TWI565759B - Colored curable resin composition - Google Patents

Description

Colored curable resin composition

The present invention relates to a coloring curable resin composition, a coloring pattern, and a color filter, and more particularly to a color filter constituting a liquid crystal display element or a solid-state imaging element, which is suitable for forming a colored image. A colored coloring resin composition, a colored pattern of the colored curable resin composition, and a color filter are used.

The colored curable resin composition is a color filter used for manufacturing a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. As such a color-curable resin composition, a color-curable resin composition containing ethyl lactate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate as a solvent is known (JP 2010-211198-A).

When the colored curable resin composition is applied to a substrate, the colored curable resin composition is applied to the substrate, and then dried under reduced pressure to form a colored composition layer, which is contained in the colored curable resin composition. Solvent Bumping to create a crater-like defect.

The present invention includes the following inventions.

[1] A colored curable resin composition comprising: a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent; and the colorant contains a compound represented by the formula (1) and a pigment, and the solvent contains diacetone alcohol The content of diacetone alcohol is 0.5% by mass or more and 50% by mass or less based on the total amount of the solvent;

[In the formula (1), R ¹ and R ² each independently represent a phenyl group which may have a substituent.

R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The hydrogen atom contained in the hydrocarbon group may be substituted by an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the -CH ₂ - contained in the above saturated hydrocarbon group may also be -O-, - CO- or -NR ¹¹ - substituted.

R ¹ and R ³ may form a ring containing a nitrogen atom together with a nitrogen atom, and R ² and R ⁴ may form a ring containing a nitrogen atom together with a nitrogen atom.

R ⁵ represents: -OH, -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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m is an integer representing 0 to 4. When m is 2 or more, a plurality of R ⁵ may be the same or different.

R ⁸ is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ .

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocyclic ring of 3 to 10 members together with a nitrogen atom.

R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

[2] The colored curable resin composition according to the above [1], wherein the solvent is further selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, and a ring. At least one of a group consisting of ketone and ethyl 3-ethoxypropionate.

[3] A color filter formed by the colored curable resin composition according to the above [1] or [2].

[4] A display device comprising the color filter according to [3].

According to the colored curable resin composition of the present invention, even after coating on a substrate, drying is carried out under reduced pressure to form a colored composition layer, and defects having a crater shape are small.

The colored curable resin composition of the present invention contains a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

The coloring agent (A) is a compound containing the formula (1) (hereinafter referred to as "compound (1)") and a pigment (A2).

The colored curable resin composition of the present invention is preferably a complex, levelling agent (F).

The colored curable resin composition of the present invention may contain a polymerization initiation aid (D1).

In the present specification, the compounds as the respective components are exemplified, and they may be used singly or in combination of plural kinds unless otherwise specified.

<Colorant (A)>

The compound (1) is represented by the above formula (1).

In R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ , examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and a octyl group. a linear alkyl group having 1 to 20 carbon atoms such as a thiol group, a fluorenyl group, a fluorenyl group, a dodecyl group, a hexadecanyl group or a hexyl group; an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a branched chain alkyl group having 3 to 20 carbon atoms such as isopentyl, neopentyl, 2-ethylhexyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms.

Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and the like. Isoyloxy and the like.

Examples of the -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tertiary butoxycarbonyl group, a hexyloxycarbonyl group, and a hexyloxycarbonyl group.

Examples of -SR ⁸ include a methylsulfanyl group, an ethylthio group, a butylthio group, a hexylthio group, a mercaptothio group, and a decylthio group.

Examples of the -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, a decylsulfonyl group, and the like. .

Examples of the -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tertiary butoxysulfonyl group, a hexyloxysulfonyl group, and 20 Alkoxysulfonyl and the like.

As -SO ₂ NR ⁹ R ¹⁰ , for example, sulfamoyl; N-methylamine sulfonyl, N-ethylamine sulfonyl, N-propylamine sulfonyl, N- Isopropylamine sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tertiary butylamine sulfonyl, N-tert-butylamine sulfonyl, N - amylamine sulfonyl, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1,2-dimethyl Propyl sulfonyl, N-(2,2-dimethylpropyl)amine sulfonyl, N-(1-methylbutyl)amine sulfonyl, N-(2-methylbutyl Aminesulfonyl, N-(3-methylbutyl)aminesulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N-(1,3-dimethyl Butyl)aminesulfonyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N -(1,4-Dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl N-1 substituted amine sulfonyl group such as hexylamine sulfonyl group, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine sulfonyl group, N,N-ethylmethylamine sulfonyl, N,N-diethylamine sulfonate N,N-propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tertiary butylmethylamine sulfonyl, N,N-butylethyl An N,N-2 substituted amine sulfonyl group such as an aminesulfonyl group, an N,N-bis(1-methylpropyl)aminesulfonyl group or an N,N-heptylmethylaminesulfonyl group.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 member nitrogen-containing heterocyclic ring together with a nitrogen atom. Examples of the hetero ring include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³ and R ⁴ include those having 1 to 10 carbon atoms in the R ⁸ saturated hydrocarbon group.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. In the group of the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms, the alkyl group having 1 to 3 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group or a different group. The propyl group; in the case of the alkoxy group having 1 to 3 carbon atoms, a methoxy group, an ethoxy group, a n-propoxy group and an isopropoxy group are exemplified.

Examples of the saturated hydrocarbon group substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a tolylmethyl group, a tolylethyl group, and a tolylpropyl group. Tolylbutyl, methoxyphenylmethyl, methoxyphenylethyl, methoxyphenylpropyl, methoxyphenylbutyl and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The saturated hydrocarbon group substituted with a halogen atom may, for example, be a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group or a chlorobutyl group.

R ³ and R ^{4 are} preferably an unsubstituted saturated hydrocarbon group having 1 to 10 carbon atoms, preferably a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. For better.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and a secondary butyl group. Tertiary butyl, isopentyl, neopentyl and the like.

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

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , ideally ⁺ N(R ¹¹ ) ₄ .

As the above ⁺ N(R ¹¹ ) ₄ , it is preferred that at least two of the four R ¹¹ are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60.

The phenyl group indicating R ¹ and R ² also has a substituent. Examples of the substituent include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO. ₂ R ⁸ , -SO ₃ R ⁸ and -SO ₂ NR ⁹ R ¹⁰ . Among these substituents, -R ^{8 is} preferred, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferred. As the case of -SO ₃ ^- Z ⁺ , -SO ₃ ^-+ N(R ¹¹ ) _{4 is} preferred.

Examples of the phenyl group having a substituent include tolyl, dimethylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, methylsulfanylphenyl, and methylsulfonium. Methyl phenyl (methylsulfonylphenyl) and the like. Among them, a phenyl group having a substituent with respect to the ortho position to the nitrogen-bonding bond is preferred.

R ¹ and R ² are independent of each other, preferably a phenyl group having a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, preferably a tolyl group or a dimethylphenyl group, ortho-tolyl group or 2,6-. Dimethylphenyl is more preferred.

R ¹ and R ³ may form a ring containing a nitrogen atom together with a nitrogen atom, and R ² and R ⁴ may form a ring containing a nitrogen atom together with a nitrogen atom. Examples of the ring containing a nitrogen atom include the following.

As R ⁵ , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ^{10 are} preferred.

R ⁶ and R ⁷ are preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.

m is preferably an integer of 0 to 2, more preferably 1 or 2.

As the compound (1), a compound represented by the formula (2) is preferred.

[In the formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 4 carbon atoms.

p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of R ^{23 's} may be the same or different from each other, and when q is 2 or more, a plurality of R ^{24 's} may be the same or different. ]

Examples of the alkyl group having 1 to 4 carbon atoms representing R ²¹ , R ²² , R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a secondary butyl group. , tertiary butyl, etc.

R ²¹ and R ²² are each preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. R ²³ and R ²⁴ are preferably a methyl group.

p and q are preferably integers of 0 to 2, more preferably 1 or 2.

As the compound (1), a compound represented by the formula (3) is preferred.

[In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms.

R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

The alkyl group having 1 to 4 carbon atoms which represents R ³¹ to R ³⁶ may be the same as the above.

R ³¹ and R ³² are each independently and preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. R ³³ to R ³⁶ are each independently and preferably a hydrogen atom or a methyl group.

The compound (1) may, for example, be a compound represented by any one of the formulae (1-1) to (1-15). Among them, from the viewpoint of excellent solubility in an organic solvent, the compound represented by the formula (1-1), the formula (1-2) or the formula (1-5) to the formula (1-12) is good.

The method for producing the compound (1) includes reacting a compound represented by the formula (1a) with a compound represented by the formula (1b) and a compound of the formula (1c) in the presence of an organic solvent or without a solvent. Methods. From the viewpoint of productivity, it is preferred to carry out the reaction in the absence of a solvent. The reaction temperature is preferably from 30 ° C to 180 ° C, more preferably from 80 ° C to 130 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 3 hours to 8 hours.

In the formulae (1b) and (1c), R ¹ to R ⁴ each have the same meaning as described above.

Examples of the organic solvent include a hydrocarbon solvent such as toluene or xylene; a halogenated hydrocarbon solvent such as chlorobenzene, dichlorobenzene or chloroform; an alcohol solvent such as methanol, ethanol or butanol; a nitro hydrocarbon solvent such as nitrobenzene; and a methyl group; A ketone solvent such as isobutyl ketone; a guanamine solvent such as 1-methyl-2-pyrrolidone;

The compound represented by the formula (1b) and the compound represented by the formula (1c) are preferably used in an amount of from 1 mol to 8 mol per mol, more preferably 1 mol, per mol of the compound represented by the formula (1a). Below 5 ears below the ear. It is possible to carry out the reaction in stages or in the same time.

From the viewpoint of easy production of the compound (1), it is preferred that the compound represented by the formula (1b) has the same structure as the compound represented by the formula (1c).

The method of obtaining the compound (1) of the objective compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture may be mixed together with an acid (for example, acetic acid or the like), and the precipitated crystals may be collected by filtration. The above acid is preferably prepared by previously adding an aqueous solution of an acid to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C or more and 50 ° C or less. Further, it is preferred to stir at the same temperature for about 0.5 to 2 hours. The crystals to be collected are washed with water or the like, and preferably dried. Further, it can be further purified by a known method such as recrystallization as needed.

Examples of the pigment (A2) include organic pigments and inorganic pigments, and examples thereof include compounds classified as pigments by a colour index (published by The Society of Dyers and Colourists).

Specific examples of the pigment include: CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242. Red pigments such as 254, 255, 264, and 265; CI pigment blue (Pigment blue) 15, 15:3, 15:4, 15:6, 60 and other blue pigments; CI Pigment Violet (Pigment violet) 1, 19, 23 , purple pigments such as 29, 32, 36, 38; CI pigment green (Pigment green) 7, 36, 58 and other green pigments.

Among them, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15:3, 15:6 is preferred; C.I. Pigment Blue 15:6 is more preferred.

The above-mentioned pigment may be carried out as needed: rosin treatment, surface treatment using a pigment derivative or a pigment dispersant into which an acidic group or a basic group is introduced, or a surface of a pigment by a polymer compound or the like The grafting treatment, the micronization treatment by a sulfuric acid micronization method, the removal treatment by an organic solvent or water for removing impurities, the removal treatment by an ion exchange method using ionic impurities, or the like. Further, the pigment is preferably one having a uniform particle diameter. A pigment can be obtained by dispersing it by containing a pigment dispersant A pigment dispersion in a uniformly dispersed state in a solution.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include a silicone type, a fluorine type, an ester type, a cationic type, an anionic type, a nonionic type, an amphoteric type, a polyester type, and a poly A surfactant such as an amine or an acrylic resin may be used alone or in combination of two or more. As the surfactant, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amines In addition to modified polyurethanes and polyethylenimines, the following trade names are available: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), and EFTOP (Mitsubishi Materials Electronics) Chemical Co., Ltd.), Megafac (made by DIC Corporation), Fluorade (made by Sumitomo 3M Co., Ltd.), Asahiguard (made by Asahi Glass Co., Ltd.), Surflon (made by AGC Seimichemical Co., Ltd.), and Solsperse (Zeneca Co., Ltd.) EFKA (manufactured by CIBA Co., Ltd.), Ajisper (manufactured by Ajinomoto FINE TECHNO Co., Ltd.), Disperbyk (manufactured by BYK CHEM Co., Ltd.), and the like.

When the pigment dispersant is used, the amount thereof is preferably 1 part by mass or less per 1 part by mass of the pigment, more preferably 0.05 part by mass or more and 0.5 part by mass or less. When the amount of the pigment dispersant used is within the above range, it is preferred because a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the compound (1) is preferably 0.1% by mass or more and 60% by mass or less, and more preferably 0.1% by mass or more and 30% by mass or less based on the total amount of the coloring agent (A).

The content of the pigment (A2) is preferably 40% by mass or more and 99.9% by mass or less based on the total amount of the coloring agent (A), and more preferably 70% by mass or more and 99.9% by mass or less.

The coloring agent (A) may contain a coloring agent different from the compound (1) and the pigment (A2), without impairing the color performance range of the colored curable resin composition of the present invention.

The content of the colorant (A) is desirably from 5 to 60% by mass, more desirably from 8 to 55% by mass, and more desirably from 10 to 50% by mass, based on the total amount of the solid content. When the content of the coloring agent (A) is within the above range, the color density at the time of the color filter is sufficient, and since a necessary amount of the resin or the polymerizable compound can be contained in the composition, a pattern having sufficient mechanical strength can be formed. Here, the "total amount of solid content" in the present specification means the amount of the solvent content removed from the total amount of the colored curable resin composition. The total amount of the solid component and the content of each component relative thereto can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but an alkali-soluble resin is preferred. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (a) (hereinafter referred to as "(a)"), and a ring having a carbon number of 2 to 4. a copolymer of an ether structure and an ethylenically unsaturated bond monomer (b) (hereinafter referred to as "(b)"); a resin [K2]: (a) and (b), and (a) Copolymerized monomer (c) (however, (a) and (b) are different.) (hereinafter referred to as "(c)"); resin [K3]: (a) and ( c) copolymer with; resin [K4]: resin which reacts (b) with the copolymer of (a) and (c); resin [K5]: copolymerizes (a) with (b) and (c) Resin for reaction; resin [K6]: a resin which reacts (a) with the copolymer of (b) and (c) and further reacts with a carboxylic anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, and the like. Kang acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrogen Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5 -carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]g 2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxyl a bicyclic unsaturated compound containing a carboxyl group such as -6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid Anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydroortho Unsaturated dicarboxylic acid anhydride such as phthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono [2-(methyl) propylene methoxyethyl ester], a monovalent or higher polycarboxylic acid unsaturated mono[(meth)acryloxyalkyl]ester such as phthalic acid mono[2-(methyl) propylene methoxyethyl ester]; such as α-(hydroxyl) An unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule of methyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride or the like is preferred from the viewpoint of copolymerization reactivity or the solubility of the available resin to the aqueous alkali solution.

In the case of (b), for example, it means a cyclic ether structure having a carbon number of 2 to 4 (for example, at least selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring. One type) a polymerizable compound with an ethylenically unsaturated bond. (b) It is preferred to use a monomer having a cyclic ether structure of 2 to 4 carbon atoms and a (meth)acryloxy group.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

(b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), having an oxetane Monomer of oxetanyl and ethylenically unsaturated bonds (b2) (hereinafter referred to as "(b2)"), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(b3)").

(b1), for example, a monomer (b1-1) having a structure in which an aliphatic unsaturated hydrocarbon having a linear or branched chain is epoxidized (hereinafter referred to as "(b1-1)" In the case of the monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(B1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and epoxy. Propyl vinyl ether, o-vinylbenzyl epoxypropyl ether, m-vinylbenzyl epoxypropyl ether, p-vinylbenzyl epoxypropyl ether, α-methyl-o-ethylene Base benzyl epoxypropyl ether, α-methyl-m-vinylbenzyl epoxypropyl ether, α-methyl-p-vinylbenzyl epoxypropyl ether, 2,3-double (ring Oxypropyloxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-double ( Epoxypropyl oxymethyl)styrene, 2,3,4-cis (glycidoxymethyl)styrene, 2,3,5-glycol(epoxypropyloxymethyl)styrene, 2 , 3,6-glycol (epoxypropyloxymethyl)styrene, 3,4,5-glycol(epoxypropyloxymethyl)styrene, 2,4,6-paraxyl (epoxypropyloxy) Methyl) styrene and the like.

(b1-2), vinyl cyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), (A) 3,4-epoxycyclohexylmethyl acrylate (example) For example, Cyclomer A400; (manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), and formula (I) The compound and the compound represented by the formula (II).

In the formulae (I) and (II), R ^a and R ^{b each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a and X ^b is a: a single ^{bond, -R c -, * - R} c -O -, * - R c -S- or * -R ^c -NH-.

R ^c is an alkanediyl group having 1 to 6 carbon atoms.

* is a bond indicating the bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, and a tertiary butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

Examples of R ^a and R ^b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group. More preferably, a hydrogen atom and a methyl group are mentioned.

As the alkanediyl, a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane- 1,5-diyl, hexane-1,6-diyl and the like.

As X ^a and X ^b , an ideal one may be exemplified by a single bond, a methylene group, an ethylidene group, a *-CH ₂ -O- group, and a *-CH ₂ CH ₂ -O- group. More preferably, a single bond and *-CH ₂ CH ₂ -O- (* is a bond indicating O).

The compound represented by the formula (I) may, for example, be a compound represented by the formula (I-1) to the formula (I-15). The ideal one can be exemplified by the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I). -15) the compound shown. More preferably, it is a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

The compound represented by the formula (II) may, for example, be a compound represented by the formula (II-1) to the formula (II-15). The ideal one can be exemplified by the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II). Compounds shown in II-15). More preferably, it is a compound represented by Formula (II-1), Formula (II-7), Formula (II-9) or Formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When a compound represented by the formula (I) and a compound represented by the formula (II) are used in combination, the content ratio [the compound represented by the formula (I): the compound represented by the formula (II)] is in the form of Mohr. The benchmark is ideally 5:95 to 95:5, more ideally 20:80 to 80:20.

As (b2), a monomer having an oxetane group and a (meth) acryloxy group is more preferable. (b2) may, for example, be 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl 3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxyethyl Oxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3-ethyl 3-propenyloxyethyloxetane and the like.

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

(b) is preferably (b1) from the viewpoint of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, from the viewpoint of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid III. Butyl methacrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate , cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl (meth) acrylate (in the technical field) The customary name is "dicyclopentanyl methacrylate". In addition, there is a case called "tricyclodecyl (meth) acrylate.), three rings [5.2.1.0 ^2,6 Terpene-8-yl (meth) acrylate (known in the art as "dicyclopentenyl (meth) acrylate).), dicyclopentyloxyethyl (meth) acrylate, Isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthalene (meth)acrylate Ester, benzyl (meth) acrylate, etc. Ethyl esters; (hydroxy) (meth) acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; diethyl maleate, diethyl fumarate a dicarboxylic acid diester such as diethyl itaconate; a bicyclo [2.2.1] hept-2-ene, a 5-methyl bicyclo [2.2.1] hept-2-ene, a 5-ethyl bicyclic ring [2.2.1] Hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2' -hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]heptane- 2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(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]hept-2-ene, 5,6-diethoxy Base ring [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-tris-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(tertiary butoxycarbonyl) ) Ring [2.2.1] hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenyl mala Imine, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimidobenzoate, N-succinimide Base-4-maleimido butyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimidopropyl Dicarbonyl ruthenium derivatives such as acid esters, N-(9-acridinyl) maleimine; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene , vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, ethylene chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butyl Alkene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl group Maleic imine, bicyclo [2.2.1] hept-2-ene, etc. are preferred.

In the resin [K1], in terms of the ratio of each structural unit, among all the structural units constituting the resin [K1], it is preferably: a structural unit derived from (a); 2 to 60 mol% is derived from The structural unit of (b); 40 to 98 mol%, more preferably: structural unit derived from (a); 10 to 50 mol% of structural unit derived from (b); 50 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 when a colored pattern is formed, and the solvent resistance of the obtained color filter are obtained. Excellent tendency.

The resin [K1] can be, for example, referred to in the document "Experimental method for polymer synthesis" (the method described in the issue of the 1st edition of the Chemicals Co., Ltd., the first issue of the Chemicals Co., Ltd., issued on March 1, 1972). Manufactured from the cited documents described in this document.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator and a solvent are used. The reaction vessel may be placed in a reaction vessel, for example, by substituting nitrogen for nitrogen, and heating and holding the mixture while stirring in a deoxidizing environment. Moreover, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and those generally used in the field can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic. The solvent (E) may be a solvent, and the solvent (E) of the color-curable resin composition of the present invention may, for example, be a solvent to be described later.

Further, the copolymer obtained may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. In particular, the solvent used in the polymerization is used by preparing the solution of the colored curable resin composition of the present invention by using the solvent contained in the colored curable resin composition of the present invention. The manufacturing steps of the colored curable resin composition of the present invention are simplified.

In the resin [K2], in terms of the ratio of each structural unit, among all the structural units constituting the resin [K2], preferred are structural units derived from (a); 2 to 45 mol% are derived from Structural unit of (b); 2 to 95 mol% of structural unit derived from (c); 1 to 65 mol%, more preferably: structural unit derived from (a); 5 to 40 mol% The structural unit derived from (b); 5 to 80 mol% of the structural unit derived from (c); 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance of the obtained color filter, The heat resistance and mechanical strength tend to be excellent.

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

In the resin [K3], among the structural units derived from the respective structural units, among all the structural units constituting the resin [K3], preferred are: structural units derived from (a); 2 to 60 mol% are derived from The structural unit of (c); 40 to 98 mol%, more preferably: structural unit derived from (a); 10 to 50 mol% of structural unit derived from (c); 50 to 90 mol%.

The resin [K3] can be produced, for example, in the same manner as the method described in the method for producing the resin [K1].

The resin [K4] can be obtained by adding (b) a cyclic ether having 2 to 4 carbon atoms to the carboxylic acid (a) after the copolymer of (a) and (c) is obtained. / or made of carboxylic anhydride.

First, it is the same as the method described in the manufacturing method of the resin [K1]. The copolymers of (a) and (c) were produced in the same manner. In this case, the ratio derived from each structural unit is preferably the same ratio as those listed in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms which is contained in (b) is reacted with a part of the carboxylic acid (a) derived from the above copolymer and/or a carboxylic anhydride.

Continuously manufacturing the copolymer of (a) and (c), replacing the ambient gas in the flask with nitrogen to form air, and reacting (b), a carboxylic acid or a carboxylic anhydride with a cyclic ether (for example, A diol [K4] can be produced by putting a polymerization inhibitor (for example, hydroquinone or the like) into a flask, for example, by reacting at 60 to 130 ° C for 1 to 10 hours.

The amount of (b) used is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. In this range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained colored pattern become Good tendency. Since the cyclic ether has high reactivity and does not easily remain unreacted (b), it is preferable to use (b1) as the (b) in the resin [K4], and it is more preferable to use (b1-1).

The amount of the above-mentioned reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

The reaction conditions such as the method of the preparation, the reaction temperature, and the time can be appropriately adjusted in consideration of the heat generation amount by the production equipment or the polymerization. Further, in the same manner as the polymerization conditions, it is possible to consider the amount of heat generated by the production equipment or polymerization, and the like. Adjust the method or reaction temperature to be properly adjusted.

The resin [K5], in the first stage, was operated in the same manner as the above-mentioned method for producing the resin [K1] to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may be a solution in which the reaction is used as it is, or a solution which is concentrated or diluted, or a solid (powder) which is taken out by reprecipitation or the like.

The ratio of the structural units derived from (b) and (c) is preferably from (b) structural units; 95% by mole derived from (c) structural units; from 5 to 95 mol%, more preferably from (b) structural units; from 10 to 90 mol% from (c) structural units; from 10 to 90 mol %.

Further, (b) having the carboxylic acid or carboxylic acid anhydride (a) having a copolymer derived from (b) and (c) is the same as the method for producing the resin [K4]. The cyclic ether reacts to obtain the resin [K5].

The amount of (a) used for the reaction of the above copolymer is preferably from 5 to 80 moles, relative to (b) 100 moles. Since the reactivity of the cyclic ether is high and the unreacted (b) does not easily remain, the (b) used in the resin [K5] is preferably (b1), more preferably (b1-1).

Resin [K6], a resin in which a carboxylic anhydride is further reacted with a resin [K5].

The carboxylic anhydride is reacted with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydroortene. Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene Anhydride, etc. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mol with respect to the amount of (a) used.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricycloacrylic acid [5.2.1.0]. ^2.6 ] resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid ring Oxypropyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer a resin such as 3-methyl-3-(methyl)propenyloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/( Methyl)acrylic acid copolymer, resin such as styrene/(meth)acrylic acid copolymer [K3]; addition of benzyl (meth)acrylate/(meth)acrylic acid copolymer to glycidyl (meth)acrylate Resin, a resin of trimethyl decyl (meth) acrylate/styrene/(meth)acrylic acid copolymer addition to glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / ( Benzyl (meth) acrylate / (meth) acrylate copolymer addition (meth) acrylate ring a resin such as an oxypropyl acrylate resin [K4]; a resin obtained by reacting a copolymer of (meth)acrylic acid with tricyclodecyl (meth) acrylate/glycidyl (meth) acrylate to make (meth)acrylic acid a resin such as a resin which reacts with a copolymer of tricyclodecyl (meth) acrylate/styrene/glycidyl methacrylate; [K5]; (meth)acrylic acid to tricyclopentadienyl (meth)acrylate A resin such as a copolymer of a copolymer/glycidyl (meth)acrylate and a resin such as a resin which is further reacted with tetrahydrophthalic anhydride [K6].

Among them, the resin (B) is preferably a resin [K1] and a resin [K2].

The polystyrene-equivalent weight average molecular weight of the resin (B) is desirably 3,000 to 100,000, more desirably 5,000 to 50,000, and more desirably 5,000 to 30,000. When the molecular weight is within the above range, the residual film ratio is high, and the solubility of the unexposed portion in the developer is good, and there is a tendency to obtain a high-resolution and high-hardness colored pattern.

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

The acid value of the resin (B) is desirably 50 to 170 mg-KOH/g, more desirably 60 to 150 mg-KOH/g, and more desirably 70 to 135 mg-KOH/g. The acid value is a measured value (mg) of potassium hydroxide required for neutralizing 1 g of the resin (B), and can be obtained, for example, by titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is desirably from 7 to 65 mass%, more desirably from 13 to 60 mass%, and more desirably from 17 to the total amount of the solid content. 55% by mass. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical derived from the polymerization initiator (D) and/or an acid, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. It is desirable to use a (meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trishydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, ginseng (2-(methyl) propylene methoxyethyl) isocyanate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol Pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate Ester and the like.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 1,500 or less.

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, still more preferably from 17 to 55% by mass, based on the total amount of the solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of formation of the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is a compound which can generate a living radical, an acid, or the like by the action of light or heat, and is not particularly limited as long as it can initiate polymerization, and a known polymerization initiator can be used.

As the polymerization initiator (D), it contains a compound selected from the group consisting of alkyl ketone (Alkylphenone), three A polymerization initiator of at least one of a compound, an acylphosphine oxide, an O-mercapto fluorene compound, and a biimidazole compound, preferably a polymerization initiator containing an O-mercapto fluorene compound The agent is better.

The aforementioned O-indenyl ruthenium compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * is a binding bond.

Examples of the O-indenyl ruthenium compound include N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imide and N-benzidine. Oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3- Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl Ethyl-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxa) Cyclopentylmethyloxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2- Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2) -Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure OXE 01, OXE 02 (above, BASF) and N-1919 (made by ADEKA) can also be used. Wherein the O-indenyl hydrazine compound is selected from the group consisting of N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyl hydrazine 1-(4-phenylthiophenyl)octane-1-one-2-imine, and N-benzylideneoxy-1-(4-phenylthiophenyl)-3- At least one of the group of cyclopentylpropan-1-one-2-imine is preferably N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1- Keto-2-imine is more preferred. In the case of these O-fluorenyl ruthenium compounds, there is a tendency to obtain a color filter having high luminance.

The aforementioned alkyl benzophenone compound has a partial structure represented by the formula (d2) Or a compound of a partial structure represented by the formula (d3). In these partial structures, the benzene ring may also have a substituent.

As the compound having a partial structure represented by the formula (d2), for example, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)- ]]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (manufactured by BASF Corporation) can also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4] -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Olefin of ketone, α,α-diethoxyethyl benzene, benzyl dimethyl ketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

As the aforementioned three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

Examples of the phosphine oxide include 2,4,6-trimethylbenzimidium diphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis (2,3). -dichlorobenzene)-4,4',5,5'-tetraphenylbiimidazole (for example, reference: JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene) Bismuthimide, 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 JPS 48-38403-B, JPS 62-174204-A, etc.), 4, 4' An imidazole compound in which a phenyl group at the 5,5'-position is substituted with a carbon alkoxy group (for example, refer to JPH07-10913-A, etc.) and the like.

Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Compound; benzophenone, o-benzonitrile benzoic acid methyl ester, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl)benzophenone a benzophenone compound such as 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine or hydrazine; 10-butyl-2-chloropurine A ketone, a benzyl group, a methyl phenylglyoxylate, a titanocene compound, or the like. These are preferably used in combination with a polymerization initiation aid (D1) (especially an amine) to be described later.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethylphosphonium phenyl dimethacrylate. Base p-toluenesulfonate, 4-acetoxyphenyl/methyl/benzylphosphonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate , bismuthium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate and the like, or nitrobenzyl tosylate, benzoin tosylate (benzoin) Tosylate) class and so on.

The content of the polymerization initiator (D) is desirably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity of the color filter is improved because of the high sensitivity and the tendency of the exposure time to be shortened.

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is a compound used to promote polymerization of a polymerizable compound which starts polymerization by a polymerization initiator, and is used for sensitization. Agent. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxy fluorene compound, a thioxanthone compound, and a carboxylic acid compound.

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

The alkoxy ruthenium compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the oxythiazinone compound include 2-isopropyloxathiazinone, 4-isopropyloxythiazinone, 2,4-diethyloxythiazinone, and 2,4. - chlorothiazinone, 1-chloro-4-propoxy oxazinone, and the like.

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

When the polymerization initiator (D1) is used, the content thereof is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Parts by mass. When the amount of the polymerization starting aid (D1) is within this range, the colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) contains diacetone alcohol (that is, 4-hydroxy-4-methylpentan-2-one), and the content of diacetone alcohol is 0.5% by mass or more and 50% by mass based on the total amount of the solvent. % or less is preferably 1% by mass or more and 30% by mass or less.

As a solvent in combination with diacetone alcohol, it is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, cyclohexanone, and 3-ethoxypropionic acid At least one of the ester groups is more preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate and ethyl lactate.

The content of the solvent (E) is desirably 70 to 95% by mass, and more desirably 75 to 92% by mass, based on the coloring curable resin composition. In other words, the solid content of the colored curable resin composition is desirably 5 to 30% by mass, more desirably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is improved, and the color density is not insufficient when the color filter is formed. Therefore, the display characteristics tend to be good, which is preferable.

<leveling agent (F)>

Examples of the leveling agent (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom.

Examples of the polyfluorene-based surfactant include a surfactant of a decane bond. Specifically, Toray Silicone DC3PA, SH7PA of the same series, DC11PA of the same series, SH21PA of the same series, SH28PA of the same series, SH29PA of the same series, SH30PA of the same series, polyether modified polyoxygenated oil SH8400 (trade name: Toray Silicone; manufactured by Toray. Dow Corning Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF- 4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), and the like.

The fluorine-based surfactant may, for example, be a surfactant of a fluorocarbon chain. Specifically, it can be mentioned: Fluorade (trade name) FC430, FC431 of the same series (manufactured by Sumitomo 3M Co., Ltd.); Megafac (business Product name) F142D, F171 of the same series, F172 of the same series, F173 of the same series, F177 of the same series, F183 of the same series, R30 of the same series, F554 of the same series (made by DIC Corporation); EFTOP (trade name) EF301, the same series of EF303, the same series of EF351, the same series of EF352 (Mitsubishi Materials Electronics Co., Ltd.); Surflon (trade name) S381, the same series S382, the same series SC101, the same series SC105 ( Asahi Glass Co., Ltd.); E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.); BM-1000, BM-1100 (all manufactured by BM Chemie Co., Ltd.).

Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, BL 20 of the same series, F475 of the same series, F477 of the same series, F443 of the same series (made by DIC Corporation), and the like.

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.05% by mass or less.

<Other ingredients>

The colored curable resin composition of the present invention may contain a filler, another polymer compound, an adhesion promoter, and an antioxidant as needed. Light stabilizers, chain transfer agents, etc., are well known in the art.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a viewpoint. The leveling agent (F), the polymerization starting aid (D1), and other components to be used are mixed and prepared.

The pigment (A2) is preferably mixed with a part or all of the solvent (E) in advance, and is dispersed by a beads mill or the like so that the average particle diameter of the pigment is about 0.2 μm or less. At this time, the pigment dispersant or a part or all of the resin (B) may be blended as needed. By mixing the components remaining in the pigment dispersion obtained in this manner to a predetermined concentration, the intended color-curable resin composition can be prepared.

The compound (1) may be prepared by dissolving a solution in a part or all of the solvent (E) in advance. It is preferred to filter the solution with a filter having a pore diameter of about 0.01 to 1 μm.

It is preferred to filter the mixed colored curable resin composition by a filter having a pore diameter of about 0.1 to 10 μm.

<Method of Manufacturing Color Filter>

Examples of the method for producing a colored pattern from the color-curable resin composition of the present invention include photolithography, ink-jet method, and printing method. Among them, photolithography is preferred. In the photolithography method, the coloring curable resin composition is applied onto a substrate to dry it. A method of drying to form a colored composition layer, exposing the colored composition layer through a photomask, and developing it. In the present invention, the colored pattern means a patterned colored coating film. In the photolithography method, the colored coating film of the cured product of the colored composition layer can be formed without using a photomask during exposure and/or without development. The colored pattern or colored coating film formed in this manner is the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more desirably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda-lime glass coated with silica, or polycarbonate or polymethyl can be used. A resin plate such as methyl acrylate or polyethylene terephthalate or ruthenium or the like, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.

The formation of the respective color pixels by the photolithography method can be carried out using known or conventional devices or conditions. For example, it can be produced in the following manner.

First, a colored curable resin composition is applied onto a substrate, and the volatile components such as a solvent are removed by heat drying (prebaking) and/or drying under reduced pressure, and dried to obtain a smooth composition layer.

The coating method can be exemplified by a spin coating method, a slit coating method, and a narrow method. Seam and spin coating methods.

The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C at a pressure of from 50 to 150 Pa. In the colored curable resin composition of the present invention, even when the drying under reduced pressure is carried out under such conditions, the effect of so-called crater-like defects is small.

The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected in accordance with the film thickness of the color filter of interest.

Next, the colored composition layer is exposed by a photomask that is used to form a colored pattern for the purpose. The pattern on the photomask is not particularly limited, and is a pattern that is used for the purpose.

As the light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm may be blocked by a filter that blocks the wavelength region, or a band-pass filter that intercepts light near 436 nm, near 408 nm, and around 365 nm may be used. The light in these wavelength regions is selectively taken out. Specific examples thereof include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, and the like.

In order to uniformly illuminate the light uniformly in the entire exposed surface, or to properly align the reticle with the substrate on which the colored composition layer is formed, a mask aligner and a stepper are used ( Stepper) and other exposure devices are preferred.

A colored pattern is formed on the substrate by contacting the exposed coloring composition layer with the developing solution and developing it. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed.

As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration of such a basic compound in an aqueous solution is desirably 0.01 to 10% by mass, preferably 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

For the development method, any one of a puddling method, a dipping method, and a spray method can be used. It is also possible to further tilt the substrate to an arbitrary angle during development.

After development, it is preferred to perform water washing.

Further, post-bake is preferably performed on the obtained coloring pattern. The post-baking temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

According to the colored curable resin composition of the present invention, a color filter having particularly few defects can be produced. The color filter is a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state imaging device.

(Example)

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.

In the case of "%" and "parts", unless otherwise specified, the mass % and mass parts are indicated.

[Synthesis Example 1]

20 parts of the compound of the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was stirred at 110 ° C for 6 hours. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour, and then crystals were precipitated. The precipitated crystals were obtained by suctioning the residue to be filtered, and dried to obtain 24 parts of the compound of the formula (1-1). The yield was 80%.

Identification of the compound of formula (1-1); (mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 603.4 exact molecular weight (Exact Mass): 602.2

[Synthesis Example 2]

Except that N-isopropyl-2,6-dimethylaniline was substituted for N-ethyl-o-toluidine, the same procedure as in Synthesis Example 1 was carried out to obtain a formula (1-6). Show compound.

Identification of compounds represented by formula (1-6)

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 659.4 exact molecular weight: 658.3

[Synthesis Example 3]

In a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (X0-1) and a compound represented by the formula (X0-2) (trade name: Chugai Aminol Fast Pink R; manufactured by a Chinese company) 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide were added, and while maintaining at 20 ° C or lower with stirring, 10.9 parts of thionyl chloride was added dropwise. After the completion of the dropwise addition, the temperature was raised to 50 ° C, the same temperature was maintained for 5 hours, and the reaction was allowed to proceed, followed by cooling to 20 ° C. The cooled reaction solution was maintained at 20 ° C or lower while stirring, and a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours and allowed to react. Next, after the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and vigorously stirred. This mixture was added while stirring a mixture of 375 parts of ion-exchanged water to precipitate crystals. Filtration of the precipitated crystals for ion exchange The water was sufficiently washed and dried under reduced pressure at 60 ° C to obtain 11.3 parts of the xanthene dye X1 (a mixture of the compound of the formula (X-1-1) to the formula (X-1-8)).

[Synthesis Example 4]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was passed through at 0.02 L/min to form a nitrogen atmosphere, and 220 parts of ethyl lactate was placed, and the mixture was heated to 70 ° C while stirring. Next, a mixture of 84 parts of methacrylic acid and 3,4-epoxytricyclo[5.2,1.0 ^2.6 ]mercaptoacrylate (the compound represented by the formula (I-1) and the compound represented by the formula (H-1). (The ratio (mol ratio) was 50:50) 336 parts were dissolved in 140 parts of ethyl lactate, and a solution was prepared. The solution was dropped for 4 hours using a dropping funnel, and the mixture was kept at 70 ° C in a flask.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 95 parts of ethyl lactate, and the other dropping funnel was used for 4 hours to drip down. Inside the flask. After completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a resin B1 solution having a solid content of 48%. The resin B1 had a weight average molecular weight of 8.0 × 10 ³ , a molecular weight distribution (Mw / Mn) of 2.5, and an acid value in terms of solid content of 104 mg - KOH / g. The resin B1 has the structural unit shown below.

The weight average of the polystyrene equivalent of the resin obtained in the synthesis example The measurement of the sub-quantity (Mw) and the number average molecular weight (Mn) was carried out under the following conditions using the GPC method.

Device; K2479 (made by Shimadzu Corporation)

Pipe string; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 mL/min

Detector; RI

Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (made by Tosoh Corporation)

The ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was taken as a molecular weight distribution.

Examples 1 to 6 and Comparative Example 1 [Preparation of coloring curable resin composition]

Each component was mixed so as to have the composition shown in Table 1, and the colored curable resin composition was obtained.

In Table 1, "A2-1" is a mixture of propylene glycol monomethyl ether acetate in an amount described in the column of "E-3 ² " in an acrylic pigment dispersant, and is dispersed in advance.

The column "E-3 ¹⁾ " indicates the total content of propylene glycol monomethyl ether acetate.

In Table 1, each component represents the following. The resin (B) is the content (parts) of the solution.

Colorant (A): 1-1: a compound represented by formula (1-1)

Colorant (A): 1-6: a compound represented by formula (1-6)

Colorant (A): X-1: xanthene dye X1

Colorant (A): A2-1: C.I. Pigment Blue 15: 6 (pigment)

Resin (B): Resin B1 solution

Polymerizable compound (C): dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.; KAYARAD (registered trademark) DPHA)

Polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation )

Solvent (E): E-1: diacetone alcohol

Solvent (E): E-2: ethyl lactate

Solvent (E): E-3: Propylene glycol monomethyl ether acetate

Solvent (E): E-4: Propylene glycol monomethyl ether

Leveling agent (F): Fluorine-based surfactant (Megafac (registered trademark) F554; DIC Corporation)

The content ratio of each solvent contained in the prepared color hardening resin composition is shown in Table 2 with respect to the total amount of the solvent contained.

<Production of coloring pattern>

The colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by a spin coating method, and then prebaked at 100 ° C for 3 minutes to obtain a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) was used, and in an atmosphere, 150 mJ/cm. The exposure amount of ² (365 nm reference) irradiated light. The mask is formed using a line width/space pattern of 100 μm. The colored composition layer after the light irradiation was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C for development for 60 seconds, and after washing with water, in an oven, Post-baking at 230 ° C for 30 minutes gave a colored pattern.

[Measurement of film thickness]

For the obtained coloring pattern, a film thickness measuring device (DEKTAK3; The film thickness was measured by Nippon Vacuum Technology Co., Ltd.).

[Colorimetric evaluation]

A color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used for the obtained coloring pattern, and the spectroscopic measurement was performed, and the XY chromaticity coordinates in the XYZ color system of CIE were measured using the characteristic coefficient of the C light source (x). , y) and tristimulus value Y. The larger the value of Y, the higher the brightness. The results are shown in Table 3.

[Defect Evaluation]

On a glass substrate (Eagle 2000; manufactured by Corning Incorporated) having a thickness of 2 μm, the film thickness after drying was 2.3 μm, and the colored curable resin composition was applied by a spin coating method, and then a vacuum dryer was used (VCD). Microtek Co., Ltd.) was dried under reduced pressure to a pressure of 100 Pa to obtain a colored composition layer. With respect to the obtained colored composition layer, the surface was observed using a surface shape optical microscope (magnification: 250 times; VF-7510; manufactured by Keyence Corporation). The number of crater-like defects on the substrate is ○ in the case of three or less, Δ in the case of three or more and ten or less, and X in the case of more than ten. The results are shown in Table 2.

[foreign object assessment]

The surface of the colored composition layer was observed by a surface shape optical microscope (magnification: 250 times; VF-7510; manufactured by Keyence Co., Ltd.) in the same manner as in the defect evaluation, and it was confirmed that the foreign matter was ○. The case where the foreign matter is not confirmed is X. The results are shown in Table 3.

The colored curable resin composition of the present invention is a defect in which a crater-like shape is less likely to occur even after coating on a substrate and drying under reduced pressure to produce a colored composition layer.

Claims (4)

A colored curable resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent; the colorant contains a compound represented by the formula (1) and a pigment, and the solvent contains diacetone alcohol The content of the diacetone alcohol is 0.5% by mass or more and 50% by mass or less based on the total amount of the solvent; In the formula (1), R ¹ and R ² each independently represent a phenyl group which may have a substituent, and R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and hydrogen contained in the saturated hydrocarbon group The atom may be substituted by an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. The -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ¹¹ -, and R ¹ and R ³ may form a ring containing a nitrogen atom together with a nitrogen atom, R ² and R ⁴ may also form a ring containing a nitrogen atom together with a nitrogen atom, and R ⁵ represents -OH, -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 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m represents an integer of 0 to 4, and m is 2 or more. When a plurality of R ^{5 's} may be the same or different from each other, R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or carbon a monovalent saturated hydrocarbon group of 1 to 20, and R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocyclic ring of 3 to 10 members together with a nitrogen atom, and R ¹¹ each independently represents a hydrogen atom and a carbon number of 1 to 20 The monovalent saturated hydrocarbon group is an aralkyl group having 7 to 10 carbon atoms. The colored hardening resin composition according to claim 1, wherein the solvent is further selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, and cyclohexanone. And at least one of the group consisting of ethyl 3-ethoxypropionate. A color filter formed by the colored curable resin composition according to claim 1 or 2. A display device comprising the color filter of claim 3 of the patent application.