1) The calculated value 'a' is 10 or higher. When the value 'a' is less than 10, the light scattering effect from inorganic microparticles is insufficient, making it difficult to provide a sufficient field of view when viewing the organic EL display device from an oblique angle. From the viewpoint of easily improving visibility when viewing the organic EL display device from an oblique angle, the value 'a' is preferably 15 or higher, more preferably 20 or higher, and even more preferably 25 or higher. Furthermore, from the viewpoint of interface reflection control, it is preferably 800 or lower, more preferably 600 or lower, even more preferably 450 or lower, and even more preferably 350 or lower.

[0014] Inorganic microparticles can be categorized as such as metals, metal oxides, ceramics, and composite materials. From the viewpoint of scattering intensity, metal oxides are preferred. The composition of this invention may contain one type of inorganic microparticle or two or more types. The inorganic microparticles may be surface-treated. By performing surface treatment on the inorganic microparticles, their dispersibility in the resin composition is improved, and it is easier to prevent the aggregation of inorganic microparticles. Examples of surface treatments that can be performed on the inorganic microparticles include treatments using silane coupling agents, silylating agents, organotitanate coupling agents, and silicone oils.

[0015] Examples of metal oxides include: silicon dioxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide. Preferred metal oxides are titanium oxide, zinc oxide, and / or silicon dioxide, more preferably titanium oxide and / or silicon dioxide, and even more preferably titanium oxide. When the composition of the present invention includes metal oxides as inorganic microparticles, it may contain one metal oxide, or it may contain two or more metal oxides.

[0016] The refractive index of inorganic microparticles at 550 nm, from the viewpoint of scattering intensity, is preferably 1.3 or higher, more preferably 1.9 or higher, and even more preferably 2.2 or higher, and even more preferably 2.5 or higher. Furthermore, from the viewpoint of interface reflection control, the refractive index of inorganic microparticles is preferably 2.8 or lower. The refractive index can be measured, for example, by elliptic polarization.

[0017] From the viewpoint of scattering intensity, the average particle size of the inorganic microparticles is preferably 0.05 μm or more, more preferably 0.10 μm or more, further preferably 0.13 μm or more, and further preferably 0.15 μm or more. Furthermore, from the viewpoint of particle sedimentation suppression, the average particle size of the inorganic microparticles is preferably 0.70 μm or less, more preferably 0.50 μm or less, further preferably 0.30 μm or less, further preferably 0.25 μm or less, and particularly preferably 0.20 μm or less. The average particle size can be determined, for example, by dynamic light scattering.

[0018] (resin) The resin contained in the composition of the present invention is not particularly limited, but it is preferably an alkali-soluble resin. The composition of the present invention may contain one resin or two or more resins. Examples of resins include the following resins [K1] to [K6].

[0019] Resin [K1]: A copolymer having a structural unit derived from at least one (a) (hereinafter sometimes referred to as "(a)") of the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylene unsaturated bond; Resin [K2]: A copolymer having structural units derived from (a) and structural units derived from (b), and structural units derived from monomer (c) (which is different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); Resin [K3]: A copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]: A copolymer having structural units formed by the addition of structural units derived from (a) to (b) and structural units derived from (c); Resin [K5]: A copolymer having a structural unit formed by adding (a) to a structural unit derived from (b) and a structural unit derived from (c); Resin [K6]: A copolymer having structural units derived from (c) by addition (a) to structural units derived from (b) and further by addition to polycarboxylic acids and / or carboxylic anhydrides.

[0020] As for (a), specifically, for example, the following can be listed: Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, trans-butenedioic acid, citraconic acid, medaconic acid, 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-cyclohexene dicarboxylic acid; 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, and other bicyclic unsaturated compounds containing carboxyl groups; Unsaturated dicarboxylic acid anhydrides such as 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, and 5,6-dicarboxylic bicyclic [2.2.1]hept-2-ene anhydride; Unsaturated mono[(meth)acrylic acid oxyethyl] esters of di- or higher polycarboxylic acids, such as mono[2-(meth)acrylic acid oxyethyl] ester and mono[2-(meth)acrylic acid oxyethyl] ester; α-(hydroxymethyl)acrylates are unsaturated acrylates containing both hydroxyl and carboxyl groups in the same molecule. Of these, acrylic acid and methacrylic acid are preferred in terms of copolymerization reactivity or the solubility of the obtained resin in alkaline aqueous solutions.

[0021] (b) refers to a polymeric compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., selected from at least one of the group consisting of an oxecyclopropane ring, an oxecyclobutane ring, and a tetrahydrofuran ring) and an ethylene-unsaturated bond. Preferably, (b) is a monolithic form of a cyclic ether having 2 to 4 carbon atoms and a (meth)acrylic acid oxy group. Furthermore, in this specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acrylyl" and "(meth)acrylate" have the same meaning.

[0022] Examples of (b) include monomers having an oxecyclopropyl group and an ethylene unsaturated bond (b1) (hereinafter sometimes referred to as "(b1)"), monomers having an oxecyclobutyl group and an ethylene unsaturated bond (b2) (hereinafter sometimes referred to as "(b2)"), and monomers having a tetrahydrofuran group and an ethylene unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)").

[0023] Examples of (b1) include monomers (b1-1) (hereinafter sometimes referred to as "(b1-1)") which have a structure formed by the epoxidation of aliphatic unsaturated hydrocarbons with straight or branched chains, and monomers (b1-2) (hereinafter sometimes referred to as "(b1-2)") which have a structure formed by the epoxidation of alicyclic unsaturated hydrocarbons.

[0024] Examples of (b1-1) 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)benzyl Ethylene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, etc.

[0025] Examples of compounds represented by (b1-2) include: vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel), 3,4-epoxycyclohexyl methyl methacrylate (e.g., Cyclomer A400; manufactured by Daicel), 3,4-epoxycyclohexyl methyl methacrylate (e.g., Cyclomer M100; manufactured by Daicel), 3,4-epoxytricyclo[5.2.1.0 2,6]decyl methacrylate, compounds represented by formula (BI), and compounds represented by formula (BII).

[0026] In formulas (BI) and (BII), Re and Rf represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, wherein the hydrogen atoms in the alkyl group may be substituted with hydroxyl groups; Xe and Xf represent single bonds, *-Rg-, *-RgO-, *-RgS-, or *-Rg-NH-; R g represents an alkyldiyl group with 1 to 6 carbon atoms; * indicates a bond with O]

[0027] Examples of alkyl groups having 1 to 4 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, and tributyl. Examples of alkyl groups formed by replacing hydrogen atoms with 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, 4-hydroxybutyl, etc. As Re and Rf, it is preferable to include hydrogen atoms, methyl groups, hydroxymethyl groups, 1-hydroxyethyl groups, 2-hydroxyethyl groups, and more preferably hydrogen atoms and methyl groups.

[0028] Examples of alkyldiyl groups include: methylene, ethyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. Xe and Xf are preferably listed as single bonds, methylene, ethyl, *-CH 2-O- and *-CH 2CH 2-O-, and more preferably listed as single bonds and *-CH 2CH 2-O- (* indicates a bond with O).

[0029] As (b2), it is more preferably a monolithic form having an oxetyl group and a (meth)propenyloxy group. Examples of (b2) include: 3-methyl-3-methpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl-3-methpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methpropenyloxyethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methpropenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, etc.

[0030] As (b3), it is more preferably a monolithic form having a tetrahydrofuran group and a (meth)acrylic acid group. Examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Biscoat V#150, manufactured by Osaka Organic Chemicals Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

[0031] Regarding (b), in the case of resin [K1] or resin [K2], (b1) is preferred in terms of further improving the reliability of the obtained color filter, such as its heat resistance and chemical resistance.

[0032] Examples of (c) include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, tributyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 2,6]decane-8-yl ester (commonly referred to as "dicyclopentyl methacrylate" in this art; sometimes also as "tricyclodecyl methacrylate"), tricyclo[5.2.1.0 2,6]decane-8-yl ester (in this field, it is commonly referred to as "dicyclopentyl methacrylate"; in addition, it is sometimes referred to as "tricyclodecyl methacrylate"). [2,6] Decen-8-yl ester (commonly referred to as "(meth)acrylate dicyclopentenyl ester"), (meth)acrylate dicyclopentyloxyethyl ester, (meth)acrylate isobornyl ester, (meth)acrylate adamantyl 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; Hydroxyl acrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; Diethyl maleate, diethyl transbutenedioic acid, diethyl itaconic acid, and other dicarboxylic acid diesters; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-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; N-Phenylacetinibimide, N-Cyclohexylcis-butenetinibimide, N-Benzylcis-butenetinibimide, N-Succinimido-3-cis-butenetinibimide benzoate, N-Succinimido-4-cis-butenetinibimide butyrate, N-Succinimido-6-cis-butenetinibimide hexanoate, N-Succinimido-3-cis-butenetinibimide propionate, N-(9-acridyl)cis-butenetinibimide, and other dicarbonyl acetimine derivatives; 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. Of these, (meth)acrylates are preferred.

[0033] The ratio of structural units derived from each of the components in resin [K1] is preferably the following among all structural units constituting resin [K1]. Structural units derived from (a): 2 mol% ~ 60 mol% Structural units derived from (b): 40 mol% ~ 98 mol% Better Structural units derived from (a): 10 mol% ~ 50 mol% Structural units derived from (b): 50 mol%~90 mol%. If the ratio of the structural units of the resin [K1] is within the range described above, there is a tendency for the color-curing resin composition to exhibit excellent storage stability, developability when forming patterns, and solvent resistance of the obtained cured film.

[0034] The resin [K1] can be manufactured, for example, by referring to the method described in the literature "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Chemical Dojin Publishing Co., 1st edition, 1st printing, published on March 1, 1972) and the references cited in that literature.

[0035] Specifically, examples include placing the specified amounts of (a) and (b), the polymerization initiator, and the solvent into a reaction vessel, for example, using nitrogen to replace oxygen to create a deoxygenated environment, and then heating and maintaining the temperature while stirring. Furthermore, the polymerization initiator and solvent used herein are not particularly limited, and those commonly used in the field can be used. For example, as polymerization initiators, examples include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile) etc.) or organic peroxides (benzoyl peroxide, tributyl peroxide-2-ethylhexanoate, etc.). As solvents, any solvent capable of dissolving the monomers is acceptable; examples include organic solvents included, as appropriate, in the color-curing resin composition of the present invention, and solvents described later.

[0036] Furthermore, the obtained copolymer can be used directly from the reaction solution, or a concentrated or diluted solution can be used, or it can be extracted in solid (powder) form by methods such as reprecipitation. In particular, during the polymerization, by using a solvent as described later in the composition included in the color-curing resin composition of the present invention, the reaction solution can be directly used in the preparation of the color-curing resin composition of the present invention, thus simplifying the manufacturing steps of the color-curing resin composition of the present invention.

[0037] The ratio of structural units derived from each of the components in resin [K2] is preferably the following among all structural units constituting resin [K2]. Structural units derived from (a): 2 mol% ~ 45 mol% Structural units derived from (b): 2 mol% ~ 95 mol% Structural units derived from (c): 1 mol% ~ 65 mol% Better Structural units derived from (a): 5 mol% ~ 40 mol% Structural units derived from (b): 5 mol% ~ 80 mol% Structural units derived from (c): 5 mol%~60 mol%. If the ratio of the structural units of the resin [K2] is within the range described, there is a tendency for the color-curing resin composition to exhibit excellent storage stability, developability when forming patterns, and solvent resistance, heat resistance, and mechanical strength of the obtained cured film.

[0038] Resin [K2] can be manufactured, for example, in the same manner as the method described as the manufacturing method of resin [K1].

[0039] The ratio of structural units derived from each of the components in resin [K3] is preferably the following among all structural units constituting resin [K3]. Structural units derived from (a): 2 mol% ~ 60 mol% Structural units derived from (c): 40 mol%~98 mol% Better Structural units derived from (a): 10 mol% ~ 50 mol% Structural units derived from (c): 50 mol%~90 mol%. Resin [K3] can be manufactured, for example, in the same manner as the method described as the manufacturing method of resin [K1].

[0040] The resin [K4] can be manufactured by obtaining a copolymer of (a) and (c) by adding a cyclic ether having 2 to 4 carbons in (b) to a carboxylic acid and / or carboxylic anhydride in (a). First, the copolymer of (a) and (c) is manufactured in the same manner as the method described for manufacturing resin [K1]. In this case, the ratio of structural units derived from each is preferably the same as the ratio listed for resin [K3].

[0041] Next, the cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer. Following the production of the copolymer of (a) and (c), the environment inside the flask is replaced with air instead of nitrogen. Then, (b), the reaction catalyst of carboxylic acid or carboxylic anhydride with cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.) and polymerization inhibitor (e.g., hydroquinone, p-methoxyphenol, etc.) are placed into the flask and reacted, for example, at 60°C to 130°C for 1 to 10 hours, thereby producing resin [K4]. Compared to (a) 100 mol, the amount of (b) used is preferably 5 mol to 80 mol, more preferably 10 mol to 75 mol. By setting it within this range, there is a tendency for a better balance between the storage stability of the curable resin composition, the developability when forming a pattern, the pattern shape, the curability at low temperatures, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern. In terms of the high reactivity of cyclic ethers and the difficulty in retaining unreacted (b), (b) used as resin [K4] is preferably (b1), and more preferably (b1-1). The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to the total amount of 100 parts by mass of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to the total amount of 100 parts by mass of (a), (b), and (c). The charging method, reaction temperature, and time, among other reaction conditions, can be appropriately adjusted taking into account factors such as the manufacturing equipment or the heat generated during polymerization. Furthermore, similarly to polymerization conditions, the charging method or reaction temperature can be appropriately adjusted taking into account factors such as the manufacturing equipment or the heat generated during polymerization.

[0042] Regarding resin [K5], as a first stage, copolymers of (b) and (c) are obtained in the same manner as resin [K1]. Similarly, the obtained copolymer can be used directly from the reaction solution, or from a concentrated or diluted solution, or extracted in solid (powder) form using methods such as reprecipitation. The ratios of structural units originating from (b) and (c) are preferably respectively, relative to the total number of moles of all structural units constituting the copolymer. Structural units derived from (b): 5 mol% ~ 95 mol% Structural units derived from (c): 5 mol%~95 mol% Better Structural units derived from (b): 10 mol% ~ 90 mol% Structural units derived from (c): 10 mol%~90 mol%. If the ratio of the structural units of the resin [K5] is within the range described, there is a tendency for the preservation stability of the color-curing resin composition, the developability when forming a pattern, the pattern shape, the curing at low temperature, and the balance of solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern to become good.

[0043] Furthermore, under the same conditions as the manufacturing method of resin [K4], the carboxylic acid or carboxylic anhydride contained in (a) and the cyclic ether derived from (b) in the copolymer of (b) and (c) are reacted to obtain resin [K5]. The amount of (a) reacting with the copolymer is preferably 5 to 100 mol relative to (b) 100 mol. In terms of the high reactivity of cyclic ethers and the difficulty in leaving unreacted (b), (b) used as resin [K5] is preferably (b1), and more preferably (b1-1).

[0044] Resin [K6] is a resin obtained by further reacting a polycarboxylic acid and / or a carboxylic anhydride with resin [K5]. The polycarboxylic acid and / or a carboxylic anhydride are further reacted with a hydroxyl group generated by the reaction of a cyclic ether derived from (b) with a carboxylic acid or a carboxylic anhydride derived from (a). Examples of polycarboxylic acids include: oxalic acid, malonic acid, succinic acid, maleic acid, trans-butenedioic acid, glutaric acid, and tricarboxylic 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 bicyclic [2.2.1]hept-2-ene anhydride. The amount of polycarboxylic acid and / or carboxylic anhydride used is preferably 0.05 mol to 1 mol, more preferably 0.1 mol to 0.5 mol, relative to the amount used in (a) of 1 mol.

[0045] The resin contained in the color-curing resin composition of the present invention is preferably a resin containing a structural unit having an ethylene unsaturated bond in the side chain (resin [K4] or resin [K5]), and more preferably a resin containing a structural unit comprising a (meth)acrylic group in the side chain. As a resin containing a structural unit comprising a (meth)acrylic group in the side chain, preferably, for example, a resin having a (meth)acrylic group as a monomer such as glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3-methyl-3-methacryloxymethyloxetane, tetrahydrofurfuryl acrylate as (b) [K4], and a resin having a (meth)acrylic group as a monomer such as acrylic acid, methacrylic acid, succinic acid mono[2-(meth)acryloxyethyl] ester as (a) [K5]. In resins [K4] and [K5], as (c), dicarbonyl amide derivatives and vinyltoluene are preferred.

[0046] The polystyrene-based weight-average molecular weight of the resin contained in the color-curing resin composition of the present invention is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and even more preferably 5,000 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, improved solubility of the unexposed portion in the developer, and improved pattern shape and pattern resolution.

[0047] The resin dispersion [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1~6, more preferably 1.2~4.

[0048] Based on solid content conversion, the acid value of the resin is preferably 10 mg-KOH / g to 170 mg-KOH / g, more preferably 20 mg-KOH / g to 150 mg-KOH / g, and even more preferably 30 mg-KOH / g 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 the resin, and can be obtained, for example, by titration using an aqueous solution of potassium hydroxide.

[0049] The resin content, relative to the total amount of solid components in the color-curing resin composition, is preferably 5% to 80% by mass, more preferably 10% to 70% by mass, even more preferably 15% to 60% by mass, and even more preferably 20% to 50% by mass. If the resin content is within the aforementioned range, there is a tendency to easily improve the curing properties of the color-curing resin composition, facilitate pattern formation, and increase the pattern resolution and residual film rate. Furthermore, the term "total amount of solid components" in this specification refers to the amount obtained by removing the solvent content from the total amount of the color-curing resin composition. The total amount of solid components and the content of each component therein can be determined, for example, by known analytical methods such as liquid chromatography or gas chromatography.

[0050] (polymeric compounds) Polymerizable compounds are compounds that can be polymerized by active free radicals and / or acids generated by self-polymerization initiators, such as compounds with polymerizable vinyl unsaturated bonds, preferably (meth)acrylate compounds.

[0051] Among them, the polymerizable compound is preferably a polymerizable compound having three or more ethylene unsaturated bonds. Examples of such polymerizable compounds include: 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)acryloxyethyl)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. From the viewpoint of pattern shape, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

[0052] From the viewpoints of easily achieving good pattern shape and easily adjusting the curing properties of the color-curing resin composition to an appropriate range, the weight average molecular weight of the polymeric compound is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

[0053] The content of the polymeric compound is preferably 3% by mass or more, more preferably 6% by mass or more, and even more preferably 9% by mass or more, and even more preferably 12% by mass or more, relative to the total amount of solid components contained in the color-curing resin composition. Furthermore, the content of the polymeric compound is preferably 50% by mass or less, more preferably 46% by mass or less, even more preferably 43% by mass or less, and even more preferably 40% by mass or less, relative to the total amount of solid components contained in the color-curing resin composition. When the content of the polymeric compound is at or above the lower limit, the curing properties of the color-curing resin composition are easily improved, and patterns are easily formed. Furthermore, when the content of the polymeric compound is at or below the upper limit, when the coating of the color-curing resin composition is exposed and cured, the degree of curing within the coating is less likely to deviate, and in particular, it can be fully cured to the depth of the coating, making it easier to obtain a good pattern shape.

[0054] When the total mass of the resin (preferably an alkali-soluble resin, more preferably resin [K1] to resin [K6]) and the polymeric compound contained in the color-curing resin composition is set to 100% by mass, the content of the polymeric compound is preferably 50% by mass or less, more preferably 47% by mass or less, further preferably 45% by mass or less, and further preferably 43% by mass or less. When the content of the polymeric compound is below the aforementioned upper limit, when the coating film of the color-curing resin composition is exposed and cured, the degree of curing within the coating film is unlikely to deviate, and in particular, it can be fully cured to the depth of the coating film, making it easy to obtain a good pattern shape.

[0055] (Polymerization initiator) Polymerization initiators are compounds that can initiate polymerization by generating active free radicals, acids, etc., through the action of light or heat. There are no particular limitations on polymerization initiators, but examples include: O-acyloxime compounds, benzyl ketone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds. Among these, O-acyloxime compounds are preferred. From the viewpoint of more easily improving the curability of the color-curing resin composition, the polymerization initiator preferably has a maximum absorption wavelength in the range of 365 nm to 390 nm, and more preferably in the range of 370 nm to 390 nm. The color-curing resin composition of the present invention may contain one polymerization initiator or two or more polymerization initiators.

[0056] O-acetylated compounds are preferred as polymerization initiators. Additionally, compounds with a carbazole skeleton and compounds with a nitro group are also preferred.

[0057] O-acetylgoxime compounds have the formula (c1): The compound whose structure is represented.

[0058] Compounds with a carbazole skeleton have the formula (c2): The compound with the indicated structure. Hereinafter, * denotes a bond.

[0059] The compound having a nitro group (-N 2O) is preferably a compound having at least one nitro group bonded to an aromatic ring, and more preferably a compound having at least one nitro group bonded to an aromatic ring contained in a carbazole skeleton.

[0060] The polymerization initiator is preferably an O-acetylgoxime compound having a carbazole skeleton. Such compounds include, for example, at least one selected from the group consisting of compounds represented by formula (c3) (hereinafter, sometimes referred to as compound (c3)) and compounds represented by formula (c4) (hereinafter, sometimes referred to as compound (c4)). In equations (c3) and (c4), Ra represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, or an aliphatic hydrocarbon group with 1 to 15 carbon atoms that may have substituents. The methylene group (-CH 2-) contained in the aliphatic hydrocarbon group may be substituted with -O-, -CO- or -S-, the methine group (-CH<) contained in the aliphatic hydrocarbon group may be substituted with -PO 3<, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group. Furthermore, in this specification, when methylene (-CH 2-) and the like are substituted to -O-, -CO-, or -S-, the carbon number refers to the carbon number before substitution. Rb represents an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have substituents, a heterocyclic group having 3 to 36 carbon atoms that may have substituents, an alkyl group having 1 to 15 carbon atoms that may have substituents, or a group having substituents formed by combining an aromatic hydrocarbon group with an alkyl diene derived from the alkyl group, wherein the methylene (-CH 2-) contained in the alkyl group may be substituted with -O-, -CO-, -S-, -SO 2-, or -NR h-. Rh represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Rc represents an aromatic hydrocarbon group with 6 to 18 carbon atoms, a heterocyclic group with 3 to 36 carbon atoms, or an alkyl group with 1 to 10 carbon atoms that may have substituents. R d represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, or a heterocyclic group with 3 to 36 carbon atoms that may have substituents. p represents an integer from 1 to 4, preferably an integer of 1 or 2, and even more preferably 1.

[0061] The aromatic hydrocarbon group represented by Ra preferably has 6 to 15 carbon atoms, more preferably 6 to 12, and even more preferably 6 to 10. Examples of such aromatic hydrocarbon groups include phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, and terphenyl, with phenyl and naphthyl being more preferred, and phenyl being even more preferred. Furthermore, the aromatic hydrocarbon group represented by Ra may have one or more substituents. Examples of substituents that are identical to those that the aromatic hydrocarbon group of Ra may have are listed.

[0062] The aliphatic hydrocarbon group represented by Ra preferably has 1 to 13 carbon atoms, more preferably 2 to 10. Examples of aliphatic hydrocarbon groups represented by Ra include: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl; and alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, and pentadecenyl. These aliphatic hydrocarbon groups can be chain-like (straight-chain or branched-chain), cyclic, or a combination of chain and cyclic groups. In addition, in the aliphatic hydrocarbon group of Ra, the methylene (-CH 2-) can be substituted to -O-, -CO- or -S-, the methine (-CH<) can be substituted to -PO 3<, and the hydrogen atoms contained in the aliphatic hydrocarbon group can be substituted with OH groups.

[0063] As represented by Ra, aliphatic hydrocarbon groups that can have substituents can include groups represented by the following formulas. In the formula, * represents a bond.

[0064] Ra is preferably a chain aliphatic hydrocarbon group that may have substituents, more preferably a chain alkyl group that does not have substituents, and even more preferably a straight-chain or branched chain alkyl group that does not have substituents.

[0065] The aromatic hydrocarbon group represented by Rb preferably has 6 to 15 carbon atoms, more preferably 6 to 12, and even more preferably 6 to 10. Examples of such aromatic hydrocarbon groups include phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, and terphenyl, with phenyl and naphthyl being more preferred, and phenyl being particularly preferred. Furthermore, the aromatic hydrocarbon group represented by Rb may also have one or more substituents. The substituents are preferably located at the ortho or para position of the aromatic hydrocarbon group. Examples of such substituents include: alkyl groups with 1 to 15 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl; and halogen atoms such as fluorine, chlorine, iodine, and bromine. The alkyl group serving as the substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 7. The alkyl group serving as the substituent can be any of a straight chain, a branched chain, or a cyclic chain, or it can be a group formed by combining a chain group and a cyclic group. The methylene group (-CH 2-) contained in the alkyl group serving as the substituent can be substituted with -O- or -S-. Furthermore, the hydrogen atom contained in the alkyl group can be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom, preferably with a fluorine atom.

[0066] Alkyl groups that are substituents for the aromatic hydrocarbon group represented by Rb can be, for example, groups represented by the following formulas. In the formula, * represents a bond.

[0067]

[0068]

[0069] Rb represents an aromatic hydrocarbon group that may have substituents, such as those represented by the following formula. In the formula, * represents a bond.

[0070]

[0071]

[0072] The aromatic hydrocarbon group represented by Rb that may have substituents is preferably the group represented by the following formula. [In the formula, Ri independently represents alkyl groups with 1 to 10 carbon atoms that can be substituted by halogen atoms, the methylene (-CH 2-) contained in Ri can be substituted to -O- or -S-, Rj independently represents alkyl groups with 1 to 10 carbon atoms that can be substituted by halogen atoms, q represents an integer from 1 to 5, and r represents an integer from 0 to 4; wherein the sum of q+r is less than 5]

[0073] As the alkyl groups represented by Ri and Rj, examples can be made of the same groups as those exemplified as substituents of aromatic hydrocarbon groups represented by Rb. Ri preferably has 2 to 8 carbon atoms, more preferably 2 to 6. Furthermore, the alkyl group represented by Rj can be any of straight-chain, branched-chain, and cyclic, preferably chain-like. Ri is preferably represented by the group represented by the formula *-Rj1-ORj2. Here, Rj2 represents an alkyl group with 1 to 10 carbon atoms that can be substituted with a halogen atom. As Rj2, it is preferably a straight-chain alkyl group with 1 to 3 carbon atoms. Rj1 represents an alkyl group with 1 to 10 carbon atoms that can be substituted with a halogen atom. As Rj1, it is preferably a straight-chain alkyl group with 1 to 3 carbon atoms. When Ri and Rj contain halogen atoms, fluorine atoms, chlorine atoms, iodine atoms, and bromine atoms can be listed as halogen atoms contained in Ri and Rj, with fluorine atoms being particularly preferred. Furthermore, when Ri and / or Rj contain halogen atoms, the number is preferably two or more and less than ten, more preferably three or more and less than six. The substitution position of the RiO- group is preferably ortho or para. The substitution position of the Rj- group is preferably ortho or para, particularly ortho. In addition, q is preferably 1~2, and more preferably 1. r is preferably 0~2, and especially preferably 0 or 1.

[0074] The heterocyclic group represented by Rb preferably has 3 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 3 to 5. Examples of such heterocyclic groups include pyrrole, furanyl, thiophene, indolyl, benzofuranyl, and carbazole. Furthermore, the heterocyclic group represented by Rb may also have one or more substituents. Examples of such substituents are those identical to those exemplified as substituents that may be present in the aromatic hydrocarbon group represented by Rb.

[0075] The alkyl group represented by Rb preferably has 1 to 12 carbon atoms. Examples of alkyl groups represented by Rb include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. These alkyl groups can be straight-chain, branched-chain, or cyclic, or they can be groups formed by combining chain and cyclic groups. In addition, in the alkyl group represented by Rb, the methylene group (-CH 2-) can be substituted with -O-, -CO-, -S-, -SO 2-, or -NR h-, and the hydrogen atom can be substituted with an OH group or an SH group.

[0076] Rh represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. This alkyl group can be chain-like (straight-chain or branched-chain), cyclic, or any of the straight-chain, branched-chain, and cyclic forms, or it can be a group formed by combining a chain group and a cyclic group. Furthermore, in the alkyl group of Rh, the methylene group (-CH2-) can be substituted with -O- or -CO-.

[0077] As represented by Rb, alkyl groups that may have substituents can specifically include groups represented by the following formulas. * indicates a bond.

[0078]

[0079] Furthermore, the number of carbon atoms in the group formed by combining the aromatic hydrocarbon group represented by Rb with the alkyl diel derived from the alkyl group represented by Rb is preferably 7 to 33, more preferably 7 to 18, and even more preferably 7 to 12. This combined group may have one or more substituents, and examples of such substituents are those identical to those exemplified as substituents that can be present in aromatic hydrocarbon groups and alkyl groups. Examples of the group formed by combining the aromatic hydrocarbon group represented by Rb with the alkyl diel derived from the alkyl group represented by Rb include aralkyl groups, specifically those represented by the following formula. In the formula, * denotes a bond.

[0080]

[0081] Wherein, Rb is preferably an aromatic hydrocarbon group that may have substituents or an alkyl group that may have substituents, and more preferably an aromatic hydrocarbon group that may have substituents.

[0082] The aromatic hydrocarbon group represented by Rc preferably has 6 to 15 carbon atoms, more preferably 6 to 12, and even more preferably 6 to 10. Examples of such aromatic hydrocarbon groups include phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, and terphenyl. The heterocyclic group represented by Rc preferably has 3 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 3 to 5. Examples of such heterocyclic groups include pyrrole, furanyl, thiophene, indolyl, benzofuranyl, and carbazole. The alkyl group represented by Rc preferably has 1 to 7 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group can be linear, branched, or cyclic, or it can be a combination of a linear group and a cyclic group.

[0083] As Rc, it is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, even more preferably a chain alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0084] The aromatic hydrocarbon group represented by Rd ​​preferably has 6 to 15 carbon atoms, more preferably 6 to 12, and even more preferably 6 to 10. Examples of such aromatic hydrocarbon groups include phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, and terphenyl, with phenyl and naphthyl being more preferred. Furthermore, the aromatic hydrocarbon group represented by R d may have one or more substituents. The substituents are preferably substituted at the ortho or para position of the aromatic hydrocarbon group. Preferably, the substituent is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically including: alkyl groups having 1 to 15 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and alkenyl groups having 1 to 15 carbon atoms such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, and decenyl. The aromatic hydrocarbon group represented by R d may preferably have an aliphatic hydrocarbon group with 1 to 7 carbon atoms. This aliphatic hydrocarbon group may be straight-chain, branched-chain, or cyclic, or it may be a group formed by combining a chain group and a cyclic group. In addition, the methylene (-CH 2-) contained in this aliphatic hydrocarbon group may be substituted with -O-, -CO-, or -S-, and the methine (-CH<) may be substituted with -N<.

[0085] As for the aliphatic hydrocarbon groups that can be present in the aromatic hydrocarbon group represented by R d, the following formulas can be used to list the groups represented by them. In the formula, * represents a bond.

[0086]

[0087] As represented by Rd, aromatic hydrocarbon groups that can have substituents can include those represented by the following formulas. In the formula, * represents a bond.

[0088]

[0089] The heterocyclic group represented by Rd ​​preferably has 3 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 3 to 5. Examples of such heterocyclic groups include pyrrole, furanyl, thiophene, indolyl, benzofuranyl, and carbazole. In addition, the heterocyclic group represented by Rd ​​may have one or more substituents, and the same group as the substituent that can be exemplified as the substituent that the aromatic hydrocarbon group represented by Rd ​​may have can be listed.

[0090] Rd is preferably an aromatic hydrocarbon group with substituents, and the substituent is preferably a chain alkyl group having 1 to 7 carbons (more preferably 1 to 3 carbons), and the number of substituents is preferably two or more and five or less.

[0091] Compounds (c3) and (c4) can be manufactured by the manufacturing methods described in Japanese Patent Publication No. 2014-500852 or International Publication No. 2008-078678.

[0092] Compound (c3) is preferably a compound with the following characteristics: Ra is an alkyl group having 1 to 15 carbon atoms that may have substituents, Rb is an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have substituents, Rc is an alkyl group having 1 to 10 carbon atoms, and p is 1 or 2. More preferably, the compound is as follows: Ra is an alkyl group having 1 to 4 carbon atoms that may have substituents, Rb is a group represented by the following formula, Rc is an alkyl group having 1 to 4 carbon atoms, and p is 1. [In the formula, Rj is an alkyl group with 1 to 3 carbon atoms, Ri is a group represented by the formula *-Rj1-ORj2 [here, Rj1 represents a straight-chain or branched aliphatic hydrocarbon group with 1 to 4 carbon atoms that can be substituted by halogen atoms, and Rj2 represents a straight-chain or branched alkyl group with 1 to 4 carbon atoms that can be substituted by halogen atoms], the hydrogen atoms contained in Ri and Rj can be substituted with halogen atoms; q and r are 1] As a commercially available compound (c3), NCI-831 (manufactured by ADEKA) can be cited as an example.

[0093] The compound (c4) is preferably a compound in which Ra is an alkyl group having 1 to 10 carbon atoms that may have substituents, Rb is an aromatic hydrocarbon group having 6 to 10 carbon atoms that may have substituents, Rc is an alkyl group having 1 to 4 carbon atoms, and Rd represents an aromatic hydrocarbon group that may have substituents. Commercially available examples of compounds (C4) include: Irgacure OXE03 (manufactured by BASF).

[0094] Benzyl ketone compounds are compounds having a partial structure represented by formula (d4) or a partial structure represented by formula (d5). In these partial structures, the benzene ring may have substituents.

[0095]

[0096] Examples of compounds having the structure represented by formula (d4) include: 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one, etc. Commercially available products such as Irgacure 369, 907, and 379 (manufactured by BASF) can also be used. Examples of compounds having the structure represented by formula (d5) include: 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, benzodiazepine dimethyl ketal, etc. In terms of sensitivity, as a benzyl ketone compound, it is preferred to be a compound having the structure represented by formula (d4).

[0097] 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 (e.g., see Japanese Patent Publication No. 6-75372, Japanese Patent Publication No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2- Biimidazole compounds containing a 4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g., see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), and biimidazole compounds with a 4,4',5,5'-phenyl group substituted with an alkoxycarbonyl group (e.g., see Japanese Patent Publication No. 7-10913, etc.). Among these, compounds represented by the following formulas and mixtures thereof are preferred.

[0098]

[0099] 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, 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.

[0100] Examples of phosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0101] The content of the polymerization initiator is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 2 to 30 parts by mass, relative to the total amount of solid components contained in the color-curing resin composition. If the content of the polymerization initiator is within the aforementioned range, it is easier to form well-shaped patterns through exposure and development, and it is also easier to improve curing properties at low temperatures. Furthermore, since there is a tendency to shorten exposure time due to increased sensitivity, the productivity of color filters and the like is improved.

[0102] (Coloring agent) The color-curing resin composition of the present invention contains at least one coloring agent. The coloring agent can be any of dyes and pigments, but preferably includes a pigment. As a pigment, known pigments can be used, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0103] Specifically, examples include: 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, etc. CI Pigment Orange includes orange pigments in grades 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73. CI Pigment Red includes red pigments in the following colors: 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, and 291. CI Pigment Blue includes blue pigments in ratios of 15, 15:3, 15:4, 15:6, 16, and 60. CI pigments include purple pigments such as 1, 19, 23, 29, 32, 36, and 38. CI pigment green (7, 36, 58, 59, etc.) CI pigment brown (23, 25, etc.) CI Pigment Black 1, 7, and other black pigments.

[0104] Pigments may also undergo surface treatments such as rosin treatment, surface treatment using pigment derivatives with introduced acidic or basic groups, grafting treatment of pigment surfaces using polymers, micronization treatment using sulfuric acid micronization, cleaning treatment using organic solvents or water to remove impurities, and removal treatment of ionic impurities using ion exchange. The pigment is preferably of uniform particle size. In addition, by containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

[0105] 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. Trade names for pigment dispersants include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (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 Co., Ltd.), etc.

[0106] When using a pigment dispersant, its amount relative to the total amount of pigment is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less. If the amount of pigment dispersant used is within the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

[0107] In the total amount of colorant, the content of pigment 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.

[0108] Coloring agents may contain dyes. As dyes, there are no particular limitations on the use of known dyes, such as solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds with hues other than pigments, as classified in dye indexes (published by The Society of Dyers and Colourists), or known dyes recorded in dyeing notes (Shikisensha Co., Ltd.). Furthermore, based on chemical structure, examples include: azo dyes, cyanide dyes, triphenylmethane dyes, xanthannaphthalene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methylene dyes, azomethylene dyes, squaric acid lactone dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

[0109] Specifically, examples include: Solvent Yellow (CI) 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI Solvent Red: 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Solvent Orange: 2, 7, 11, 15, 26, 56, 77, 86; CI Solvent Violet: 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; Solvent Blue (CI) 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Solvent Green dyes include CI solvent dyes 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35. 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, 1 57, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red: 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 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; CI Acid Orange: 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet: 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; 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; Acid Green (CI) dyes include 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, and 109. CI Direct Yellow: 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red: 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange: 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet: 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI (Direct Blue) 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 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; CI Direct Green dyes include 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82. CI Disperse Yellow: 51, 54, 76; CI Disperse Violet 26, 27; CI Disperse Blue (CI) disperse dyes such as 1, 14, 56, and 60. CI Basic Red 1, 10; CI Basic Blue: 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; CI Basic Violet 2; CI Basic Red 9; CI Basic Green 1 and other CI basic dyes, CI Reactive Yellow: 2, 76, 116; CI Reactive Orange 16; CI reactive dyes such as Reactive Red 36, CI Mordant Yellow: 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI Mordant Red: 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI Mordant Orange: 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; Mordant Blue (CI) 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI Mordant Green includes CI mordant dyes in grades 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, and 53. CI vat green (Vat Green 1) and other CI vat dyes, etc.

[0110] The dye content is preferably 50% by mass or less relative to the total amount of colorant, more preferably 30% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, or may be 0% by mass.

[0111] 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, relative to the total amount of solid components in the color-curing resin composition. If the content of the colorant is within the range described above, the color concentration is sufficient when producing a color filter, and the composition contains the required amount of resin or polymeric compound, thus enabling the formation of patterns with sufficient mechanical strength.

[0112] Especially in color-curing resin compositions requiring high color intensity, the colorant content is preferably 4% to 60% by mass, more preferably 6% to 56% by mass, further preferably 8% to 53% by mass, and even more preferably 10% to 50% by mass, relative to the total solid content of the curing resin composition. If the colorant content is within the aforementioned range, a particularly high color concentration can be achieved when producing color filters, while simultaneously allowing the composition to contain the required amount of resin or polymeric compound, thus enabling the formation of patterns with sufficient mechanical strength.

[0113] In the color-curing resin composition of the present invention, the colorant is preferably a xaton dye. A xaton dye is a dye comprising a compound having a xaton skeleton within its molecule. Preferably, the xaton dye is a dye comprising a compound represented by formula (I) (hereinafter, sometimes referred to as "compound (I)").

[0114] In formula (I), R1 to R4 independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents, wherein the -CH2- contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR11-; R 5 represents -OH, -SO 3 -, -SO 3H, -SO 3 -Z +, -CO 2H, -CO 2 -Z +, -CO 2R 8, -SO 3R 8, or -SO 2NR 9R 10; R6 and R7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer from 0 to 5; when m is 2 or higher, multiple R 5s can be the same or different; 'a' represents an integer that is either 0 or 1; X represents a halogen atom; Z+ represents +N(R 11) 4, Na+, or K+, and the four R 11 values ​​can be the same or different; R 8 represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which hydrogen atoms can be substituted by halogen atoms; R9 and R10 independently represent a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents. The -CH2- contained in the saturated hydrocarbon group may be substituted by -O-, -CO-, -NH-, or -NR8-. R9 and R10 may bond with the adjacent nitrogen atom to form a heterocycle with 3 to 10 members. R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms.

[0115] Compound (I) may also be its tautomer. When using compound (I), the content of compound (I) in the zetan dye is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, and most preferably 100% by mass, relative to the amount of solid component of the colorant contained in the color-curing resin composition.

[0116] Examples of monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms in R1 to R4 include: straight-chain alkyl groups such as methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups with 2 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. When substituents are present, the number of carbon atoms in the saturated hydrocarbon group is the number of carbon atoms that also include the substituents. Substituents that can exist in saturated hydrocarbon groups include: halogen atoms, -OH, -OR 8, -SO 3 -, -SO 3H, -SO 3 -Z +, -CO 2H, -CO 2R 8, -SR 8, -SO 2R 8, -SO 3R 8, -SO 2NR 9R 10, or -Si(OR 12)(OR 13)(OR 14). R 12, R 13, and R 14 independently represent monovalent saturated hydrocarbon groups with 1 to 4 carbon atoms, and the hydrogen atoms in these saturated hydrocarbon groups can be substituted by halogen atoms.

[0117] Phenyl is an example of a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms in R1 to R4. Examples of monovalent aromatic hydrocarbon groups with substituents include tolyl, xylyl, mesitylene, propylphenyl, and butylphenyl. When substituents are present, the number of carbon atoms in the aromatic hydrocarbon group includes the number of carbon atoms in the substituent. Examples of substituents that can be present in aromatic hydrocarbon groups include: halogen atoms, -R8, -OH, -OR8, -SO3-, -SO3H, -SO3-Z+, -CO2H, -CO2R8, -SR8, -SO2R8, -SO3R8, -SO2NR9R10, or -Si(OR12)(OR13)(OR14).

[0118] Examples of monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms in R8 to R11 include: straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

[0119] The monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms in R9 and R10 may have substituents. Examples of such substituents include hydroxyl groups and halogen atoms.

[0120] Examples of monovalent saturated hydrocarbon groups with 1 to 4 carbons in R12 to R14 include: straight-chain alkyl groups such as methyl, ethyl, propyl, and butyl; and alicyclic saturated hydrocarbon groups with 1 to 4 carbons such as isopropyl and isobutyl.

[0121] Z+ is +N(R11)4, Na+, or K+, preferably +N(R11)4. Preferably, at least two of the four R11 groups in +N(R11)4 are monovalent saturated hydrocarbon groups with 5 to 20 carbon atoms. Furthermore, the total number of carbon atoms in the four R11 groups is preferably 20 to 80, more preferably 20 to 60. When +N(R11)4 is present in compound (I), if the R11 groups are these groups, a color filter with few foreign matter can be formed from the negative resist composition of the present invention containing compound (I).

[0122] Examples of -OR 8 include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, 2-ethylhexoxy, and eicosyloxy.

[0123] Examples of -CO 2R 8 include: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tributoxycarbonyl, hexoxycarbonyl, and eicosyloxycarbonyl.

[0124] Examples of -SR 8 compounds include: methylthio, ethylthio, butylthio, hexylthio, decylthio, eicosylthio, etc. Examples of -SO₂R₈ include: methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl. Examples of -SO 3R 8 include: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tributoxysulfonyl, hexoxysulfonyl, and eicosylsulfonyl.

[0125] As for -SO 2NR 9R 10, for example, the following can be listed: aminesulfonyl; N-Methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylaminesulfonyl, N-butylaminesulfonyl, N-isobutylaminesulfonyl, N-dibutylaminesulfonyl, N-tert-butylaminesulfonyl, N-pentylaminesulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl)aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonyl N-(3-methylbutyl)aminosulfonyl, N-cyclopentylaminosulfonyl, N-hexylaminosulfonyl, N-(1,3-dimethylbutyl)aminosulfonyl, N-(3,3-dimethylbutyl)aminosulfonyl, N-heptylaminosulfonyl, N-(1-methylhexyl)aminosulfonyl, N-(1,4-dimethylpentyl)aminosulfonyl, N-octylaminosulfonyl, N-(2-ethylhexyl)aminosulfonyl, N-(1,5-dimethyl)hexylaminosulfonyl, N-(1,1,2,2-tetramethylbutyl)aminosulfonyl and other N-1 substituted aminosulfonyl groups; N,N-dimethylaminesulfonyl, N,N-ethylmethylaminesulfonyl, N,N-diethylaminesulfonyl, N,N-propylmethylaminesulfonyl, N,N-isopropylmethylaminesulfonyl, N,N-tert-butylmethylaminesulfonyl, N,N-butylethylaminesulfonyl, N,N-bis(1-methylpropyl)aminesulfonyl, N,N-heptylmethylaminesulfonyl, and other N,N-2-substituted aminesulfonyl groups.

[0126] As -Si(OR 12)(OR 13)(OR 14), examples include: trimethoxysilyl, triethoxysilyl, etc.

[0127] R 5 is preferably -CO 2H, -CO 2 -Z +, -CO 2R 8, -SO 3 -, -SO 3 -Z +, -SO 3H, or SO 2NHR 9, and more preferably -SO 3 -, -SO 3 -Z +, -SO 3H, or SO 2NHR 9.

[0128] m represents an integer from 0 to 5, preferably from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0129] As alkyl groups having 1 to 6 carbon atoms in R6 and R7, alkyl groups having 1 to 6 carbon atoms among the listed alkyl groups can be included, preferably alkyl groups having 1 to 2 carbon atoms. R6 and R7 are more preferably hydrogen atoms.

[0130] Examples of aralkyl groups with 7 to 10 carbon atoms in R11 include benzyl, phenylethyl, and phenylbutyl.

[0131] 'a' represents an integer of 0 or 1, preferably 0.

[0132] As compound (I), it is preferably a compound represented by the enumerable formula (Ia) (hereinafter also referred to as "compound (Ia)"). The compound represented by formula (Ia) may be used without combining with compounds other than compound (Ia) in compound (I) (hereinafter sometimes referred to as "compound (Ib)"), or it may be used in combination with compound (Ib) described later. In addition, compound (Ia) may also be used in combination with two or more compounds. In formula (Ia), Ra1 and Ra4 are each independently monovalent aromatic hydrocarbon groups that may have two or fewer monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms; Ra2 and Ra3 are independently hydrogen atoms, methyl groups, or ethyl groups, respectively; R5~R7, m, a, and X represent the same meaning as described above.

[0133] Ra1 and Ra4 can be listed as monovalent aromatic hydrocarbon groups without substituents, or monovalent aromatic hydrocarbon groups having two or fewer monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms. Preferably, they are monovalent aromatic hydrocarbon groups having two or fewer monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms.

[0134] Examples of monovalent aromatic hydrocarbon groups without substituents include phenyl. Examples of monovalent aromatic hydrocarbon groups having two or fewer monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms include toluene, xylene, and mesitylene. The number of carbon atoms in this aromatic hydrocarbon group is preferably 7 to 20, more preferably 7 to 16, further preferably 7 to 10, and most preferably 8. The number of carbon atoms in this aromatic hydrocarbon group includes the number of carbon atoms in the substituents. Preferably, this aromatic hydrocarbon group does not have substituents other than the saturated aliphatic hydrocarbon group.

[0135] The number of saturated aliphatic hydrocarbon groups bonded to the aromatic hydrocarbon group is preferably 1 to 2, more preferably 2. The saturated aliphatic hydrocarbon group is preferably bonded to the ortho or meta position relative to the bond of the aromatic hydrocarbon group, more preferably to the ortho position. Examples of saturated aliphatic hydrocarbon groups include those without substituents. The number of carbon atoms in the saturated aliphatic hydrocarbon group is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.

[0136] Examples of Ra2 and Ra3 include: hydrogen atoms, methyl groups, and ethyl groups, with hydrogen atoms or methyl groups being preferred, and hydrogen atoms being even more preferred.

[0137] As compound (Ib), it is preferably the compound represented by formula (Ib1) (hereinafter sometimes referred to as "compound (Ib1)"). Compound (Ib1) is preferably used in combination with compound (Ia), but may also be used without compound (Ia). That is, the zeolite dye may be compound (Ia) and / or compound (Ib1), preferably compound (Ia), or compound (Ia) and compound (Ib1), and more preferably compound (Ia). In formula (Ib1), Rb1 to Rb4 independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents. At least one saturated hydrocarbon group or aromatic hydrocarbon group contained in Rb1 to Rb4 has a halogen atom, -OH, -OR 8, -CO 2H, -CO 2R 8, -SO 3-, -SO 3H, -SO 3-Z+, -SR 8, -SO 2R 8, -SO 3R 8, -SO 2NR 9R 10, or -Si(OR 12)(OR 13)(OR 14) as a substituent, or at least one aromatic hydrocarbon group contained in Rb1 to Rb4 has three or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents. R5~R10, R12~R14, m, a, and X represent the same meaning as described above.

[0138] Rb1 and Rb4 can be represented by hydrogen atoms in the same group as R1 and R4, monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms that may have substituents, or aromatic hydrocarbon groups having three or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents. Preferably, they are monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms that have substituents, or aromatic hydrocarbon groups having three or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents.

[0139] The number of carbons in the monovalent saturated hydrocarbon group having 1 to 20 carbons that may have substituents is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 7. The number of carbons in the saturated aliphatic hydrocarbon group also includes the number of carbons in the substituents. As substituents, halogen atoms, -OH, -OR 8, -CO 2H, -CO 2R 8, -SO 3-, -SO 3H, -SO 3-Z+, -SR 8, -SO 2R 8, -SO 3R 8, -SO 2NR 9R 10, or -Si(OR 12)(OR 13)(OR 14) are preferred, more preferably -OH, -OR 8, -CO 2H, -CO 2R 8, -SO 3-, -SO 3H, -SO 3-Z+, -SR 8, -SO 2R 8, -SO 3R 8, or -Si(OR 12)(OR 13)(OR 14), further preferably -OH, -OR 8, -CO 2H, -CO 2R 8, or -Si(OR 12)(OR 13)(OR 14), and most preferably -Si(OR 12)(OR 13)(OR 14). 13)(OR 14). In each saturated aliphatic hydrocarbon group, the number of substituents is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.

[0140] The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms of substituents preferably has 7 to 20 carbon atoms, more preferably 7 to 16, further preferably 7 to 12, further preferably 7 to 10, particularly preferably 7 to 8, and most preferably 8. The number of carbon atoms in the aromatic hydrocarbon group also includes the number of carbon atoms in the substituents. As substituents, preferred ones are monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms, halogen atoms, -OH, -OR 8, -CO 2H, -CO 2R 8, -SO 3 -, -SO 3H, -SO 3 -Z +, -SR 8, -SO 2R 8, -SO 3R 8, -SO 2NR 9R 10, or -Si(OR 12)(OR 13)(OR 14), more preferably monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms, -OH, -OR 8, -CO 2H, -CO 2R 8, -SO 3 -, -SO 3H, -SO 3 -Z +, -SR 8, -SO 2R 8, -SO 3R 8, or -SO 2NR 9R 10. Preferably, the substituent is a monovalent saturated aliphatic hydrocarbon group with 1 to 4 carbon atoms, such as -OR 8, -SO 3-, -SO 3H, -SO 3-Z+, -SR 8, -SO 2R 8, -SO 3R 8, or -SO 2NR 9R 10. In each aromatic hydrocarbon group, the number of substituents is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 2. The substituents are preferably bonded to the ortho and / or meta positions relative to the bond of the aromatic hydrocarbon group, more preferably to the ortho position.

[0141] The aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents preferably has 9 to 20 carbon atoms, more preferably 9 to 13, further preferably 9 to 12, and most preferably 9. The number of carbon atoms in the aromatic hydrocarbon group also includes the number of carbon atoms in the substituents. The aromatic hydrocarbon group preferably does not have substituents other than the saturated aliphatic hydrocarbon group. In each aromatic hydrocarbon group, the number of saturated aliphatic hydrocarbon groups is preferably 3 to 5, more preferably 3 to 4, and most preferably 3. The saturated aliphatic hydrocarbon group is preferably bonded to the ortho and / or para positions relative to the bonding bond of the aromatic hydrocarbon group, more preferably to the ortho and para positions. The number of carbon atoms in the monovalent saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.

[0142] Rb2 and Rb3 are preferably hydrogen atoms from the same group as R2 and R3, or monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents. More preferably, they are monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, and even more preferably, they are monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that have substituents.

[0143] The number of carbons in the monovalent saturated hydrocarbon group having 1 to 20 carbons that may have substituents is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The number of carbons in the saturated aliphatic hydrocarbon group also includes the number of carbons in the substituents. As substituents, the following are preferred: halogen atoms, -OH, -OR 8, -CO 2H, -CO 2R 8, -SO 3 -, -SO 3H, -SO 3 -Z +, -SR 8, -SO 2R 8, -SO 3R 8, -SO 2NR 9R 10, or -Si(OR 12)(OR 13)(OR 14), more preferably -OH, -OR 8, -CO 2H, -CO 2R 8, -SO 3 -, -SO 3H, -SO 3 -Z +, -SR 8, -SO 2R 8, -SO 3R 8, or -Si(OR 12)(OR 13)(OR 14), further preferably -OH, -OR 8, -CO 2H, -CO 2R 8, or -Si(OR 12)(OR 13)(OR 14), and most preferably -CO 2H or -CO 2R 8. In each saturated aliphatic hydrocarbon group, the number of substituents is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.

[0144] As compound (Ia), it is preferred to be of formula (Iax) and compounds No. 1 to No. 15 specifically designated in Table 1.

[0145] [Table 1] No. R ax1 R ax2 R ax3 R ax4 1 Ph H H Ph 2 Ph CH 3 CH 3 Ph 3 Ph CH 3CH 2 CH 3CH 2 Ph 4 o-Tolyl H H o-Tolyl 5 o-Tolyl CH 3 CH 3 o-Tolyl 6 o-Tolyl CH 3CH 2 CH 3CH 2 o-Tolyl 7 m-Tolyl H H m-Tolyl 8 m-Tolyl CH 3 CH 3 m-Tolyl 9 m-Tolyl CH 3CH 2 CH 3CH 2 m-Tolyl 10 p-Toluene H H p-Toluene 11 p-Toluene CH 3 CH 3 p-Toluene 12 p-Toluene CH 3CH 2 CH 3CH 2 p-Toluene 13 2,6-Dimethylyl H H 2,6-Dimethylyl 14 2,6-Dimethylyl CH 3 CH 3 2,6-Dimethylyl 15 2,6-Dimethylyl CH 3CH 2 CH 3CH 2 2,6-Dimethylyl

[0146] The symbols in the formula refer to the following bases (where * represents a bond).

[0147] As compound (Ib1), it is preferred to be compound (Ibx) and compounds No. 16 to No. 35 specifically specified in Table 2, as well as compounds represented by formulas A3-1 to A3-8.

[0148] [Table 2] No. R bx1 R bx2 R bx3 R bx4 16 CH 3 CH 3 CH 3 PrTMS 17 CH 3CH 2 CH 3CH 2 CH 3 PrTMS 18 CH 3CH 2 CH 3CH 2 CH 3CH 2 PrTMS 19 Ph PrCOOH PrCOOH Ph 20 o-Tolyl PrCOOH PrCOOH o-Tolyl twenty one m-Tolyl PrCOOH PrCOOH m-Tolyl twenty two p-Toluene PrCOOH PrCOOH p-Toluene twenty three 2,6-Dimethylyl PrCOOH PrCOOH 2,6-Dimethylyl twenty four MT1 H H MT1 25 MT1 CH 3 CH 3 MT1 26 MT1 CH 3CH 2 CH 3CH 2 MT1 27 MT2 H H MT2 28 MT2 CH 3 CH 3 MT2 29 MT2 CH 3CH 2 CH 3CH 2 MT2 30 MT3 H H MT3 31 MT3 CH 3 CH 3 MT3 32 MT3 CH 3CH 2 CH 3CH 2 MT3 33 2,4,6-Trimethylbenzene H H 2,4,6-Trimethylbenzene 34 2,4,6-Trimethylbenzene CH 3 CH 3 2,4,6-Trimethylbenzene 35 2,4,6-Trimethylbenzene CH 3CH 2 CH 3CH 2 2,4,6-Trimethylbenzene

[0149] The symbols in the formula refer to the following bases (where * indicates a key).

[0150]

[0151] (Polymerization Initiator) The color-curing resin composition of the present invention may further contain at least one polymerization initiator (E). The polymerization initiator is a compound or sensitizer used to promote the polymerization of a polymerizable compound that is initiated by the polymerization initiator. When the polymerization initiator (E) is included, it is usually used in combination with a polymerization initiator (C). Examples of polymerization initiators (E) include: 4,4'-bis(dimethylamino)benzophenone (commonly known as milchnerone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthiotonone, N-phenylglycine, etc.

[0152] When using these polymerization initiators, their content is preferably 0.1 to 30 parts by mass, and 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 high sensitivity, and there is a tendency to improve the productivity of color filters, etc.

[0153] (Leveling agent) The color-curing resin composition of the present invention may further contain at least one leveling agent. Examples of leveling agents include silicone-based surfactants, fluorinated surfactants, and silicone-based surfactants having fluorine atoms. These may also have polymerizable groups on their side chains.

[0154] As silicone-based surfactants, examples include surfactants with 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, and Toray silicone SH8400 (trade name: Toray Dow Corning). (manufactured by Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

[0155] Examples of fluorinated surfactants include surfactants with intramolecular fluorocarbon chains. Specifically, examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, and Megafac RS- 718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics & Chemicals), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC (formerly Asahi Glass)) and E5844 (manufactured by Daikin Fine Chemicals Research Institute), etc.

[0156] As silicone-based surfactants containing fluorine atoms, examples include surfactants with intramolecular siloxane bonds and fluorocarbon chains. Specifically, examples include: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC).

[0157] When a leveling agent is included, the leveling agent content is preferably 0.0005% to 0.2% by mass, and more preferably 0.0008% to 0.1% by mass, relative to the total amount of the color-curing resin composition. If the leveling agent content is within the aforementioned range, the flatness of the color filter, etc., can be good.

[0158] When the color-curing resin composition of the present invention containing the aforementioned components is cured to form a cured film, the haze value of the cured film, when converted to a thickness of 2 μm, is preferably 8% to 50%, more preferably 10% to 45%, further preferably 13% to 40%, and even more preferably 17% to 35%. The curing conditions for curing the composition to form a cured film are not particularly limited if sufficient curing can be achieved; for example, curing at 70°C or above for 15 minutes or more. Furthermore, the haze value of the cured film can be measured using a haze meter.

[0159] (solvent) The color-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- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing both -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

[0160] 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, etc.

[0161] 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, etc.

[0162] Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, ethyl 2-methoxy-2-methylpropionate, ethyl 2-methoxy-2-methylpropionate, 3-methoxy-butylacetate, 3-methyl-3-methoxy-butylacetate, 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, and diethylene glycol monobutyl ether acetate, etc.

[0163] 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.

[0164] Examples of alcohol solvents include: methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

[0165] Examples of aromatic hydrocarbon solvents include: benzene, toluene, xylene, and mesitylene.

[0166] Examples of acetylamine solvents include: N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0167] As a solvent, it is preferably one or more selected from the group consisting of ether solvents, ether ester solvents and ketone solvents, more preferably ether solvents and ether ester solvents, and even more preferably propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

[0168] Relative to the total amount of the color-curing resin composition of the present invention, the solvent content is preferably 30% to 80% by mass, more preferably 35% to 75% by mass. In other words, the solid content of the color-curing resin composition is preferably 20% to 70% by mass, more preferably 25% to 65% by mass. If the solvent content is within the aforementioned range, the flatness during coating becomes good. Furthermore, for example, in the case of containing a colorant, the color concentration will not be insufficient when forming a color filter, thus tending to improve display characteristics.

[0169] (Other ingredients) The curable resin composition of the present invention may, as needed, contain fillers, other polymeric compounds, adhesion promoters, antioxidants such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol), light stabilizers, chain transfer agents such as n-dodecyl mercaptan, and other additives known in the art.

[0170] <Method for manufacturing color-curing resin composition> The color-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 inorganic microparticles, as well as polymerization initiation aids, solvents, leveling agents and other components as needed. The colorant can be prepared using the aforementioned pigment dispersion. The target curable resin composition can be prepared by mixing the remaining components into the pigment dispersion at a predetermined concentration. Furthermore, the mixed curable resin composition is preferably filtered using a filter with a pore size of approximately 0.01 μm to 10 μm.

[0171] <Method for manufacturing hardened film> Methods for manufacturing colored patterns and other hardened films from the color-curing resin composition of the present invention include photolithography, inkjet printing, and printing. Photolithography is preferred. Photolithography involves coating the color-curing resin composition onto a substrate, drying it to form a color composition layer, and then exposing and developing the color composition layer through a photomask. In photolithography, by not using a photomask during exposure and / or not performing development, a colored coating film, which is a hardened film of the color-curing resin composition layer, can be formed. The resulting colored patterns or colored coating films can be used as color filters. The thickness of the hardened membrane, such as that of a color filter, is not particularly limited and can be adjusted appropriately according to the purpose or application, for example, from 0.1 μm to 30 μm, preferably from 0.1 μm to 20 μm, and even more preferably from 0.5 μm to 6 μm.

[0172] As a substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass with a silicon dioxide coating are used; or resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used; silicon is used; and aluminum, silver, or silver / copper / palladium alloy thin films are formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc., can also be formed on these substrates.

[0173] The creation of individual color pixels using photolithography can be performed under known or conventional equipment or conditions. For example, it can be done in the following manner. First, the coloring resin composition is coated onto the substrate and dried by removing volatile components such as solvents through heating and drying (pre-baking) and / or vacuum drying to obtain a smooth coloring composition layer. Examples of coating methods include: spin coating, slot coating, and a combination of slot and spin coating. The preferred temperature for heating and drying is 30°C to 120°C, more preferably 50°C to 110°C. The preferred heating time is 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When performing vacuum drying, it is preferable to carry out the process at a pressure of 50 Pa to 150 Pa and a temperature range of 20°C to 25°C. 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.

[0174] Subsequently, the photomask used to form the target color pattern is exposed to the layer of coloring components. The pattern on the photomask is not particularly limited, and a pattern appropriate to the target application is used. The light source used for exposure is preferably a light source that produces light with wavelengths of 250 nm to 450 nm. For example, light with wavelengths less than 350 nm can be cut off using a filter that cuts off that wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts those wavelength ranges. Specifically, examples of light sources include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps. Furthermore, the exposure amount based on a wavelength of 365 nm is preferably 50 J / cm² to 300 J / cm², more preferably 60 J / cm² to 200 J / cm², and even more preferably 65 J / cm² to 180 J / cm². In order to uniformly irradiate the entire exposed surface with parallel light, or to accurately align the photomask with the substrate on which the color composition layer is formed, it is preferable to use exposure devices such as a mask aligner and a stepper.

[0175] A colored pattern is formed on a substrate by developing the exposed colored composition layer in a developing solution. During development, the unexposed portions of the colored composition layer dissolve in the developing solution and are removed. The developing solution is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. 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. The development method can be any of the following: liquid coating, immersion, or spraying. Furthermore, the substrate can be tilted at any angle during development. After development, it is best to wash with water.

[0176] Furthermore, it is preferable to perform a post-baking process on the obtained colored pattern. To form the color filter used in an organic EL display device, the post-baking temperature 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 from 1 minute to 120 minutes, more preferably from 5 minutes to 60 minutes.

[0177] The thickness of the coating after baking is preferably less than 3 μm, and more preferably less than 2.5 μm. There is no particular limitation on the lower limit of the coating thickness, which is usually greater than 0.3 μm, and can also be greater than 0.5 μm.

[0178] The cured film of the color-curable resin composition of the present invention, obtained after post-baking, has a haze value of preferably 8% to 50%, more preferably 10% to 45%, further preferably 13% to 40%, and further preferably 17% to 35% when converted to a thickness of 2 μm. 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-curable resin composition of the present invention.

[0179] The hardened film obtained by hardening the curable resin composition of the present invention is preferably used as a color filter contained in a color filter substrate, and more preferably as a color filter for an organic EL display device with a large cavity structure. [Example]

[0180] The present invention is further illustrated below with examples and comparative examples, but the invention is not limited to these examples. In the examples, unless otherwise specified, the content or even the percentage and parts of the amount used are indicated as a mass basis.

[0181] <Weight Average Molecular Weight> The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined using gel permeation chromatography (GPC) under the following conditions. The ratio (Mw / Mn) of the polystyrene-converted weight-average molecular weight (Mw) obtained under the following conditions is taken as the molecular weight distribution. Device: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40℃ Solvent: Tetrahydrofuran [THF] Flow rate: 1.0 mL / min Solid content concentration of the tested liquid: 0.001% by mass to 0.01% by mass Injection volume: 50 μL Detector: RI Calibration standard materials: TSK Standard Polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0182] <Synthesis Example 1: Preparation of Pigment Dispersion (A1)> mix: CI Pigment Red 291 8.6 parts CI Pigment Yellow 139 3.5 parts 3.9 parts acrylic pigment dispersant 84 parts of propylene glycol monomethyl ether acetate A bead mill was used to fully disperse the pigment, thereby obtaining a pigment dispersion (A1).

[0183] <Synthesis Example 2: Preparation of Pigment Dispersion (A2)> mix: CI Pigment Green 59 9.6 parts CI Pigment Yellow 150 1.7 parts CI Pigment Yellow 139 1.5 parts 3.1 parts acrylic pigment dispersant 84 parts of propylene glycol monomethyl ether acetate The pigment was then fully dispersed using a bead mill to obtain a pigment dispersion (A2).

[0184] <Synthesis Example 3: Preparation of Pigment Dispersion (A3)> mix: CI Pigment Blue 16 9.8 parts Pink Base (manufactured by Taiyo Fine Chemical Co., Ltd.) 1.6 parts 4.6 parts of acrylic pigment dispersant 84 parts of propylene glycol monomethyl ether acetate A bead mill was used to fully disperse the pigment, thereby obtaining a pigment dispersion (A3).

[0185] <Synthesis Example 4: Preparation of Pigment Dispersion (A4)> mix: CI Pigment Green 36 3.9 parts CI Pigment Yellow 185 7.9 parts 4.3 parts acrylic pigment dispersant 84 parts of propylene glycol monomethyl ether acetate The pigment was then fully dispersed using a bead mill to obtain a pigment dispersion (A4).

[0186] <Synthesis Example 5: Preparation of Pigment Dispersion (A5)> mix: CI Pigment Red 254 6.2 parts CI Pigment Red 177 6.2 parts 3.6 parts acrylic pigment dispersant 84 parts of propylene glycol monomethyl ether acetate The pigment was then fully dispersed using a bead mill to obtain a pigment dispersion (A5).

[0187] <Synthesis Example 6: Preparation of Pigment Dispersion (A6)> mix: CI Pigment Blue 15:6 12.1 parts CI Pigment Violet 23 0.6 parts 3.3 parts acrylic pigment dispersant 84 parts of propylene glycol monomethyl ether acetate The pigment was then fully dispersed using a bead mill to obtain a pigment dispersion (A6).

[0188] <Synthesis Example 7: Preparation of Resin> In a flask containing a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 277 parts of propylene glycol monomethyl ether acetate were added. The mixture was stirred while being purged with nitrogen, and the temperature was raised to 120°C. Subsequently, the substance obtained by adding 35.3 parts of tributyl peroxide to a monomer mixture comprising 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentyl methacrylate was added dropwise to the flask via a dropwise funnel over 2 hours. After the addition was completed, the mixture was further stirred at 120°C for 30 minutes to carry out a copolymerization reaction, generating an addition copolymer. Then, the flask was purged with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine, and 0.8 parts of p-methoxyphenol were added to the addition copolymer solution. The reaction was continued at 110°C for 10 hours, during which the epoxy groups derived from glycidyl methacrylate reacted with acrylic acid to cleave the epoxy groups, simultaneously introducing polymerizable unsaturated bonds into the side chains of the polymer. Subsequently, 24.2 parts of succinic anhydride were added to the reaction system, and the reaction was continued at 110°C for 1 hour, allowing the hydroxyl groups generated by the cleavage of the epoxy groups to react with the succinic anhydride, introducing carboxyl groups into the side chains to obtain the polymer. Finally, 383.3 parts of propylene glycol monomethyl ether acetate were added to the reaction solution to obtain a polymer solution with a polymer solids concentration of 40%. The obtained resin had a polystyrene-converted weight-average molecular weight of 6400.

[0189] <Scattering intensity in Mie scattering> The scattering intensity X in the Mie scattering of inorganic microparticles was calculated using Mieplot (see http: / / www.philiplaven.com / mieplot.htm), a program for calculating scattering intensity in Mie scattering, under conditions of unpolarized light, a light source wavelength of 550 nm, and a scattering angle of 0 degrees.

[0190] <Examples 1-6, Reference Examples 1-3, and Comparative Examples 1-3> (1) Preparation of color-curing resin composition The components listed in Table 3 are mixed in the amounts specified in Table 3 to obtain a color-curing resin composition. Furthermore, in preparing the color-curing resin composition, propylene glycol monomethyl ether acetate is mixed in such a way that the solid content of the color-curing resin composition is 14% by weight. The units for the amounts of each component in Table 3 are "parts by mass," and the amounts of pigment dispersions (A1) to (A6), resin (B), polymerizable compound (C), polymerization initiator (D), metal oxide (E), and leveling agent (F) are amounts converted from solid content.

[0191] The polymerizable compound (C), polymerization initiator (D1), polymerization initiator (D2), inorganic microparticles (E), and leveling agent (F) used in the examples, reference examples, and comparative examples are shown below. Polymerizable compound (C): Dipentaerythritol hexaacrylate - Dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "A-9550") Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine (PBG-327; oxime compound; manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) Polymerization initiator (D-2): a compound represented by the following formula Inorganic microparticles (E): Titanium oxide (metal oxide, average particle size 161 nm, scattering intensity 8.0, refractive index 2.7) Leveling agent (F): Polyether-modified silicone oil (trade name "Toray Silicone SH8400" manufactured by Toray Dow Corning (stock)).

[0192] [Table 3] Pigment dispersion Resin B Aggregation compound C Polymerization initiator Inorganic microparticles Leveling agent type Coloring dose Dispersed dose D1 D2 E F Reference Example 1 A1 53 17 40 26 3 1 - 0.1 Example 1 A1 53 17 37 25 2 1 5 0.1 Example 2 A1 53 17 36 twenty four 2 1 6 0.1 See Example 2 A2 50 12 43 29 - 6 - 0.1 Example 3 A2 50 12 41 28 - 6 3 0.1 Example 4 A2 50 12 41 27 - 5 4 0.1 See Example 3 A3 16 6 68 46 - 3 - 0.1 Example 5 A3 16 6 67 44 - 3 3 0.1 Example 6 A3 16 6 66 44 - 3 4 0.1 Comparative Example 1 A4 42 15 18 38 3 - twenty four 0.1 Comparative Example 2 A5 42 12 9 50 3 - twenty four 0.1 Comparative Example 3 A6 42 11 11 50 3 - twenty four 0.1

[0193] <Formulation of Hardened Film> On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the colored curable resin compositions prepared in the above manner were spin-coated to a thickness of 2 μm after baking. The substrate was then pre-baked at 90°C for 1 minute to form a colored composition layer. After cooling, the colored composition layer formed on the substrate was irradiated with light at an exposure dose of 100 mJ / cm² (365 nm reference) under atmospheric conditions using an exposure machine (TME-150RSK; manufactured by Topcon). After irradiation, the substrate was baked in an oven at 85°C for 30 minutes to obtain a colored curable film. The haze and field of view when viewed from an oblique angle were evaluated according to the following criteria. The results are shown in Table 4. Furthermore, regarding the curable films of Comparative Examples 1 to 3, since patterns could not be formed, the field of view when viewed from an oblique angle was not evaluated.

[0194] <Measurement of Haze> The haze of the obtained colored hardened film was measured using a haze meter HZ-2 (manufactured by Suga Testing Equipment Co., Ltd.).

[0195] <Patterned Evaluation> During the exposure process of the hardened film, a photomask with 10 μm lines and spatial patterns is used. The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 24°C for 60 seconds, and then washed with water to obtain the colored pattern. ○: Can form patterns. ×: Unable to form a pattern.

[0196] <Evaluation of the field of view when observing from an oblique angle> A sheet with a specific pattern cut out is placed 5 cm below the colored curing film. Light is shone from below the sheet, allowing light that passes through the specific pattern to pass through the curing film. Then, the clarity of the pattern visible on the curing film surface is evaluated from above the curing film at an angle of approximately 60 degrees relative to the plane of the curing film. ○: The pattern is visible. ×: Pattern cannot be identified.

[0197] [Table 4] Patterning Haze [%] Oblique field of vision Reference Example 1 ○ 0.2 × Example 1 ○ 15.5 ○ Example 2 ○ 19.4 ○ See Example 2 ○ 0.2 × Example 3 ○ 13.5 ○ Example 4 ○ 18.9 ○ See Example 3 ○ 0.2 × Example 5 ○ 16.5 ○ Example 6 ○ 22.5 ○ Comparative Example 1 × 67.5 - Comparative Example 2 × 83.3 - Comparative Example 3 × 93.5 -

[0198] <Examples 7 to 12 and Comparative Examples 4 to 7> The types of inorganic microparticles were changed to those shown in Table 5, and the amount of inorganic microparticles added was changed to 5% by mass. Otherwise, the coloring curable resin composition and the cured film were prepared in the same manner as in Example 3. Furthermore, the haze and oblique field of view of the obtained cured film were evaluated in the same manner as above. The results are shown in Table 5. In addition, the evaluation results for patterning were all ○. In the case of Example 12, compared with other examples, due to the use of large-particle-size inorganic microparticles, a tendency for particles to easily settle was observed.

[0199] [Table 5] Inorganic microparticles Haze [%] Oblique field of vision type Refractive index Particle size [nm] Scattering intensity Comparative Example 4 TiO2 2.7 69 0.9 0.3 × Example 7 TiO2 2.7 110 4.2 9.3 〇 Example 8 TiO2 2.7 161 8.0 33.3 ◎ Example 9 TiO2 2.7 207 24.8 30.5 ◎ Example 10 TiO2 2.7 243 46.3 30.3 ◎ Example 11 TiO2 2.7 299 81.0 30.7 ◎ Comparative Example 5 ZrO 2 2 46 0.01 0.3 × Comparative Example 6 ZnO 2 1.9 69 0.2 0.3 × Comparative Example 7 SiO 2 1.4 95 0.26 0.2 × Example 12 SiO 2 1.4 422 596.5 10.2 〇

Claims

1. A color-curing resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic microparticles, wherein the resin is a resin [K6] having: a structural unit formed by adding structural units derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylene unsaturated bond to a monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and further adding to a polycarboxylic acid and / or carboxylic anhydride; a structural unit derived from monomer (a) and a structural unit derived from monomer (b); and a structural unit derived from a monomer (c) that can copolymerize with monomer (a), wherein monomer (c) is different from monomer (a) and monomer (b); and wherein the inorganic microparticles have an average particle size of 0.05 μm or more and 0.50 μm or less. When the scattering intensity in the Mie scattering of the inorganic microparticles is set as X, and the content of the inorganic microparticles relative to the solid component of the color curable resin composition is set as Y (mass%), X is 4 or more, Y is 15 or less, and the value a calculated by formula (1): a = X × Y (1) is 10 or more.

2. The color-curing resin composition as claimed in claim 1, wherein the inorganic microparticles are metal oxides.

3. The color-curing resin composition as claimed in claim 1, wherein the inorganic microparticles have a refractive index of 1.3 or higher.

4. The color-curing resin composition as claimed in claim 1, wherein the content of the polymeric compound is 0.1% to 50% by mass relative to the solid content of the color-curing resin composition.

5. The color-curing resin composition as claimed in claim 1, wherein the haze value of the cured film of the color-curing resin composition is 8% to 40% when converted to a thickness of 2 μm.

6. A curing film, which is a curing film of a colored curing resin composition as described in any one of claims 1 to 5.

7. The hardened film as claimed in claim 6, wherein it has a haze value of 8% to 40% when converted to a thickness of 2 μm.

8. The hardened film as described in claim 6 constitutes a color filter contained in a color filter substrate.

9. A display device comprising a hardened film as described in claim 6.