TW202323446A - Colored curable resin composition, cured film of colored curable resin composition, and display device capable of providing an organic EL display device capable of providing a sufficiently good field of view even when viewed from an oblique direction - Google Patents

Abstract

The present invention provides a colored curable resin composition having sufficient curability and capable of providing a color filter. The color filter can provide an organic EL display device capable of providing a sufficiently good field of view even when viewed from an oblique direction. A colored curable resin composition comprises a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, wherein when the scattering intensity of the Mie scattering of the inorganic fine particles is X, and when the content of the inorganic fine particles relative to the solid content of the colored curable resin composition is Y mass%, X is 4 or more, Y is 15 or less, and the value a calculated by the formula (1) is 10 or more. a=X×Y (1).

Description

Colored curable resin composition, cured film of colored curable resin composition, and display device

The present invention relates to a colored curable resin composition, a cured film of the colored curable resin composition, and a display device.

An organic electroluminescence (EL) display device is a display device including, for example, an organic EL film formed on a substrate. The organic EL film includes: a hole transport layer; Green (G) and blue (B) light-emitting layers, and electron transport layers. It is a device that utilizes the following mechanism: By applying voltage to the electrodes at both ends of the organic EL film, electrons flow from the cathode to the organic EL film, holes flow from the anode to the organic EL film, and electrons and holes flow between the light-emitting layer. The luminescent molecules recombine so that the luminescent molecules emit light. In order to increase the intensity of the emitted light of each color, a macrocavity structure is adopted in which the optical path length between the upper and lower electrodes matches the wavelength of the light of each color. By using the microcavity structure, the resonance effect of light between the electrodes can be utilized, and the spectrum of the light taken out to the outside becomes steep and high-intensity, and the brightness and color purity of each color of RGB are improved. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-33963

[Problem to be Solved by the Invention] In particular, in an organic EL display device having an organic EL film with a microcavity structure, as described above, the spectrum of light taken out to the outside becomes steep and high-intensity, so that the intensity of color or color development can be improved. , but sometimes a sufficient field of view cannot be obtained when viewing the display device from an oblique direction. In addition, as in Patent Document 1, in order to achieve a sufficient field of view, it has also been studied to use a resin composition containing organic fine particles to manufacture color filters. However, if organic fine particles are added, there will be problems when manufacturing color filters from the resin composition. In some cases, sufficient curability cannot be obtained, or it may be difficult to form a pattern with a predetermined resolution.

Therefore, an object of the present invention is to provide a colored curable resin composition that can provide a color filter that can provide a sufficiently good color even when viewed from an oblique direction, and has sufficient curability. Field of view organic EL display device. [Means to solve the problem]

The inventors of the present invention have found that the object can be achieved by the curable resin composition of the present invention described below. That is, the following aspects are included in the present invention. [1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, wherein when the Mie scattering of the inorganic fine particles is When the scattering intensity in (Mie scattering) is X, and the content of the inorganic fine particles relative to the solid content of the colored curable resin composition is Y mass %, X is 4 or more, Y is 15 or less, and Formula 1): a=X×Y （1） The calculated value a is 10 or more. [2] The colored curable resin composition according to [1], wherein the inorganic fine particles are metal oxides. [3] The colored curable resin composition according to [1] or [2], wherein the inorganic fine particles have a refractive index of 1.3 or more. [4] The colored curable resin composition according to any one of [1] to [3], wherein the inorganic fine particles have an average particle diameter of 0.05 μm to 0.70 μm. [5] The colored curable resin composition according to any one of [1] to [4], wherein the content of the polymerizable compound is 0% by mass to 50% by mass relative to the solid content of the colored curable resin composition. quality%. [6] The colored curable resin composition according to any one of [1] to [5], wherein the cured film of the curable resin composition has a haze value of 8% to 40% when converted to a thickness of 2 μm. %. [7] A cured film of the colored curable resin composition according to any one of [1] to [6]. [8] The cured film according to [7], which has a haze value of 8% to 40% when converted to a thickness of 2 μm. [9] The cured film according to [7] or [8], constituting a color filter contained in a color filter substrate. [10] A display device comprising the cured film according to any one of [7] to [9]. [Effect of the invention]

According to the present invention, it is possible to provide a colored curable resin composition that can provide a color filter that can provide a sufficiently good field of view even when viewed from an oblique direction, and has sufficient curability. Organic EL display device.

Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of this invention is not limited to embodiment demonstrated here, Various changes are possible in the range which does not deviate from the summary of this invention. In addition, when a plurality of upper limit values and lower limit values are described for a specific parameter, any upper limit value and lower limit value of these upper limit values and lower limit values may be combined to make a preferable range of values.

＜Colored curable resin composition＞ The colored curable resin composition of the present invention is a colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, and when the Mie scattering of the inorganic fine particles is When X is the scattering intensity of X, and the content of the inorganic fine particles relative to the solid content of the colored curable resin composition is Y mass %, X is 4 or more, Y is 15 or less, and the formula (1): a=X×Y （1） The calculated value a is 10 or more. In addition, the colored curable resin composition of this invention is also called the composition of this invention below.

(inorganic microparticles) The colored curable resin composition of the present invention contains at least one kind of inorganic fine particles. In this specification, inorganic fine particles are generally inorganic particles having an average particle diameter of 10 μm or less. The average particle diameter of the inorganic fine particles is not particularly limited as long as it is 10 μm or less, and may be a micron-order average particle diameter or a nanometer-order average particle diameter. The average particle diameter of the inorganic fine particles is preferably at most 1 μm, more preferably at most 0.70 μm. The composition of the present invention may contain one kind of inorganic fine particles, or may contain two or more kinds of inorganic fine particles. Here, when the scattering intensity of the Mie scattering of the inorganic fine particles is X, and the content of the inorganic fine particles relative to the solid content of the colored curable resin composition is Y mass %, X is 4 Above, Y is below 15, and by formula (1): a=X×Y （1） The calculated value a is 10 or more.

The scattering intensity X in Mie scattering of inorganic fine particles is a value calculated under the conditions of non-polarized light, light source wavelength 550 nm, and scattering angle 0 degree. For example, Mieplot, which is a calculation program for the scattering intensity in Mie scattering, can be used. (Refer to http://www.philiplaven.com/mieplot.htm) to calculate. The larger the scattering intensity X is, the higher the effect of light scattering is. When the scattering intensity X is less than 4, the light-scattering effect by the inorganic fine particles becomes insufficient, and it becomes difficult to sufficiently secure a field of view when viewing the organic EL display device from an oblique direction. The scattering intensity of the inorganic fine particles contained in the composition of the present invention is 4 or more from the viewpoint of securing the visibility when viewing the organic EL display device from an oblique direction. The value of the scattering intensity X is 4 or more, preferably 5 or more, more preferably 6 or more, and still more preferably 7 or more, from the viewpoint of easily improving the visibility of the organic EL display device. In addition, when the value of X is large, the visibility when observing the organic EL display device from an oblique direction, and the curability when forming a color filter from the composition of the present invention are also likely to improve. The upper limit of the scattering intensity X is not particularly limited, but is preferably 10,000 or less, more preferably 1,000 or less, further preferably 300 or less, and still more preferably 100 or less from the viewpoint of interface reflection control.

The content (Y% by mass) of the inorganic fine particles relative to the solid content of the colored curable resin composition is 15% by mass or less. When the content of the inorganic fine particles exceeds 15% by mass, it is difficult to improve the curability when forming a color filter from the colored curable resin composition, and the color intensity in the obtained color filter tends to decrease. From the viewpoint of curability when forming a color filter and color-developing properties of the color filter, the content (Y% by mass) of the inorganic fine particles relative to the solid content of the colored curable resin composition is preferably 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 8 mass % or less, More preferably, it is 6 mass % or less.

According to the scattering intensity (X) in the Mie scattering of the inorganic fine particles, and the content (Y% by mass) of the inorganic fine particles relative to the solid content of the colored curable resin composition, formula (1): a=X×Y （1） The calculated value a is 10 or more. When the value a is less than 10, the light-scattering effect by the inorganic fine particles is insufficient, and it is difficult to provide a sufficient field of view when viewing the organic EL display device from an oblique direction. The value a is preferably at least 15, more preferably at least 20, and still more preferably at least 25, from the viewpoint of easily improving the visibility when the organic EL display device is viewed obliquely. In addition, from the viewpoint of interface reflection control, it is preferably 800 or less, more preferably 600 or less, further preferably 450 or less, still more preferably 350 or less.

Examples of the inorganic fine particles include inorganic fine particles such as metals, metal oxides, ceramics, and composite materials, and the inorganic fine particles are preferably metal oxides from the viewpoint of scattering strength. The composition of the present invention may contain one kind of inorganic fine particles, or may contain two or more kinds of inorganic fine particles. Inorganic fine particles may be surface-treated. By surface-treating the inorganic fine particles, the dispersibility in the resin composition is improved, and the aggregation of the inorganic fine particles can be easily prevented. Examples of the surface treatment that can be performed on the inorganic fine particles include treatment with a silane coupling agent, a silylating agent, an organic titanate-based coupling agent, silicone oil, and the like.

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. The metal oxide is preferably titanium oxide, zinc oxide and/or silicon dioxide, more preferably titanium oxide and/or silicon dioxide, and still more preferably titanium oxide. When the composition of the present invention contains a metal oxide as the inorganic fine particles, it may contain one kind of metal oxide, or may contain two or more kinds of metal oxides.

The refractive index of the inorganic microparticles is preferably at least 1.3, more preferably at least 1.9, further preferably at least 2.2, and still more preferably at least 2.5, from the viewpoint of the scattering intensity at 550 nm. In addition, from the viewpoint of interface reflection control, the refractive index of the inorganic fine particles is preferably 2.8 or less. The refractive index can be measured, for example, by ellipsometry.

From the viewpoint of scattering intensity, the average particle diameter of the inorganic fine particles is preferably at least 0.05 μm, more preferably at least 0.10 μm, still more preferably at least 0.13 μm, still more preferably at least 0.15 μm. In addition, from the viewpoint of particle sedimentation suppression, the average particle diameter of the inorganic fine particles is preferably 0.70 μm or less, more preferably 0.50 μm or less, further preferably 0.30 μm or less, still more preferably 0.25 μm or less, particularly preferably 0.20 μm or less. μm or less. The average particle diameter can be measured by a dynamic light scattering method, for example.

(resin) The resin contained in the composition of the present invention is not particularly limited, but is preferably an alkali-soluble resin. The composition of the present invention may contain one kind of resin, or may contain two or more kinds of resins. As resin, the following resin [K1] - resin [K6] etc. are mentioned, for example.

Resin [K1]: has a structural unit derived from at least one (a) (hereinafter, sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a source A copolymer composed of structural units of a monomer (b) (hereinafter, sometimes referred to as "(b)") having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond; Resin [K2]: Contains a structural unit derived from (a) and a structural unit derived from (b), and a monomer derived from (c) copolymerizable with (a) (wherein, with (a) and (b) ) different) (hereinafter, sometimes referred to as "(c)") copolymers of structural units; Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]: a copolymer having a structural unit derived from (b) added to a structural unit derived from (a) and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit derived from (a) added to a structural unit derived from (b) and a structural unit derived from (c); Resin [K6]: a copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a polyvalent carboxylic acid and/or carboxylic anhydride.

As (a), specifically, examples include: Acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid and other unsaturated monocarboxylic acids; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6- Tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; 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 carboxyl-containing bicyclic unsaturated compounds; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic Acid anhydrides; Mono-[2-(meth)acryloxyethyl] succinate, mono-[2-(meth)acryloxyethyl] phthalate and other dibasic or higher polycarboxylic acids unsaturated mono[(meth)acryloxyalkyl]esters; Unsaturated acrylic esters, such as α-(hydroxymethyl)acrylates, which contain hydroxyl and carboxyl groups in the same molecule. Among these, acrylic acid, methacrylic acid, and the like are preferable from the viewpoint of copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

(b) means, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and ethylenic A polymeric compound with an unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group. In addition, in this specification, "(meth)acrylic acid" means at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Expressions such as "(meth)acryl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond, Monomer (b2) with an unsaturated bond (hereinafter, sometimes referred to as "(b2)"), and monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b3) )")wait.

Examples of (b1) include monomers (b1-1) having a structure obtained by epoxidizing a linear or branched aliphatic unsaturated hydrocarbon (hereinafter sometimes referred to as "(b1-1 )"), a monomer (b1-2) having a structure obtained by epoxidizing an alicyclic unsaturated hydrocarbon (hereinafter, sometimes referred to as "(b1-2)").

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-methylene Benzyl benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl) base) styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyl oxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4, 5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene and the like.

Examples of (b1-2) include: vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Daicel (manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cyclomer A400; manufactured by Daicel), (meth)acrylic acid 3,4 - Epoxycyclohexylmethyl ester (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), 3,4-epoxytricyclo[ ^5.2.1.02,6 ]decane (meth)acrylate Esters, compounds represented by formula (BI), compounds represented by formula (BII), and the like.

[式（BI）及式（BII）中，R ^e及R ^f表示氫原子、或碳數1～4的烷基，該烷基中所含的氫原子可經羥基取代； X ^e及X ^f表示單鍵、*-R ^g-、*-R ^g-O-、*-R ^g-S-或*-R ^g-NH-； R ^g表示碳數1～6的烷二基； *表示與O的鍵結鍵]

[In formula (BI) and formula (BII), R ^e and R ^f represent a hydrogen atom, or an alkyl group with 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X ^e and X ^f Represents a single bond, *-R ^g -, *-R ^g -O-, *-R ^g -S- or *-R ^g -NH-; R ^g represents an alkanediyl group with 1 to 6 carbons; * represents an alkanediyl group with Bonding key of O]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1 -Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like. As R ^e and R ^f , preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are used, more preferably a hydrogen atom and a methyl group are used.

Examples of the alkanediyl group include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5 -diyl, hexane-1,6-diyl, etc. As X ^e and X ^f , preferably a single bond, methylene, ethylidene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably a single bond, * -CH ₂ CH ₂ -O- (* indicates a bonding bond with O).

(b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloxy group. Examples of (b2) include: 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methyl Acryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl Oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.

(b3) is more preferably a monomer having a tetrahydrofuryl group and a (meth)acryloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

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

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second-butyl (meth)acrylate, second-butyl (meth)acrylate, Tributyl, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (this technical field Among them, it is called "dicyclopentyl (meth)acrylate" as a common name; in addition, it is sometimes called "tricyclodecanyl (meth)acrylate"), tricyclo[5.2 (meth)acrylate .1.0 ^2,6 ]decen-8-yl ester (in this technical field, it is called "dicyclopentenyl (meth)acrylate" as a common name), dicyclopentyl (meth)acrylate Oxyethyl ester, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, Allyl (meth)acrylate, Propargyl (meth)acrylate, Phenyl (meth)acrylate, (Meth)acrylic acid esters such as naphthyl (meth)acrylate, benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Meth)acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; 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-hydroxy Methylbicyclo[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-bis(hydroxymethyl)bicyclo[ 2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]heptene -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( 3-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide Imine Benzoate, N-Succinimidyl-4-maleimide Butyrate, N-Succinimidyl-6-Maleimide Hexanoate, N -Succinimide-3-maleimide propionate, N-(9-acridyl)maleimide and other dicarbonyl imide derivatives; Styrene, α -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, formaldehyde Acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among these, (meth)acrylates are preferable.

The ratio of the structural units derived from each in the resin [K1] is preferably Structural unit derived from (a): 2 mol% to 60 mol% Structural unit derived from (b): 40 mol% to 98 mol%, better to Structural unit derived from (a): 10 mol% to 50 mol% Structural unit derived from (b): 50 mol% to 90 mol%. When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance of the obtained cured film tend to be excellent.

For the resin [K1], for example, the method and Manufactured by citing references recorded in this document.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and oxygen is replaced with nitrogen gas to create a deoxygenated environment, while stirring The method of heating and keeping warm at the same time. In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, Those commonly used in this field can be used. For example, examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides. Oxides (benzoyl peroxide, tertiary butyl peroxy-2-ethylhexanoate, etc.), as solvents, as long as they can dissolve each monomer, can be listed as the coloring agent included in the present invention as the case may be. The organic solvent in the curable resin composition, the solvent described later, and the like.

In addition, the obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like. In particular, at the time of this polymerization, by using, as a solvent, a solvent as described below which is optionally included in the composition contained in the colored curable resin composition of the present invention, the solution after the reaction can be used as it is in the present invention. The production of the colored curable resin composition of the present invention can therefore simplify the production steps of the colored curable resin composition of the present invention.

The ratio of the structural units derived from each in the resin [K2] is preferably in all structural units constituting the resin [K2] Structural unit derived from (a): 2 mol% to 45 mol% Structural unit derived from (b): 2 mol% to 95 mol% Structural unit derived from (c): 1 mol% to 65 mol%, better to Structural unit derived from (a): 5 mol% to 40 mol% Structural unit derived from (b): 5 mol% to 80 mol% Structural unit derived from (c): 5 mol% to 60 mol%. When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the solvent resistance, heat resistance and mechanical properties of the obtained cured film are improved. Tendency to be excellent in strength.

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

The ratio of the structural units derived from each in the resin [K3] is preferably in all structural units constituting the resin [K3] Structural unit derived from (a): 2 mol% to 60 mol% Structural unit derived from (c): 40 mol% to 98 mol%, better to Structural unit derived from (a): 10 mol% to 50 mol% Structural unit derived from (c): 50 mol% to 90 mol%. Resin [K3] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid in (a) and/or carboxylic anhydrides. First, the copolymer of (a) and (c) is manufactured similarly to the method described as the manufacturing method of resin [K1]. In this case, the ratios of the structural units derived from each are preferably the same ratios as those listed for the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer. After producing the copolymer of (a) and (c), the atmosphere in the flask was replaced from nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic acid anhydride and cyclic ether (for example, tris(dimethyl Aminomethyl)phenol, triphenylphosphine, etc.) and polymerization inhibitors (such as hydroquinone, p-methoxyphenol, etc.) are put into the flask, and reacted at 60℃～130℃ for 1 hour～ 10 hours, by which the resin [K4] can be produced. The usage-amount of (b) is preferably 5 mol to 80 mol, more preferably 10 mol to 75 mol, based on 100 mol of (a). By setting it within this range, the storage stability of the curable resin composition, the developability at the time of pattern formation, the pattern shape, the curability at low temperature, and the solvent resistance, heat resistance, and mechanical strength of the obtained pattern are present. And the balance of sensitivity tends to be good. (b1) is preferable as (b1) used for resin [K4], and (b1-1) is more preferable at the point that the reactivity of a cyclic ether is high and unreacted (b) is hard to remain|survive. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). Reaction conditions, such as a charging method, reaction temperature, and time, can be adjusted suitably in consideration of production facilities, heat generation by polymerization, and the like. In addition, in the same manner as the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of production equipment, heat generation due to polymerization, and the like.

Regarding the resin [K5], as a first stage, a copolymer of (b) and (c) was obtained in the same manner as the method for producing the resin [K1]. In the same manner as above, the obtained copolymer may be used as a solution after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like. The ratios of the structural units derived from (b) and (c) relative to the total molar number of all structural units constituting the copolymer are preferably Structural unit derived from (b): 5 mol% to 95 mol% Structural unit derived from (c): 5 mol% to 95 mol%, better to Structural unit derived from (b): 10 mol% to 90 mol% Structural unit derived from (c): 10 mol% to 90 mol%. When the ratio of the structural unit of the resin [K5] is in the above range, there are preservation stability of the colored curable resin composition, developability when forming a pattern, pattern shape, curability at low temperature, and stability of the obtained pattern. The balance of solvent resistance, heat resistance, mechanical strength, and sensitivity tends to be good.

Furthermore, the carboxylic acid or carboxylic acid anhydride contained in (a) and the cyclic ether derived from (b) contained in the copolymer of (b) and (c) are prepared under the same conditions as the production method of resin [K4]. Reaction, whereby the resin [K5] can be obtained. The amount of (a) used to react with the copolymer is preferably 5 mol to 100 mol relative to 100 mol of (b). (b1) is preferable as (b1) used for resin [K5], and (b1-1) is more preferable at the point that the reactivity of a cyclic ether is high and unreacted (b) is hard to remain|survive.

Resin [K6] is resin obtained by further reacting polyhydric carboxylic acid and/or carboxylic anhydride with resin [K5]. Furthermore, polyhydric carboxylic acid and/or carboxylic acid anhydride and the hydroxyl group produced by reaction of the cyclic ether originating in (b) and the carboxylic acid or carboxylic anhydride originating in (a) are made to react. Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, tricarballylic acid, and the like. 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, 5,6-dicarboxybicyclo[2.2.1] Hept-2-ene anhydride, etc. The usage-amount of polyhydric carboxylic acid and/or carboxylic acid anhydride is preferably 0.05-1 mole with respect to 1 mole of usage-amount of (a), More preferably, it is 0.1-0.5 mole.

The resin contained in the colored curable resin composition of the present invention is preferably a resin containing a structural unit having an ethylenically unsaturated bond in a side chain (resin [K4] or resin [K5]), more preferably A resin containing a structural unit including a (meth)acryl group in a side chain. As a resin containing a structural unit containing a (meth)acryl group in a side chain, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3 - a monomer having a (meth)acryloyl group such as methyl-3-methacryloxymethyloxetane, tetrahydrofurfuryl acrylate, etc. as the resin [K4] of (b), And a resin [K5] using a monomer having a (meth)acryl group such as acrylic acid, methacrylic acid, or mono[2-(meth)acryloxyethyl]succinate as (a) . Among the resin [K4] and the resin [K5], as (c), dicarbonyl imide derivatives and vinyl toluene are preferable.

The polystyrene-equivalent weight average molecular weight of the resin contained in the colored curable resin composition of the present invention is preferably from 3,000 to 100,000, more preferably from 4,000 to 50,000, and still more preferably from 5,000 to 30,000. If the weight average molecular weight of the resin is within the above range, the hardness of the cured film of the composition of the present invention is improved, the residual film rate is high, the solubility of the unexposed part to the developing solution becomes good, and the pattern shape is improved, and the pattern is smooth. Tendency to improve resolution.

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

In terms of solid content, 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 more preferably 30 mg-KOH/g KOH/g～135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin is preferably from 5% by mass to 80% by mass, more preferably from 10% by mass to 70% by mass, and still more preferably from 15% by mass to 60% by mass, based on the total amount of solids in the curable colored resin composition. , and more preferably 20% by mass to 50% by mass. When the content of the resin is within the above range, it is easy to improve the curability of the colored curable resin composition, it is easy to form a pattern, and the resolution of the pattern and the residual film ratio tend to be improved. In addition, "the total amount of solid content" in this specification means the amount which removed the content of the solvent from the total amount of a colored curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography (Liquid Chromatography) or gas chromatography (Gas Chromatography), for example.

(polymeric compound) The polymerizable compound is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator, for example, compounds having polymerizable ethylenically unsaturated bonds, etc., preferably (meth)acrylic acid ester compounds.

Among them, the polymerizable compound is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate Esters, Tris(2-(Meth)acryloxyethyl)isocyanurate, Ethylene glycol modified pentaerythritol tetra(meth)acrylate, Ethylene glycol modified dipentaerythritol hexa(methyl) Acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate (meth)acrylates. Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable from the viewpoint of pattern shape.

The weight average molecular weight of the polymerizable compound is preferably from 150 to 2,900, more preferably from 250 to Below 1,500.

The content of the polymerizable compound is preferably at least 3% by mass, more preferably at least 6% by mass, further preferably at least 9% by mass, and still more preferably at least 9% by mass relative to the total amount of solids contained in the colored curable resin composition. 12% by mass or more. In addition, the content of the polymerizable compound is preferably at most 50% by mass, more preferably at most 46% by mass, still more preferably at most 43% by mass, and further preferably at most 43% by mass based on the total amount of solids contained in the colored curable resin composition. More preferably, it is 40 mass % or less. When content of a polymeric compound is more than the said minimum, it becomes easy to improve the curability of a colored curable resin composition, and it becomes easy to form a pattern. In addition, when the content of the polymerizable compound is not more than the above-mentioned upper limit, when the coating film of the colored curable resin composition is exposed to light and the coating film is cured, the degree of hardening in the coating film is unlikely to vary. It can fully harden to the deep part of the coating film, and it is easy to obtain a good pattern shape.

When the total mass of the resin (preferably alkali-soluble resin, more preferably resin [K1] to resin [K6]) contained in the colored curable resin composition and the mass of the polymerizable compound is 100% by mass , the content of the polymerizable compound is preferably at most 50% by mass, more preferably at most 47% by mass, further preferably at most 45% by mass, even more preferably at most 43% by mass. When the content of the polymerizable compound is below the above upper limit, when the coating film of the colored curable resin composition is exposed to light and the coating film is cured, the degree of hardening in the coating film is unlikely to vary, and in particular, sufficient It hardens to the deep part of the coating film, and it is easy to obtain a good pattern shape.

(polymerization initiator) The polymerization initiator is a compound that can generate active radicals, acids, etc. by the action of light or heat to initiate polymerization. Although it does not specifically limit as a polymerization initiator, O-acyl oxime compound, a phenalkone compound, a biimidazole compound, a triazine compound, and an acyl phosphine oxide compound are mentioned. Among them, O-acyl oxime compounds are preferred. From the viewpoint of improving the curability of the colored curable resin composition more easily, the polymerization initiator preferably has a maximum absorption wavelength in the range of 365 nm to 390 nm, and more preferably has a wavelength in the range of 370 nm to 390 nm. Maximum absorption wavelength. The colored curable resin composition of the present invention may contain one kind of polymerization initiator, or may contain two or more kinds of polymerization initiators.

As a polymerization initiator, an O-acyl oxime compound is preferable. In addition, the polymerization initiator is also preferably a compound having a carbazole skeleton, and is also preferably a compound having a nitro group.

所表示的結構的化合物。 The O-acyl oxime compound has the formula (c1):

Compounds of the indicated structure.

所表示的結構的化合物。以下，*表示鍵結鍵。 A compound having a carbazole skeleton has the formula (c2):

Compounds of the indicated structure. Hereinafter, * represents a bonding key.

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

式（c3）及式（c4）中， R ^a表示可具有取代基的碳數6～18的芳香族烴基或可具有取代基的碳數1～15的脂肪族烴基，所述脂肪族烴基中所含的亞甲基（-CH ₂-）可經取代為-O-、-CO-或-S-，所述脂肪族烴基中所含的次甲基（-CH＜）可經取代為-PO ₃＜，所述脂肪族烴基中所含的氫原子可經OH基取代。 再者，在本說明書中，在亞甲基（-CH ₂-）等經取代為-O-、-CO-或-S-等的情況下，碳數是指經取代前的碳數。 R ^b表示可具有取代基的碳數6～18的芳香族烴基、可具有取代基的碳數3～36的雜環基、可具有取代基的碳數1～15的烷基、或將芳香族烴基與由該烷基衍生的烷二基組合而成的可具有取代基的基，所述烷基中所含的亞甲基（-CH ₂-）可經取代為-O-、-CO-、-S-、-SO ₂-或-NR ^h-。R ^h表示碳數6～18的芳香族烴基、碳數3～36的雜環基或碳數1～10的烷基。 R ^c表示可具有取代基的碳數6～18的芳香族烴基、碳數3～36的雜環基或碳數1～10的烷基。 R ^d表示可具有取代基的碳數6～18的芳香族烴基或可具有取代基的碳數3～36的雜環基。 p表示1～4的整數，較佳為表示1或2的整數，更佳為表示1。 The polymerization initiator is more preferably an O-acyl oxime compound having a carbazole skeleton. As such compounds, for example, compounds selected from 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) )) At least one of the group consisting of.

In formula (c3) and formula (c4), R ^a represents an aromatic hydrocarbon group with 6 to 18 carbons that may have substituents or an aliphatic hydrocarbon group with 1 to 15 carbons that may have substituents, and in the aliphatic hydrocarbon group The methylene group (-CH ₂ -) contained in it can be substituted by -O-, -CO- or -S-, and the methine group (-CH<) contained in the aliphatic hydrocarbon group can be substituted by - PO ₃ <, the hydrogen atoms contained in the aliphatic hydrocarbon group may be substituted by OH groups. In addition, in this specification, when a methylene group ( _-CH2- ) etc. are substituted with -O-, -CO-, -S- etc., a carbon number means the carbon number before substitution. R ^b represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or an aromatic A group that may have a substituent formed by a combination of a hydrocarbon group and an alkanediyl group derived from the alkyl group, and the methylene group (-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 carbons, a heterocyclic group having 3 to 36 carbons, or an alkyl group having 1 to 10 carbons. R ^c represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbons, a heterocyclic group having 3 to 36 carbons, or an alkyl group having 1 to 10 carbons. R ^d represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms. p represents an integer of 1-4, preferably represents an integer of 1 or 2, more preferably represents 1.

The carbon number of the aromatic hydrocarbon group represented by R ^a becomes like this. Preferably it is 6-15, More preferably, it is 6-12, More preferably, it is 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and terphenyl, more preferably phenyl and naphthyl, and still more preferably phenyl. In addition, the aromatic hydrocarbon group represented by R ^a may have one or two or more substituents. Examples of the substituent include the same substituents that the aromatic hydrocarbon group of R ^a may have.

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

As the aliphatic hydrocarbon group which may have a substituent represented by R ^a , a group represented by the following formula etc. are mentioned. In the formula, * represents a bonding bond.

R ^a is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and still more preferably a linear or branched chain alkyl group having no substituent.

The carbon number of the aromatic hydrocarbon group represented by R ^b becomes like this. Preferably it is 6-15, More preferably, it is 6-12, More preferably, it is 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl and the like, more preferably phenyl and naphthyl, particularly preferably phenyl. In addition, the aromatic hydrocarbon group represented by R ^b may have one or two or more substituents. The substituent is preferably substituted at the ortho or para position of the aromatic hydrocarbon group. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl C1-15 alkyl groups such as tetradecyl groups, tetradecyl groups, and pentadecyl groups; halogen atoms such as fluorine atoms, chlorine atoms, iodine atoms, and bromine atoms; and the like. The carbon number of the alkyl group as the substituent is preferably 1-10, more preferably 1-7. The alkyl group as the substituent may be any of linear, branched and cyclic, and may be a combination of a linear group and a cyclic group. The methylene group (—CH ₂ —) contained in the alkyl group as the substituent may be substituted with —O— or —S—. In addition, the hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom, and is preferably substituted with a fluorine atom.

As an alkyl group which is a substituent of the aromatic hydrocarbon group represented by R ^b , the group represented by the following formula etc. are mentioned, for example. In the formula, * represents a bonding bond.

As the aromatic hydrocarbon group which may have a substituent represented by ^Rb , the group represented by the following formula etc. are mentioned, for example. In the formula, * represents a bonding bond.

[式中，R ⁱ分別獨立地表示可經鹵素原子取代的碳數1～10的烷基，R ⁱ所含的亞甲基（-CH ₂-）可經取代為-O-或-S-，R ^j分別獨立地表示可經鹵素原子取代的碳數1～10的烷基，q表示1～5的整數，r表示0～4的整數；其中，q+r的合計為5以下] The aromatic hydrocarbon group represented by R ^b which may have a substituent is preferably a group represented by the following formula.

[In the formula, R ⁱ each independently represent an alkyl group with 1 to 10 carbons that may be substituted by a halogen atom, and the methylene group (-CH ₂ -) contained in R ⁱ may be substituted by -O- or -S- , R ^{and j} each independently represent an alkyl group with 1 to 10 carbon atoms that may be substituted by a halogen atom, q represents an integer of 1 to 5, and r represents an integer of 0 to 4; wherein, the total of q+r is 5 or less]

Examples of the alkyl group represented by R ⁱ and R ^j include the same groups as the alkyl group exemplified as the substituent of the aromatic hydrocarbon group represented by R ^b . The carbon number of R ⁱ is preferably 2-8, more preferably 2-6. In addition, the alkyl group represented by R ^j may be any of linear, branched, and cyclic, and is preferably chain. R ⁱ is preferably a group represented by the formula *-R ^j1 -OR ^j2 . Here, R ^j2 represents an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom. R ^j2 is preferably a linear alkyl group having 1 to 3 carbon atoms. R ^j1 represents an alkylene group having 1 to 10 carbon atoms which may be substituted by a halogen atom. R ^j1 is preferably a linear alkylene group having 1 to 3 carbon atoms. When R ⁱ and R ^j contain a halogen atom, examples of the halogen atom contained in R ⁱ and R ^j include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, particularly preferably a fluorine atom. In addition, when R ⁱ and/or R ^j contain halogen atoms, the number thereof is preferably two or more and ten or less, and more preferably three or more and six or less. The substitution position of the R ⁱ O- group is preferably the ortho or para position. The substitution position of the R ^j -group is preferably an ortho position or a para position, particularly preferably an ortho position. In addition, q is preferably 1-2, more preferably 1. r is preferably 0-2, particularly preferably 0 or 1.

The carbon number of the heterocyclic group represented by R ^b is preferably 3-20, more preferably 3-10, still more preferably 3-5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, and carbazolyl. In addition, the heterocyclic group represented by R ^b may have one or two or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent that the aromatic hydrocarbon group represented by R ^b may have.

The carbon number of the alkyl group represented by R ^b is preferably 1-12. Examples of the alkyl group represented by R ^b include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl , tridecyl, tetradecyl and pentadecyl, etc. These alkyl groups may be linear, branched, or cyclic, and may be a combination of a linear group and a cyclic group. In addition, in the alkyl group represented by R ^b , the methylene group (-CH ₂ -) may be substituted with -O-, -CO-, -S-, -SO ₂ - or -NR ^h -, and the hydrogen atom may be OH group or SH group substitution.

R ^h represents an alkyl group having 1 to 10 carbons, preferably an alkyl group having 1 to 5 carbons, more preferably an alkyl group having 1 to 3 carbons. The alkyl group can be chain (straight chain or branched chain), also can be cyclic, also can be any of straight chain, branched chain and cyclic, can also be a chain base and ring The base formed by the combination of bases. In addition, in the alkyl group of ^Rh , the methylene group (-CH ₂ -) may be substituted with -O- or -CO-.

As the alkyl group which may have a substituent represented by ^Rb , the group represented by the following formula etc. are mentioned specifically,. * Indicates a bonded bond.

Furthermore, the carbon number of the group formed by combining the aromatic hydrocarbon group represented by R ^b and the alkanediyl group derived from the alkyl group represented by R ^b is preferably 7-33, more preferably 7-18, and even more preferably 7 to 12. This combined group may have one or two or more substituents, and examples of the substituents include the same groups as those exemplified as the substituents that the aromatic hydrocarbon group and the alkyl group may have. Examples of the combination of the aromatic hydrocarbon group represented by R ^b and the alkanediyl group derived from the alkyl group represented by R ^b include aralkyl groups, and specific examples include groups represented by the following formula. In the formula, * represents a bonding bond.

Among these, R ^b is preferably an optionally substituted aromatic hydrocarbon group or an optionally substituted alkyl group, more preferably an optionally substituted aromatic hydrocarbon group.

The carbon number of the aromatic hydrocarbon group represented by R ^c is preferably 6-15, more preferably 6-12, and still more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and terphenyl. The carbon number of the heterocyclic group represented by R ^c is preferably 3-20, more preferably 3-10, and still more preferably 3-5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, and carbazolyl. The carbon number of the alkyl group represented by R ^c is preferably 1-7, more preferably 1-5, and still more preferably 1-3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. This alkyl group may be any of linear, branched and cyclic, and may be a combination of a linear group and a cyclic group.

R ^c is preferably a chained alkyl group, more preferably a chained alkyl group having 1 to 5 carbons, still more preferably a chained alkyl group having 1 to 3 carbons, particularly preferably a methyl group.

The number of carbon atoms in the aromatic hydrocarbon group represented by R ^d is preferably from 6-15, more preferably from 6-12, and still more preferably from 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and terphenyl, and more preferably phenyl and naphthyl. In addition, the aromatic hydrocarbon group represented by ^Rd may have one or two or more substituents. The substituent is preferably substituted at the ortho or para position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and Alkyl groups with 1 to 15 carbons such as decyl; alkenyl groups with 1 to 15 carbons such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl and decenyl wait. The carbon number of the aliphatic hydrocarbon group that the aromatic hydrocarbon group represented by ^Rd may have is more preferably 1 to 7, and the aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic, and may also be chain A group formed by combining a shape group and a ring group. In addition, the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be substituted with -O-, -CO- or -S-, and the methine group (-CH<) may be substituted with -N< .

As an aliphatic hydrocarbon group which the aromatic hydrocarbon group represented by ^Rd may have, the group represented by the following formula etc. are mentioned. In the formula, * represents a bonding bond.

As the aromatic hydrocarbon group which may have a substituent represented by ^Rd , the group represented by the following formula etc. are mentioned. In the formula, * represents a bonding bond.

The carbon number of the heterocyclic group represented by R ^d is preferably 3-20, more preferably 3-10, and still more preferably 3-5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, and carbazolyl. In addition, the heterocyclic group represented by ^Rd may have one or two or more substituents, and examples of the substituents include the same groups as exemplified as substituents that the aromatic hydrocarbon group represented by ^Rd may have. .

Among them, R ^d is preferably an aromatic hydrocarbon group with a substituent, and as the substituent, it is preferably a chain alkyl group with 1 to 7 carbons (more preferably 1 to 3 carbons), and the number of substituents is relatively small. Preferably, there are two or more and five or less.

Compound (c3) and compound (c4) can be produced by the production method described in Japanese Patent Application Publication No. 2014-500852 or International Publication No. 2008-078678.

[式中，R ^j為碳數1～3的烷基，R ⁱ為式*-R ^j1-O-R ^j2所表示的基〔此處，R ^j1表示碳數1～4的直鏈狀或分支狀的可經鹵素原子取代的脂肪族烴基，R ^j2表示碳數1～4的直鏈狀或分支狀的可經鹵素原子取代的烷基〕，R ⁱ及R ^j中所含的氫原子可經取代為鹵素原子；q及r為1] 作為化合物（c3）的市售品，可列舉NCI-831（艾迪科（ADEKA）公司製造）。 The compound (c3) is preferably the following compound: R ^a is an alkyl group having 1 to 15 carbons which may have a substituent, R ^b is an aromatic hydrocarbon group having 6 to 18 carbons which may have a substituent, and R ^c is a carbon An alkyl group with a number of 1 to 10, and p is 1 or 2, more preferably a compound as follows: R ^a is an alkyl group with a carbon number of 1 to 4 that may have a substituent, R ^b is a group represented by the following formula, R ^c is an alkyl group having 1 to 4 carbon atoms, and p is 1.

[In the formula, R ^j is an alkyl group with 1 to 3 carbons, and R ⁱ is a group represented by the formula *-R ^j1 -OR ^j2 [Here, R ^j1 represents a linear or branched chain with 1 to 4 carbons an aliphatic hydrocarbon group that can be substituted by a halogen atom, R ^j2 represents a straight-chain or branched alkyl group with 1 to 4 carbon atoms that can be substituted by a halogen atom], and the hydrogen atoms contained in R ⁱ and R ^j can be Substitution is a halogen atom; q and r are 1] Examples of commercially available compounds of the compound (c3) include NCI-831 (manufactured by ADEKA).

The compound (c4) is preferably the following compound: R ^a is an alkyl group having 1 to 10 carbons which may have a substituent, R ^b is an aromatic hydrocarbon group having 6 to 10 carbons which may have a substituent, and R ^c is a carbon An alkyl group having a number of 1 to 4, and R ^d represents an aromatic hydrocarbon group which may have a substituent. As a commercial item of a compound (c4), Irgacure OXE03 (made by BASF company) is mentioned.

The phenylalkyl ketone compound is a compound 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 a substituent.

Examples of compounds having a structure represented by formula (d4) include: 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamine Base-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. Commercially available products such as Irgacure 369, 907, and 379 (above, manufactured by BASF) may also be used. As a compound having a structure represented by formula (d5), 2-hydroxyl-2-methyl-1-phenylpropane-1-one, 2-hydroxyl-2-methyl-1-[4-( 2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomers, α,α-diethoxyacetophenone, benzoyl dimethyl ketal, etc. From the viewpoint of sensitivity, as the phenylalkyl ketone compound, a compound having a structure represented by formula (d4) is preferable.

Examples of the biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-bis Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2' -bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4', 5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl) Biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), 4,4',5,5'-position phenyl substituted by alkoxycarbonyl Imidazole compounds (for example, refer to Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like. Among them, compounds represented by the following formulas and mixtures thereof are preferred.

Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) base)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene Base]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1 ,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. .

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

The content of the polymerization initiator is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and still more preferably 2 parts by mass relative to the total amount of solids contained in the colored curable resin composition. Parts by mass to 30 parts by mass. When the content of the polymerization initiator is within the above range, it is easy to form a pattern with a good shape by exposure and image development, and it is easy to improve the curability at low temperature. In addition, since the exposure time tends to be shortened due to high sensitivity, the productivity of color filters and the like is improved.

(Colorant) The colored curable resin composition of the present invention contains at least one colorant. The coloring agent may be any of dyes and pigments, but preferably includes pigments. As the pigment, known pigments can be used, for example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

Specifically, C.I. Pigment Yellow (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 and other yellow pigments; C.I. Pigment Orange (Pigment Orange) 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Red (Pigment Red) 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, 291 and other red pigments; C.I. Pigment Blue (Pigment Blue) 15, 15:3, 15:4, 15:6, 16, 60 and other blue pigments; C.I. Pigment Violet (Pigment Violet) 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. Pigment green (pigment green) 7, 36, 58, 59 and other green pigments; C.I. Pigment brown (pigment brown) 23, 25 and other brown pigments; C.I. Pigment black (pigment black) 1, 7 and other black pigments, etc.

If necessary, the pigment may be subjected to rosin treatment, surface treatment using a pigment derivative with an acidic group or a basic group introduced, grafting treatment of the pigment surface with a polymer compound, etc., microparticles by sulfuric acid micronization method, etc. chemical treatment, cleaning treatment with an organic solvent or water for removal of impurities, removal treatment of ionic impurities with ion exchange, etc. The pigment preferably has a uniform particle size. In addition, by containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Lubrizol Chemical Co., Ltd.) (Manufactured by Lubrizol), EFKA (manufactured by CIBA), Ajisper (manufactured by Ajinomoto Fine-Techno), Diss Disperbyk (manufactured by BYK-chemie), etc.

When a pigment dispersant is used, the amount used is preferably from 1% by mass to 100% by mass, more preferably from 5% by mass to 50% by mass, based on the total amount of the pigment. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency for the pigment dispersion liquid of the uniform dispersion state to be obtained.

The pigment content is preferably at least 50% by mass, more preferably at least 70% by mass, still more preferably at least 90% by mass, particularly preferably at least 95% by mass, and may be 100% by mass in the total amount of the colorant.

Colorants may contain dyes. Known dyes can be used without particular limitation as the dye, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds having a hue other than pigments classified in the Dye Index (published by The Society of Dyers and Colourists), or dyeing notes (Shikisensha Co., Ltd.) Known dyes described in . In addition, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, Nitromethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. Solvent Yellow (Solvent Yellow) 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; C.I. 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; C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86; C.I. Solvent Violet (Solvent Violet) 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94 , 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent Green (Solvent Green) 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. solvent dyes, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99 ,111,112,113,114,116,119,123,128,134,135,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178 ,179,184,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251 ; C.I. 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; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42 , 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93 ,93:1,96,99,100,102,103,104,108,109,110,112,113,117,119,120,123,126,127,129,130,131,138,140,142 ,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; C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63 , 65, 80, 104, 105, 106, 109 and other C.I. acid dyes, C.I. 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; C.I. Direct Red (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; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Violet (Direct Violet) 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80 ,81,84,85,86,90,93,94,95,97,98,99,100,101,106,107,108,109,113,114,115,117,119,120,137,149 ,150,153,155,156,158,159,160,161,162,163,164,165,166,167,168,170,171,172,173,188,189,190,192,193,194 ,195,196,198,199,200,201,202,203,207,209,210,212,213,214,222,225,226,228,229,236,237,238,242,243,244 , 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Green (Direct Green) 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other C.I. direct dyes, C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. Disperse Blue (Disperse Blue) 1, 14, 56, 60 and other C.I. disperse dyes, C.I. Basic Red (Basic Red) 1, 10; C.I. Basic Blue (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; C.I. Basic Violet 2; C.I. Basic Red (Basic Red) 9; C.I. basic green (Basic Green) 1 and other C.I. basic dyes, C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. reactive dyes such as C.I. reactive red (Reactive Red) 36, C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. 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; C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 ; C.I. 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; C.I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40 , 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; C.I. Mordant Green (Mordant Green) 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other C.I. mordant dyes, C.I. Vat Green (Vat Green) 1, etc. C.I. Vat dyes, etc.

The content of the dye is preferably at most 50% by mass, more preferably at most 30% by mass, still more preferably at most 10% by mass, particularly preferably at most 5% by mass, or may be 0% by mass based on the total amount of the colorant.

The content of the coloring agent is preferably from 5% by mass to 60% by mass, more preferably from 8% by mass to 55% by mass, and still more preferably from 10% by mass to 50% by mass, based on the total amount of solids in the colored curable resin composition. %. When the content of the colorant is within the above range, the color density is sufficient when forming a color filter, and a required amount of resin or polymerizable compound can be contained in the composition, so that a pattern with sufficient mechanical strength can be formed.

In particular, in a colored curable resin composition requiring a richer color, the content of the colorant is preferably 4% by mass to 60% by mass, more preferably 6% by mass, based on the total amount of solid content of the curable resin composition. % to 56% by mass, more preferably 8% to 53% by mass, more preferably 10% to 50% by mass. If the content of the colorant is within the above range, a particularly high color density can be achieved when a color filter is made, and at the same time, a required amount of resin or polymerizable compound can be contained in the composition, so that a color filter with sufficient mechanical strength can be formed. pattern.

In the colored curable resin composition of the present invention, the colorant preferably contains a xanthene dye. A xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule. The xanthene dye is preferably a dye containing a compound represented by formula (I) (hereinafter, may be referred to as "compound (I)").

[In formula (I), R ¹ to R ⁴ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have a substituent, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms that may have a substituent The -CH ₂ - contained in the saturated hydrocarbon group can be substituted by -O-, -CO- or -NR ¹¹ -; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ , or -SO ₂ NR ⁹ R ¹⁰ ; R ⁶ and R ⁷ independently represent a hydrogen atom or a carbon number An alkyl group of 1 to 6; m represents an integer of 0 to 5; when m is 2 or more, multiple R ⁵ can be the same or different; a represents an integer of 0 or 1; X represents a halogen atom; Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ , or K ⁺ , the four R ¹¹ can be the same or different; R ⁸ represents a monovalent saturated hydrocarbon group with 1 to 20 carbons, and the hydrogen atoms contained in the saturated hydrocarbon group can be replaced by halogen atoms Substitution; R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group with a carbon number of 1 to 20 that may have substituents, and the -CH ₂ - contained in the saturated hydrocarbon group can be modified by -O-, -CO- , -NH-, or -NR ⁸ -substitution, R ⁹ and R ¹⁰ can be bonded together and form a 3- to 10-membered heterocyclic ring with adjacent nitrogen atoms; R ¹¹ represents a hydrogen atom with 1 to 20 carbon atoms A monovalent saturated hydrocarbon group, or an aralkyl group with 7 to 10 carbons]

Compound (I) may also be its tautomer. When the compound (I) is used, the content of the compound (I) in the xanthene dye is preferably at least 50% by mass, more preferably 70% by mass or more, more preferably 90% by mass or more, most preferably 100% by mass.

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in R ¹ to R ⁴ include methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, deca Straight-chain alkyl groups such as dialkyl, hexadecyl, and eicosyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; cyclopropyl C2-20 alicyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecanyl. When having a substituent, the carbon number of the saturated hydrocarbon group is the number of carbons also including the substituent. Examples of substituents that a saturated hydrocarbon group may have include halogen atoms, -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ¹⁰ , or -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ). R ¹² , R ¹³ and R ¹⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and hydrogen atoms contained in the saturated hydrocarbon group may be substituted by halogen atoms.

Examples of the monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms in R ¹ to R ⁴ include phenyl groups. Examples of the monovalent aromatic hydrocarbon group having a substituent include a toluyl group, xylyl group, mesityl group, propylphenyl group, and butylphenyl group. When having a substituent, the carbon number of the aromatic hydrocarbon group is the number including the carbon number of the substituent. Examples of substituents that the aromatic hydrocarbon group may have include halogen atoms, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, - CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ¹⁰ , or -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ).

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in R ⁸ to R ¹¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Straight-chain alkyl groups such as dodecyl, hexadecyl, and eicosyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl ; C3-20 alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecanyl.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ may have a substituent. Examples of the substituent include a hydroxyl group and a halogen atom.

Examples of monovalent saturated hydrocarbon groups having 1 to 4 carbon atoms in R ¹² to R ¹⁴ include: linear alkyl groups such as methyl, ethyl, propyl, and butyl; branched groups such as isopropyl and isobutyl; An alicyclic saturated hydrocarbon group having 1 to 4 carbon atoms such as a chain alkyl group.

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ . Preferably, at least two of the four R ¹¹ in ⁺ N(R ¹¹ ) ₄ are monovalent saturated hydrocarbon groups with 5 to 20 carbons. In addition, the total carbon number of four R ^11s is preferably from 20 to 80, more preferably from 20 to 60. When ⁺ N(R ¹¹ ) ₄ exists in the compound (I), if R ¹¹ is these groups, a color filter with less foreign matter can be formed from the negative resist composition of the present invention containing the compound (I) light sheet.

Examples of -OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, di Decyloxy.

Examples of -CO ₂ R ⁸ include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl and eicosyloxycarbonyl.

Examples of -SR ⁸ include methylthio, ethylthio, butylthio, hexylthio, decylthio, eicosylthio and the like. Examples of -SO ₂ R ⁸ include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosylsulfonyl. Examples of -SO ₃ R ⁸ include: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl, ethanol Alkoxysulfonyl.

Examples of -SO ₂ NR ⁹ R ¹⁰ include: sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropyl group Aminosulfonyl group, N-butylaminosulfonyl group, N-isobutylsulfamoyl group, N-second butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group Aminosulfonyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1,2-dimethylpropyl) base) sulfamoyl group, N-(2,2-dimethylpropyl) sulfamoyl group, N-(1-methylbutyl) sulfamoyl group, N-(2-methylbutyl) Aminosulfonyl, N-(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3-dimethylbutyl ) sulfamoyl group, N-(3,3-dimethylbutyl) sulfamoyl group, N-heptyl sulfamoyl group, N-(1-methylhexyl) sulfamoyl group, N-( 1,4-Dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5-dimethyl)hexyl N-1 substituted sulfamoyl group such as sulfamoyl group, N-(1,1,2,2-tetramethylbutyl)sulfamoyl group; N,N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl, N,N-diethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-tert-butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptyl N, N-2 substituted sulfamoyl, such as methylsulfamoyl, etc.

Examples of -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ) include trimethoxysilyl groups, triethoxysilyl groups, and the like.

R ⁵ is preferably -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H, or SO ₂ NHR ⁹ , more preferably - SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or SO ₂ NHR ⁹ .

m represents the integer of 0-5, Preferably it is 1-4, More preferably, it is 1 or 2, More preferably, it is 1.

The alkyl group having 1 to 6 carbons in R ⁶ and R ⁷ may include an alkyl group having 1 to 6 carbons among the alkyl groups listed above, preferably an alkyl group having 1 to 2 carbons. R ⁶ and R ⁷ are more preferably hydrogen atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include benzyl, phenylethyl, phenylbutyl and the like.

a represents an integer of 0 or 1, preferably 0.

[式（Ia）中， R ^a1及R ^a4分別獨立地為可具有兩個以下的碳數為1～4的一價飽和脂肪族烴基的一價芳香族烴基； R ^a2及R ^a3分別獨立地為氫原子、甲基、或乙基； R ⁵～R ⁷、m、a、及X表示與所述相同的含義] As the compound (I), preferably, a compound represented by the formula (Ia) (hereinafter also referred to as "compound (Ia)") is exemplified. The compound represented by formula (Ia) may not be used in combination with compounds other than compound (Ia) in compound (I) (hereinafter sometimes referred to as "compound (Ib)"), and compound (Ia) may be used in combination with Compounds (Ib) are used in combination. Moreover, compound (Ia) can also be used in combination of 2 or more types.

[In formula (Ia), R ^a1 and R ^a4 are each independently a monovalent aromatic hydrocarbon group that may have two or less monovalent saturated aliphatic hydrocarbon groups with carbon numbers of 1 to 4; R ^a2 and R ^a3 are each independently is a hydrogen atom, a methyl group, or an ethyl group; R ⁵ to R ⁷ , m, a, and X represent the same meanings as described above]

Examples of R ^a1 and R ^a4 include a monovalent aromatic hydrocarbon group having no substituent in the same group as R ¹ and R ⁴ above, or a monovalent saturated aliphatic group having 2 or less carbon atoms and having 1 to 4 carbon atoms. A monovalent aromatic hydrocarbon group of a hydrocarbon group. Among them, a monovalent aromatic hydrocarbon group having two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms is preferred.

A phenyl group is mentioned as a monovalent aromatic hydrocarbon group which does not have a substituent. Examples of the monovalent aromatic hydrocarbon group having two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms include toluyl group, xylyl group, mesityl group and the like. The carbon number of the aromatic hydrocarbon group is preferably 7-20, more preferably 7-16, still more preferably 7-10, most preferably 8. The carbon number of the aromatic hydrocarbon group includes the carbon number of the substituent. The aromatic hydrocarbon group preferably does not have a substituent other than the saturated aliphatic hydrocarbon group.

The number of the saturated aliphatic hydrocarbon groups bonded to the aromatic hydrocarbon groups is preferably 1-2, more preferably 2. The saturated aliphatic hydrocarbon group is preferably bonded at the ortho or meta position, more preferably at the ortho position, with respect to the bond of the aromatic hydrocarbon group. As this saturated aliphatic hydrocarbon group, the saturated aliphatic hydrocarbon group which does not have a substituent is mentioned. The carbon number of the saturated aliphatic hydrocarbon group is preferably 1-4, more preferably 1-3, still more preferably 1-2, most preferably 1.

Examples of R ^a2 and R ^a3 include a hydrogen atom, a methyl group, and an ethyl group. Among these, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred.

[式（Ib1）中，R ^b1～R ^b4分別獨立地表示氫原子、可具有取代基的碳數1～20的一價飽和烴基、或者可具有取代基的碳數6～20的一價芳香族烴基， R ^b1～R ^b4中所含的至少一個飽和烴基或芳香族烴基具有鹵素原子、-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、或-Si(OR ¹²)(OR ¹³)(OR ¹⁴)作為取代基，或者R ^b1～R ^b4中所含的至少一個芳香族烴基具有三個以上的碳數為1～4的一價飽和脂肪族烴基作為取代基， R ⁵～R ¹⁰、R ¹²～R ¹⁴、m、a及X表示與所述相同的含義] The compound (Ib) is preferably a compound represented by the formula (Ib1) (hereinafter sometimes referred to as "compound (Ib1)"). Compound (Ib1) is preferably used in combination with compound (Ia), and may not be used in combination with compound (Ia). That is, the xanthene dye can be compound (Ia) and/or compound (Ib1), preferably compound (Ia), or compound (Ia) and compound (Ib1), more preferably compound (Ia).

[In the formula (Ib1), R ^b1 to R ^b4 independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with a carbon number of 1 to 20 that may have a substituent, or a monovalent aromatic hydrocarbon group with a carbon number of 6 to 20 that may have a substituent. At least one saturated hydrocarbon group or aromatic hydrocarbon group contained in R ^b1 to R ^b4 has a halogen atom, -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ¹⁰ , or -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ) as substitutions or at least one aromatic hydrocarbon group contained in R ^b1 to R ^b4 has three or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbons as substituents, R ⁵ to R ¹⁰ , R ¹² to R ¹⁴ , m, a and X represent the same meaning as described]

Examples of R ^b1 and R ^b4 include hydrogen atoms in the same groups as R ¹ and R ⁴ , monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, and C 6 to 20 carbon atoms that may have substituents. 20 monovalent aromatic hydrocarbon groups, or aromatic hydrocarbon groups having three or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms as substituents. Among them, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms having a substituent, or a monovalent aromatic hydrocarbon group having three or more carbon atoms having 1 to 4 carbon atoms is preferred. An aromatic hydrocarbon group having a monovalent saturated aliphatic hydrocarbon group as a substituent.

The carbon number of the monovalent saturated hydrocarbon group having 1-20 carbon atoms which may have a substituent is preferably 1-10, more preferably 2-8, still more preferably 2-7. The number of carbons in the saturated aliphatic hydrocarbon group includes the number of carbons in the substituent. As the substituent, a halogen atom, -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -SR ⁸ , - SO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ¹⁰ , or -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ), more preferably -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , or -Si(OR ¹² )(OR ¹³ ) (OR ¹⁴ ), further preferably -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , or -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ), most preferably -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ). In each saturated aliphatic hydrocarbon group, the number of substituents is preferably 1-5, more preferably 1-3, still more preferably 1-2, most preferably 1.

The carbon number of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent is preferably 7 to 20, more preferably 7 to 16, still more preferably 7 to 12, still more preferably 7 to 10, particularly preferably 7 to 8, with 8 being the best. The carbon number of the aromatic hydrocarbon group includes the carbon number of the substituent. The substituent is preferably a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ¹⁰ , or -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ), more Preferably a monovalent saturated aliphatic hydrocarbon group with 1 to 4 carbons, -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , or -SO ₂ NR ⁹ R ¹⁰ . Further preferred are monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , or -SO ₂ NR ⁹ R ¹⁰ . In each aromatic hydrocarbon group, the number of substituents is preferably 1-5, more preferably 1-3, still more preferably 1-2, most preferably 2. The substituent is preferably bonded at the ortho-position and/or meta-position, more preferably at the ortho-position, with respect to the bonding bond of the aromatic hydrocarbon group.

The carbon number of the aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbons as a substituent is preferably 9 to 20, more preferably 9 to 13, still more preferably 9 to 12, and most preferably 9 to 20. The best is 9. The carbon number of the aromatic hydrocarbon group includes the carbon number of the substituent. The aromatic hydrocarbon group preferably does not have a substituent other than the saturated aliphatic hydrocarbon group. In each aromatic hydrocarbon group, the number of the saturated aliphatic hydrocarbon groups is preferably 3-5, more preferably 3-4, most preferably 3. The saturated aliphatic hydrocarbon group is preferably bonded at the ortho-position and/or para-position with respect to the bond of the aromatic hydrocarbon group, more preferably at the ortho-position and para-position. The carbon number of the monovalent saturated aliphatic hydrocarbon group is preferably 1-5, more preferably 1-3, still more preferably 1-2, most preferably 1.

R ^b2 and R ^b3 preferably include a hydrogen atom in the same group as R ² and R ³ above, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Among them, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is more preferred, and a monovalent saturated hydrocarbon group having a substituent having 1 to 20 carbon atoms is still more preferred.

The carbon number of the monovalent saturated hydrocarbon group having 1-20 carbon atoms which may have a substituent is preferably 1-10, more preferably 1-6, still more preferably 1-4. The carbon number of the saturated aliphatic hydrocarbon group is the number of carbons also including the substituent. As the substituent, preferably, a halogen atom, -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ^{8 ,} -SO ₃ ^- , -SO ₃ H, -SO ₃ -Z ⁺ , -SR can be mentioned. ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ¹⁰ , or -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ), more preferably -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^{-Z +} , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , or -Si(OR ¹² )( OR ¹³ )(OR ¹⁴ ), further preferably -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , or -Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ), most preferably -CO ₂ H or -CO ₂ R ⁸ . In each saturated aliphatic hydrocarbon group, the number of substituents is preferably 1-5, more preferably 1-3, still more preferably 1-2, most preferably 1.

Compound (Ia) is preferably Compound No. 1 to Compound No. 15 specified in Formula (Iax) and Table 1.

[Table 1] No. R ^ax1 R ^ax2 R ^ax3 R ^ax4 1 Ph h h Ph 2 Ph _{CH3 CH3} Ph 3 Ph CH ₃ CH ₂ CH ₃ CH ₂ Ph 4 o-tolyl h h o-tolyl 5 o-tolyl _{CH3 CH3} o-tolyl 6 o-tolyl CH ₃ CH ₂ CH ₃ CH ₂ o-tolyl 7 m-tolyl h h m-tolyl 8 m-tolyl _{CH3 CH3} m-tolyl 9 m-tolyl CH ₃ CH ₂ CH ₃ CH ₂ m-tolyl 10 p-tolyl h h p-tolyl 11 p-tolyl _{CH3 CH3} p-tolyl 12 p-tolyl CH ₃ CH ₂ CH ₃ CH ₂ p-tolyl 13 2,6-Xylyl h h 2,6-Xylyl 14 2,6-Xylyl _{CH3 CH3} 2,6-Xylyl 15 2,6-Xylyl CH ₃ CH ₂ CH ₃ CH ₂ 2,6-Xylyl

The symbols in the formula mean the following groups (hereinafter, * represents a bonding bond).

As compound (Ib1), compounds represented by formula (Ibx) and compound No. 16 to compound No. 35 specified in Table 2, and formula A3-1 to formula A3-8 are preferable.

[Table 2] No. ^{Rbx1 Rx2 Rx3 wxya} 16 _{CH3 CH3 CH3} PrTMS 17 CH ₃ CH ₂ CH ₃ CH _{2 CH3} PrTMS 18 CH ₃ CH ₂ CH ₃ CH ₂ CH ₃ CH 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-tolyl PrCOOH PrCOOH p-tolyl twenty three 2,6-Xylyl PrCOOH PrCOOH 2,6-Xylyl twenty four MT1 h h MT1 25 MT1 _{CH3 CH3} MT1 26 MT1 CH ₃ CH ₂ CH ₃ CH ₂ MT1 27 MT2 h h MT2 28 MT2 _{CH3 CH3} MT2 29 MT2 CH ₃ CH ₂ CH ₃ CH ₂ MT2 30 MT3 h h MT3 31 MT3 _{CH3 CH3} MT3 32 MT3 CH ₃ CH ₂ CH ₃ CH ₂ MT3 33 2,4,6-Mesitylyl h h 2,4,6-Mesitylyl 34 2,4,6-Mesitylyl _{CH3 CH3} 2,4,6-Mesitylyl 35 2,4,6-Mesitylyl CH ₃ CH ₂ CH ₃ CH ₂ 2,4,6-Mesitylyl

The symbols in the formula refer to the following groups (the following * represents a bonding bond).

(polymerization initiation aid) The colored curable resin composition of the present invention may further contain at least one polymerization initiation aid (E). A polymerization initiation aid is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound whose polymerization is started by a polymerization initiator. When containing a polymerization start aid (E), it is usually used in combination with a polymerization start agent (C). Examples of polymerization initiation aids (E) include: 4,4'-bis(dimethylamino)benzophenone (commonly known as Michelerone), 4,4'-bis(diethylamine) base) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, etc.

When these polymerization initiation aids are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin and the polymerizable compound. . When the amount of the polymerization initiation adjuvant is within this range, a pattern can be formed with further high sensitivity, and there is a tendency that the productivity of color filters and the like is improved.

(leveling agent) The colored curable resin composition of the present invention may further contain at least one leveling agent. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, and the like. These may have a polymeric group in a side chain.

Examples of the silicone-based surfactant include those having a siloxane bond in the molecule, and the like. Specifically, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (trade name; Toray Dow Corning (shares) ) manufacturing), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Industry Co., Ltd. material (Momentive Performance Materials Japan) Co., Ltd.) etc.

Examples of the fluorine-based surfactant include those having a fluorocarbon chain in the molecule, and the like. Specifically, examples include: Fluorad (registered trademark) FC430, Fluorad (Fluorad) FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac ) F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop ) EF352 (manufactured by Mitsubishi Materials Corporation), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (AGC (stock) manufacturing (formerly Asahi Glass (stock)) and E5844 (Daikin Fine Chemical (Daikin Fine Chemical) Research Institute (stock) manufacturing), etc.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, examples include: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477 and Megafac F443 (DIC ) (share) manufacturing) etc.

When a leveling agent is included, the content of the leveling agent is preferably 0.0005% by mass to 0.2% by mass, more preferably 0.0008% by mass to 0.1% by mass, based on the total amount of the colored curable resin composition. When content of a leveling agent exists in the said range, the flatness of a color filter etc. can be made favorable.

When the colored curable resin composition of the present invention containing the above components is cured to form a cured film, the haze value of the cured film is preferably 8% to 50% when converted to a thickness of 2 μm, more preferably 8% to 50%. It is preferably 10% to 45%, more preferably 13% to 40%, and still more preferably 17% to 35%. The curing conditions when curing the composition to form a cured film are not particularly limited as long as sufficient curing is achieved, for example, at 70° C. or higher for 15 minutes or longer. In addition, the haze value of a cured film can be measured with a haze meter.

(solvent) The colored curable resin composition of the present invention may further contain at least one solvent. The solvent is not particularly limited, and those commonly used in this field can be used. For example, ester solvents (solvents containing -COO- and not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (solvents containing -O- in the molecule) Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (containing OH in the molecule and not containing -O-, -CO - and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, Isopropyl butyrate, Ethyl butyrate, Butyl butyrate, Methyl pyruvate, Ethyl pyruvate, Propyl pyruvate, Methyl acetylacetate, Ethyl acetylacetate, Cyclo Hexanol acetate and γ-butyrolactone, etc.

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, Ethylene 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 ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenetole and methyl anisole, etc.

Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ester, Propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Diethyl 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.

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, etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

As a solvent, it is preferable to include at least one selected from the group consisting of ether solvents, ether ester solvents, and ketone solvents, more preferably include ether solvents and ether ester solvents, and further preferably include propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

The content of the solvent is preferably from 30% by mass to 80% by mass, more preferably from 35% by mass to 75% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the solid content of the colored curable resin composition is preferably from 20% by mass to 70% by mass, more preferably from 25% by mass to 65% by mass. If the content of the solvent is within the above range, the flatness at the time of coating becomes good. In addition, for example, when a colorant is contained, the color density will not be insufficient when forming a color filter, so there is a change in display characteristics. good tendencies.

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

<Manufacturing method of colored curable resin composition> The colored curable resin composition of the present invention can be prepared, for example, by mixing a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, and if necessary, a polymerization initiation aid, a solvent, Leveling agents and other ingredients. A colorant can be prepared using the pigment dispersion liquid. The intended curable resin composition can be prepared by mixing the remaining components in the pigment dispersion so as to have a predetermined concentration. In addition, the mixed curable resin composition is preferably filtered through a filter having a pore diameter of about 0.01 μm to 10 μm.

＜Manufacturing method of cured film＞ As a method of producing a cured film such as a colored pattern from the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, and the like are exemplified. Among them, photolithography is preferred. Photolithography is a method in which the colored curable resin composition is coated on a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In photolithography, by not using a photomask and/or not performing development during exposure, a colored coating film that is a cured film of the colored curable resin composition layer can be formed. A cured film such as a colored pattern or a colored coating film thus formed can be used as a color filter. The film thickness of the cured film, for example, the film thickness of the color filter is not particularly limited, and can be appropriately adjusted according to the purpose or use, for example, 0.1 μm to 30 μm, preferably 0.1 μm to 20 μm, and more preferably 0.5 μm. μm～6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass whose surface is coated with silica; or polycarbonate, polymethyl methacrylate, polyparaffin Resin plates such as ethylene phthalate; silicon; aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the above-mentioned substrates. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of pixels of each color by photolithography can be carried out under known or commonly used devices or conditions. For example, it can be produced as follows. First, the colored resin composition is coated on a substrate, and then dried by removing volatile components such as solvents by heating (pre-baking) and/or drying under reduced pressure to obtain a smooth colored composition layer. As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned. The temperature at the time of heating and drying is preferably from 30°C to 120°C, more preferably from 50°C to 110°C. In addition, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. When performing reduced-pressure drying, it is preferable to carry out at the temperature range of 20-25 degreeC under the pressure of 50 Pa-150 Pa. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the intended color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on this photomask is not specifically limited, The pattern corresponding to the intended use is used. As a light source used for exposure, the light source which emits the light of the wavelength of 250 nm - 450 nm is preferable. For example, for light less than 350 nm, use a filter that cuts off this wavelength range, or for light around 436 nm, around 408 nm, or around 365 nm, use a bandpass filter that extracts these wavelength ranges for selection Sexual take out. Specifically, as a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned. In addition, the exposure dose at a wavelength of 365 nm is preferably 50 J/cm ² to 300 J/cm ² , more preferably 60 J/cm ² to 200 J/cm ² , and still more preferably 65 J/cm 2 ² to 180 J/cm ² . It is preferable to use a mask aligner and a stepper in order to uniformly irradiate the entire exposure surface with parallel light rays or to perform accurate alignment between the mask and the substrate on which the colored composition layer is formed. ) and other exposure devices.

A colored pattern is formed on the substrate by making the exposed colored composition layer contact a developing solution for development. By image development, the unexposed part of a coloring composition layer dissolves in a developing solution, and is removed. As a developing solution, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, or the like is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01% by mass to 10% by mass, more preferably 0.03% by mass to 5% by mass. Furthermore, the developer may also contain a surfactant. The developing method may be any one of a liquid covering method, a dipping method, a spraying method, and the like. Furthermore, the board|substrate can also be inclined at arbitrary angles at the time of image development. After image development, it is preferable to perform water washing.

Furthermore, it is preferable to post-bak the obtained colored pattern. In order to form a color filter used in an organic EL display device, the post-baking temperature may be lower than 200°C, preferably lower than 170°C, more preferably lower than 150°C. In the present invention, post-baking is preferably performed at a lower temperature, for example, at a temperature of 130° C. or lower. The lower limit of the post-baking temperature is preferably at least 70°C, more preferably at least 75°C. The post-baking time is preferably from 1 minute to 120 minutes, more preferably from 5 minutes to 60 minutes.

The film thickness of the coating film after the post-baking is, for example, preferably 3 μm or less, more preferably 2.5 μm or less. The lower limit of the film thickness of the coating film is not particularly limited, but it is usually 0.3 μm or more, and may be 0.5 μm or more.

The cured film of the colored curable resin composition of the present invention obtained after the post-baking has preferably 8% to 50%, more preferably 10% to 45%, and still more preferably 13% when converted to a thickness of 2 μm. ~40%, and more preferably 17%~35% haze value. The haze value of the cured film can be measured with a haze meter. The present invention also provides a cured film of the colored curable resin composition of the present invention.

The cured film obtained by curing the curable resin composition of the present invention is preferably used as a color filter contained in a color filter substrate, more preferably used as an organic EL having a large cavity structure Color filters for display devices. [Example]

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to these examples. In the examples, unless otherwise specified, % and parts indicating the content and the amount used are based on mass.

＜Weight average molecular weight＞ The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using the gel permeation chromatography (GPC) method under the following conditions. The ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained under the following conditions was defined as the molecular weight distribution. Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: Tetrahydrofuran [THF] Flow rate: 1.0 mL/min Solid component concentration of the liquid to be tested: 0.001% by mass to 0.01% by mass Injection volume: 50 μL Detector: RI Standard material for calibration: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

<Synthesis Example 1: Preparation of Pigment Dispersion (A1)> mix: C.I. Pigment Red 291 8.6 parts C.I. Pigment Yellow 139 3.5 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 84 parts, And the pigment was fully dispersed using a bead mill to obtain a pigment dispersion (A1).

<Synthesis Example 2: Preparation of Pigment Dispersion (A2)> mix: C.I. Pigment Green 59 9.6 parts C.I. Pigment Yellow 150 1.7 parts C.I. Pigment Yellow 139 1.5 parts Acrylic pigment dispersant 3.1 parts Propylene glycol monomethyl ether acetate 84 parts, And the pigment was fully dispersed using a bead mill to obtain a pigment dispersion (A2).

<Synthesis Example 3: Preparation of Pigment Dispersion Liquid (A3)> Mixing: CI Pigment Blue 16 9.8 parts of Pink Base (manufactured by Taiyo Fine Chemical Co., Ltd.) 1.6 parts of acrylic pigment dispersant 4.6 parts of propylene glycol 84 parts of monomethyl ether acetate, and the pigment was fully dispersed using a bead mill to obtain a pigment dispersion (A3).

<Synthesis Example 4: Preparation of Pigment Dispersion (A4)> mix: C.I. Pigment Green 36 3.9 parts C.I. Pigment Yellow 185 7.9 parts Acrylic pigment dispersant 4.3 parts Propylene glycol monomethyl ether acetate 84 parts, And the pigment was fully dispersed using a bead mill to obtain a pigment dispersion (A4).

<Synthesis Example 5: Preparation of Pigment Dispersion (A5)> mix: C.I. Pigment Red 254 6.2 parts C.I. Pigment Red 177 6.2 parts Acrylic pigment dispersant 3.6 parts Propylene glycol monomethyl ether acetate 84 parts, And the pigment was fully dispersed using a bead mill to obtain a pigment dispersion (A5).

<Synthesis Example 6: Preparation of Pigment Dispersion (A6)> mix: C.I. Pigment Blue 15:6 12.1 parts C.I. Pigment Violet 23 0.6 parts Acrylic pigment dispersant 3.3 parts Propylene glycol monomethyl ether acetate 84 parts, And the pigment was fully dispersed using a bead mill to obtain a pigment dispersion (A6).

<Synthesis Example 7: Preparation of Resin> Into a flask including a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 277 parts of propylene glycol monomethyl ether acetate were added, stirred while replacing nitrogen, and the temperature was raised to 120°C. Then, 35.3 parts of peroxy-2-ethylhexyl acrylate will be added to the monomer mixture containing 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate and 12.3 parts of dicyclopentyl methacrylate. The substance obtained from tert-butyl hexanoate was added dropwise to the flask from the dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further carried out at 120° C. for 30 minutes to perform a copolymerization reaction to produce an addition copolymer. Then, the inside of the flask was replaced with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine, and 0.8 parts of p-methoxyphenol were put into the addition copolymer solution, and the reaction was continued at 110°C for 10 hours. The epoxy group derived from glycidyl methacrylate reacts with acrylic acid to cleave the epoxy group and introduce a polymerizable unsaturated bond into the side chain of the polymer. Next, 24.2 parts of succinic anhydride was added to the reaction system, and the reaction was continued at 110° C. for 1 hour to react the hydroxyl groups generated by cleavage of epoxy groups with succinic anhydride to introduce carboxyl groups into side chains to obtain polymers. Finally, 383.3 parts of propylene glycol monomethyl ether acetate were added to the reaction solution to obtain a polymer solution having a polymer solid content concentration of 40%. The polystyrene conversion weight average molecular weight of the obtained resin was 6400.

<Scattering intensity in Mie scattering> Using Mieplot (refer to http://www.philiplaven.com/mieplot.htm), which is a calculation program for the scattering intensity in Mie scattering, calculate the inorganic Scattering intensity X in Mie scattering of fine particles.

<Example 1 to Example 6, Reference Example 1 to Reference Example 3, and Comparative Example 1 to Comparative Example 3> (1) Preparation of colored curable resin composition Each component described in Table 3 was mixed so as to have the compounding amount described in Table 3, and a colored curable resin composition was obtained. In addition, when preparing a colored curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition might become 14 weight%. The unit of the compounding amount of each component in Table 3 is "parts by mass", pigment dispersion liquid (A1) ~ pigment dispersion liquid (A6), resin (B), polymerizable compound (C), polymerization initiator (D) , Metal oxide (E) and leveling agent (F) are prepared in terms of solid content.

無機微粒子（E）：氧化鈦（金屬氧化物，平均粒徑161 nm，散射強度8.0，折射率2.7） 調平劑（F）：聚醚改質矽酮油（東麗道康寧（Toray Dow Corning）（股）製造的商品名「東麗矽酮（Toray Silicone）SH8400」）。 The polymerizable compound (C), polymerization initiator (D1), polymerization initiator (D2), inorganic fine particles (E) and leveling agent (F) used in Examples, Reference Examples, and Comparative Examples are as follows. Polymerizable compound (C): dipentaerythritol hexaacrylate-dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-9550") Polymerization initiator (D-1): N-acetyl Oxyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine (PBG-327; oxime compound; Changzhou Qiangli Electronic New Materials Co., Ltd.) polymerized 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 (Toray Dow Corning) (stock) manufactured under the trade name "Toray Silicone (Toray Silicone) SH8400").

[table 3] Pigment dispersion Resin B polymeric compound C polymerization initiator Inorganic particles leveling agent type colorant amount Disperse 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 Reference 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 Reference 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

＜Preparation of cured film＞ On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) Coating by spin coating so that the film thickness after baking becomes 2 μm The colored curable resin compositions of Examples, Comparative Examples, and Reference Examples prepared in the above manner were then prebaked at 90° C. for 1 minute to form a colored composition layer. After standing to cool, the colored composition layer formed on the substrate was exposed to an exposure dose of 100 mJ/cm ² (365 nm benchmark) for light irradiation. After light irradiation, post-baking was performed in an oven at 85° C. for 30 minutes to obtain a colored cured film. The haze of the obtained cured film and the visual field at the time of oblique observation were evaluated according to the following reference|standard. The obtained results are shown in Table 4. In addition, since the cured film of the comparative example 1 - the comparative example 3 cannot form a pattern, the evaluation of the visual field at the time of observation from an oblique direction was not implemented.

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

＜Evaluation of patterning＞ At the time of exposure to form a cured film, as a photomask, one with a line and space pattern of 10 μm was used, and the colored composition layer after light irradiation was mixed with 0.12% of nonionic surfactant and 0.04% of potassium hydroxide. The colored pattern was obtained by dipping and developing at 24° C. for 60 seconds in an aqueous developing solution, and then washing with water. ○: Pattern formation is possible. ×: No pattern can be formed.

<Evaluation of visual field when viewed obliquely> A sheet with a specific pattern cut out is placed 5 cm below the colored cured film, and light is irradiated from below the sheet to transmit the light that has passed through the specific pattern through the cured film. Next, from the inclined direction of about 60 degrees with respect to the cured film plane above the cured film, the sharpness of the texture visible on the cured film surface was evaluated. ◯: Pattern can be recognized. ×: The pattern cannot be discriminated.

[Table 4] patterned Haze[%] oblique view Reference example 1 ○ 0.2 x Example 1 ○ 15.5 ○ Example 2 ○ 19.4 ○ Reference example 2 ○ 0.2 x Example 3 ○ 13.5 ○ Example 4 ○ 18.9 ○ Reference example 3 ○ 0.2 x Example 5 ○ 16.5 ○ Example 6 ○ 22.5 ○ Comparative example 1 x 67.5 - Comparative example 2 x 83.3 - Comparative example 3 x 93.5 -

<Example 7 to Example 12 and Comparative Example 4 to Comparative Example 7> A colored curable resin composition and a cured film were prepared in the same manner as in Example 3 except that the type of the inorganic fine particles was changed to those shown in Table 5, and the amount of the inorganic fine particles added was changed to 5% by mass. Moreover, the haze and oblique visual field of the obtained cured film were evaluated similarly to the above. The obtained results are shown in Table 5. In addition, the evaluation results of patterning were all ◯. In the case of Example 12, since inorganic fine particles having a larger particle diameter were used than those in other Examples, it was found that the particles tended to settle easily.

[table 5] Inorganic particles Haze[%] oblique vision type Refractive index Particle size [nm] Scattering intensity Comparative example 4 TiO ₂ 2.7 69 0.9 0.3 x Example 7 TiO ₂ 2.7 110 4.2 9.3 〇 Example 8 TiO ₂ 2.7 161 8.0 33.3 ◎ Example 9 TiO ₂ 2.7 207 24.8 30.5 ◎ Example 10 TiO ₂ 2.7 243 46.3 30.3 ◎ Example 11 TiO ₂ 2.7 299 81.0 30.7 ◎ Comparative Example 5 _ZrO2 2 46 0.01 0.3 x Comparative Example 6 _ZnO2 1.9 69 0.2 0.3 x Comparative Example 7 SiO ₂ 1.4 95 0.26 0.2 x Example 12 SiO ₂ 1.4 422 596.5 10.2 〇

Claims (10)

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and inorganic fine particles, wherein when the Mie scattering of the inorganic fine particles is When the strength is X, and the content of the inorganic fine particles relative to the solid content of the colored curable resin composition is Y mass %, X is 4 or more and Y is 15 or less, and formula (1): a=X×Y （1） The calculated value a is 10 or more. The colored curable resin composition according to claim 1, wherein the inorganic fine particles are metal oxides. The colored curable resin composition according to claim 1, wherein the inorganic fine particles have a refractive index of 1.3 or higher. The colored curable resin composition according to claim 1, wherein the inorganic fine particles have an average particle diameter of 0.05 μm to 0.70 μm. The colored curable resin composition according to claim 1, wherein the content of the polymerizable compound is 0.1% by mass to 50% by mass relative to the solid content of the colored curable resin composition. The colored curable resin composition according to claim 1, 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. A cured film is a cured film of the colored curable resin composition according to any one of claim 1 to claim 6. The cured film according to claim 7, which has a haze value of 8% to 40% when converted to a thickness of 2 μm. The cured film according to claim 7 constitutes a color filter included in a color filter substrate. A display device comprising the cured film as claimed in Claim 7.