TW201522447A - Colored curable resin composition - Google Patents

Abstract

Provided is a colored curable resin composition comprising (A) a colorant containing green dye, (B) a resin, (C) a polymerizable compound, (D) a polymerization initiator, (E) a solvent and (G) a colorless metal urnplex.

Description

Colored curable resin composition

The present invention relates to a colored curable resin composition and the like.

Japanese Laid-Open Patent Publication No. 2012-168258 discloses a colored curable resin composition comprising a compound represented by formula (h-6), a binder resin, a solvent, a polymerization initiator, and a curing agent, and is formed. A color filter included in a liquid crystal display device or the like, or a solid-state image sensor.

The present invention provides the following [1] to [9].

[1] A colored curable resin composition comprising a green dye-containing color former (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a colorless metal Complex (G).

[2] The colored curable resin composition according to [1], wherein the green dye is at least one selected from the group consisting of a squarylium dye, an anthraquinone dye, and a triarylmethane dye.

[3] The colored curable resin composition according to [2], wherein the green dyeing The material is a squaric acid dye.

[4] The colored curable resin composition according to the above [1], wherein the colorant (A) further comprises at least one selected from the group consisting of a green pigment, a yellow pigment, and a yellow dye.

[5] The colored curable resin composition according to [4], wherein the coloring agent (A) further contains a yellow pigment.

[6] The colored curable resin composition according to [5], wherein the yellow pigment is C.I. Pigment Yellow 138.

[7] A coating film formed of the color-curable resin composition according to [1] to [6].

[8] A color filter formed of the colored curable resin composition according to [1] to [6].

[9] A display device comprising the color filter according to [8].

The color filter made of the colored curable resin composition of the present invention is excellent in heat resistance, and is therefore suitable for use as a color filter of a display device such as a liquid crystal display device.

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a colorless metal complex (G). .

<Colorant (A)>

The colorant (A) contains a green dye.

The green dye can be a direct dye or a mordant dye. The green dye is not particularly limited, and examples thereof include green dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. The green dye may, for example, be classified as a green dye by the Colour Index (published by The Society of Dyens and Colourists), that is, a compound having a hue other than the CI pigment, or a dye recorded in a dyeing notebook (Dyeing Note). Know the green dye.

The chemical structure of the green dye is not particularly limited, and examples of the dye include a triarylmethane dye, an anthraquinone dye, a cyanin dye, a phthalocyanine dye, a naphthoquinone dye, a quinonimine dye, and a methine group. Dyes, methine azo dyes, squaric acid dyes, acridine dyes, and the like.

Among them, a squaraine dye, an anthraquinone dye, and a triarylmethane dye are preferred, and a squaraine dye is more preferred.

The squaric acid dye is not particularly limited, and a green dye having a squaric acid structure can be used. For example, a compound described in JP-A-2013-76926 can be used.

Specifically, a compound represented by the following formula is mentioned.

In the formula (AII-a), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may have a substituent or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ⁵ to R ⁸ each independently represent a hydrogen atom, a hydroxyl group, a mercapto or a trifluoromethyl group, or an alkoxy group having 1 to 4 carbon atoms.

X ¹ and X ² are each independently represented by -N(Xa)(Xb) [wherein, Xa and Xb are each independently an alkyl group having 1 to 20 carbon atoms (the methylene group constituting the alkyl group may be The group represented by an oxygen atom substituted) or an alkoxy group having 1 to 20 carbon atoms.

In the formula (AII-a), the saturated hydrocarbon group may, for example, be an alkyl group having 1 to 20 carbon atoms and an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

The alkyl group may be either a straight chain or a branched chain. Specific 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, and an octyl group.

The alicyclic hydrocarbon group may be either a monocyclic or a polycyclic ring, or may have an alkyl group in the ring. Specific examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.

Examples of the substituent in the phenyl group include a halogen atom such as a fluorine atom, a chlorine atom or an iodine atom; a halogen alkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; a methoxy group or an ethoxy group; An alkoxy group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; a hydroxyl group or the like.

R ¹ to R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.

R ⁵ to R ⁸ are each independently a hydrogen atom, a hydroxyl group, a decyl group or a trifluoromethyl group or an alkoxy group having 1 to 4 carbon atoms, preferably a hydrogen atom or a hydroxyl group.

In the formula (AII-a), the group represented by X ¹ and X ² may be a group represented by the formula (A2-1) to the formula (A2-7). * is a bond that is bonded to a carbon atom.

Further, a group represented by the formula (A3-1) to the formula (A3-6) can be given. * is a bond that is bonded to a carbon atom.

The compound represented by the formula (AII-a) may, for example, be a compound (AII-1) to a compound (AII-14) having a substituent shown in Table 1.

Among the compound (AII-1) to the compound (AII-14), the compound (AII-1) to the compound (AII-7) are preferred from the viewpoint of raw material availability, and the compound (AII-2) is further used. Better.

In addition, the compound represented by the formula (AII-a) may, for example, be a compound (AII-15) to a compound (AII-68) having a substituent represented by Tables 2 and 3.

Among the compound (AII-15) to the compound (AII-68), the compound (AII-16), the compound (AII-23), the compound (AII-29) and the compound (AII-62) are based on the viewpoint of raw material availability. It is preferred that the compound (AII-23) and the compound (AII-29) are more preferred.

As the anthraquinone dye, a green dye having a fluorene structure can be used, and examples thereof include the following compounds.

As the triarylmethane dye, a green dye having a triarylmethane structure can be used, and examples thereof include the following compounds.

The colored curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a green pigment, a yellow pigment, and a yellow dye as the colorant (A), and more preferably further contains a yellow pigment.

For the green pigment, CI Pigment Green 1 (CIPigment Green; which is described below with the exception of CI Pigment Green), which is classified as a pigment by the Colour Index (published by The Society of Dyens and Colourists), 2, 4, and 7 , 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and other pigments. Among them, C.I. Pigment Green 58 is preferred.

The yellow pigment may be exemplified by CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 , 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and the like. Among them, C.I. Pigment Yellow 138 is preferred.

Yellow dyes can be classified as CI Solvent Yellow, CI Acid Yellow, CI Direct Yellow, CI mordant by Colour Index (The Society of Dyens and Colourists). Compound of CIMordant Yellow, coumarin dye, metal-containing azo dye, pyridone azo dye, barbituric azo dye, quinophthalone dye, methine Dyes, indigo dyes.

Specifically, CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI acid yellow 1, 3, 7, 9, 11 , 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128 , 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202 , 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI direct dye yellow 2, 33, 34, 35, 38, 39 , 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI mordant yellow 5, 8, 10 , 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

The coumarin dye may, for example, be the following dye.

The metal-containing azo dye may, for example, be a dye as described below.

The pyridone azo dye may, for example, be the following dye.

The barbiturate azo dye may, for example, be a dye as described below.

The quinophthalone dye may, for example, be the following dye.

The methine dye may, for example, be the following dye.

The indigo dye may, for example, be the following dye.

Yellow dye, preferably coumarin dye, metal containing A nitrogen dye, a pyridone azo dye, a barbiturate azo dye, a quinoline yellow dye, a methine dye, and an indigo dye.

The content of the green dye in the colorant (A) is usually 10 to 100% by mass.

In the colorant (A), the content of at least one dye selected from the group consisting of a squaraine dye, an anthraquinone dye, and a triarylmethane dye is 20 to 100% by mass based on the total amount of the colorant (A). Preferably, 40 to 100% by mass is more preferably 50 to 100% by mass.

In the coloring agent (A), at least one selected from the group consisting of a green pigment, a yellow pigment, and a yellow dye, and at least one selected from the group consisting of a squaraine dye, an anthraquinone dye, and a triarylmethane dye. The ratio of the content of the dye is preferably 60:40 to 99.9:0.1 and more preferably 70:30 to 99:1 based on the mass. At this ratio, the color filter formed of the colored curable resin composition containing the colorant (A) obtained is high in brightness and relatively good in contrast.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, still more preferably 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 of the color filter is sufficient, and the necessary amount of the resin (B) or the polymerizable compound (C) can be contained in the composition, so that it can be formed. A pattern with sufficient mechanical strength.

Here, the "total amount of solid content" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component relative thereto can be, for example, liquid chromatography It is measured by a conventional analytical method such as a method or a 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 unsaturated carboxylic acids and unsaturated carboxylic anhydrides (Ba) (hereinafter sometimes referred to as "(Ba)"), and cyclic ether having a carbon number of 2 to 4 a copolymer of a monomer (Bb) (hereinafter sometimes referred to as "(Bb)")) having an ethylenically unsaturated bond; a resin [K2]; (Ba), (Bb) and a copolymerizable with (Ba) a copolymer of a monomer (Bc) (but (Ba) and (Bb) are different) (hereinafter sometimes referred to as "(Bc)"); a resin [K3]; a copolymer of (Ba) and (Bc); a resin [K4]; a resin which reacts (Bb) with a copolymer of (Ba) and (Bc); a resin [K5]; a resin which reacts a copolymer of (Ba) with (Bb) and (Bc); a resin [K6 a resin obtained by reacting (Ba) with a copolymer of (Bb) and (Bc) and then reacting with a carboxylic acid anhydride.

Specific examples of (Ba) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-(o-), m-(m-), and p-(p-)benzoic acid vinyl ester. Acids; maleic acid, fumaric acid, pyrocitric acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3, 4, 5, Unsaturated dicarboxylic acids such as 6-tetrahydrofurfuric acid, 1,2,3,6-tetrahydrofurfuric acid, dimethyltetrahydrofurfuric acid, 1, 4-cyclohexene dicarboxylic acid; methyl-5- Norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5 -methylbicyclo[2.2.1] Hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy- a bicyclic unsaturated compound containing a carboxyl group such as 6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, pyroic 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 Unsaturated dicarboxylic anhydrides such as anhydride; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, decanoic acid mono [2-(methyl) propylene oxyethyl] ester, etc. The monocarboxylic acid unsaturated mono[(meth)acryloxyalkylalkyl]ester; α-(hydroxymethyl)acrylic acid, etc., an unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity or the solubility of the obtained resin in an aqueous alkali solution.

(Bb) means a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) A polymerizable compound having an ethylenically unsaturated bond. (Bb) is preferably a monomer having a cyclic ether having 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)acryloyl) and "(meth)acrylate" have the same meaning.

Examples of (Bb) include an oxiranyl group and an ethylenic group. An unsaturatedly bonded monomer, a monomer having an oxycyclobutane group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond, and the like.

(Bb) is based on the fact that the reliability of heat resistance and chemical resistance of the color filter can be further improved, and it is preferable to use a monomer having an oxirane group and an ethylenically unsaturated bond.

(Bc), (meth)acrylic acid methyl ester, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid tertiary butyl Ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, cyclopentyl (meth)acrylate, Cyclohexyl methacrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] 癸-8-ester (a common name in the art is ( Methyl)dicyclopentanyl acrylate. Also, sometimes referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.1.02 ^2,6 ]nonene-8-ester (The conventional name in the technical field is "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isodecyl (meth)acrylate, and gold (meth)acrylate. Alkane ester, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc. (methyl) Acrylates; 2-hydroxyethyl (meth)acrylate, 2-hydroxyl (meth)acrylate a hydroxy group-containing (meth) acrylate such as propyl ester; a dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or 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]heptane- 2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[ 2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di (hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2- Alkene, 5-hydroxy 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tri-butoxy Carbonylbicyclo[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(tris-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1] a bicyclic unsaturated compound such as 2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, 3-maleimide benzene N-succinimide formate, N-succinimide, 4-maleimide butyrate, N-succinimide, 6-maleimide caproate, 3-maleimide Dicarbonyl ruthenium derivatives such as N-succinimide propionate and N-(9-acridinyl)maleimide; styrene, α-methylstyrene, m-methylstyrene , p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, based on copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaine Imine, bicyclo [2.2.1] hept-2-ene, etc. are preferred.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricycloacrylate [5.2.1.0]. ^2.6 ] Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide Copolymer, 3-methyl-3-(methyl)propenyloxymethyloxycyclobutane/(meth)acrylic acid/styrene copolymer, etc. [K2]; benzyl (meth)acrylate/ (meth)acrylic acid copolymer, styrene/(meth)acrylic copolymer, etc. [K3]; benzyl (meth)acrylate/(meth)acrylic acid copolymer addition (meth)acrylic acid epoxy a propyl ester resin, a trimethyl decyl (meth) acrylate/styrene/(meth)acrylic acid copolymer, a (meth)acrylic acid propylene acrylate resin, and a tricyclodecyl (meth) acrylate. /Methyl (meth)acrylate/(meth)acrylic acid copolymer addition (meth)acrylic acid a resin such as a propylene acrylate resin [K4]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/glycidyl methacrylate with (meth)acrylic acid; a resin such as a resin obtained by reacting a copolymer of tricyclodecyl acrylate/styrene/glycidyl methacrylate with (meth)acrylic acid [K5]; a tricyclodecyl (meth) acrylate A resin such as a resin such as a resin obtained by reacting a copolymer of (meth)acrylic acid propylene acrylate with (meth)acrylic acid and then reacting with tetrahydrophthalic anhydride [K6].

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

Resin [K1] can be referred to the literature "Experimental method of polymer synthesis" (Dazu Takashi, (share) chemical person release, the first edition of the first brush, 1972 It is manufactured by the method described in the document issued on March 1st, and the references described in the document.

The obtained copolymer may be directly used as a solution after the reaction, or may be a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. In particular, when the polymerization is carried out by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the solution after the reaction can be directly used in the formulation of the colored curable resin composition of the present invention, so that the present invention can be used. The manufacturing steps of the color-curable resin composition of the invention are simplified.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion to the developer is good, and the resolution of the coloring pattern tends to be improved.

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

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

The content of the resin (B) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid content. If the content of the resin (B) is within the above range, then A color pattern can be formed, and the resolution of the coloring pattern and the tendency of the residual film rate to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenic unsaturated bond, etc. The acrylate compound is preferred.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol. Alcohol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentenol octa (meth) acrylate, tripentyltetraol hexa (meth) acrylate, tetraxin Pentaerythritol deca (meth) acrylate, tetrapentaerythritol 九 (meth) acrylate, tris(2-(methyl) propylene oxyethyl) isocyanurate, ethylene glycol modification Neopentyl alcohol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified neopentyl alcohol tetra (meth) acrylate, propylene glycol modified two new Pentaerythritol hexa(meth)acrylate, caprolactone-modified neopentyltetrakis(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, 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) relative to the solid content The total amount is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, still more preferably 17 to 55 mass%. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of formation of the coloring pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

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

The polymerization initiator which generates a living radical may, for example, be an acyloxime compound, an alkylphenone compound, or the like. (triazine) compound, acylphosphine oxide compound and biimidazole compound.

The above O-indenyl hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine or N-benzylformyloxy group. 1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]B Alkan-1-amine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxol Methoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methyl Benzyl hydrazino)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2-methyl) Benzomethylene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as IRGACURE (registered trademark) OXE01, OXE02 (above, BASF) and N-1919 (made by ADEKA) can also be used. among them, O-indenyl hydrazine compound is based on N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzylideneoxy-1 -(4-phenylthiophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentane- At least one selected from the group consisting of 1-keto-2-imine is preferably N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2- The imine is more preferred. If the O-indenyl compound is used for this purpose, there is a tendency for a color filter having high luminance to be obtained.

The phenylalkanone compound may, for example, be 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propan-1-one or 2-dimethylamino group- 1-(4-(N-morpholinyl)phenyl)-2-benzylidenebutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)-methyl 1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy 2-methyl-1-phenylpropan-1-one, 2-hydroxy 2-methyl 1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy 2-methyl-1-(4-isopropenylphenyl) An oligomer of propan-1-one, α,α-diethoxyacetophenone, benzyldimethylketal, and the like. Commercial products such as IRGACURE (registered trademark) 369, 907, and 379 (manufactured by BASF Corporation) can also be used.

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-piperonyl-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.

As the sulfhydrylphosphine oxide compound, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like can also be used. Commercial products such as IRGACURE (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di) Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-double (2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)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 (refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.), 4 An imidazole compound in which a phenyl group at the 4', 5, 5'-position is substituted with an alkoxycarbonyl group (see Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.).

Examples of the polymerization initiator which generates an acid include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethyloxyphenylene. Methyl hydrazine p-toluene sulfonate, 4-ethyl methoxy phenyl. methyl. Benzyl hydrazine hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyl sulfonium p-toluene sulfonate, diphenyl sulfonium hexafluoroantimonate Salts such as salts, nitrobenzyl tosylate, benzoin tosylate, and the like.

Further, the polymerization initiator (D) may be benzoin or ampere Benzoin compounds such as ketone methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; diphenyl ketone, methyl o-benzyl benzoate, 4-phenyl diphenyl ketone , 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl)diphenyl ketone, 2,4,6-three a diphenyl ketone compound such as methyl diphenyl ketone; an anthraquinone compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine or camphor; 10-butyl-2-chloroacridone, diphenylethylene Benzil, phenylglyoxylate, titanocene, and the like.

a polymerization initiator (D) to contain an O-indenyl hydrazine compound, a phenyl ketene compound, and three A polymerization initiator of at least one selected from the group consisting of a compound, a mercaptophosphine oxide compound, and a biimidazole compound is preferred, and a polymerization initiator containing an O-indenylphosphonium compound is more preferable.

The content of the polymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 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 is increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Solvent (E)>

The solvent (E) is not particularly limited and can be used for a solvent which is usually used in the field. For example, an ester solvent (a solvent containing -COO- or a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), and an ether ester solvent (including in-molecular- a solvent for COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule, a solvent not containing -COO-), an alcohol solvent (containing OH in the molecule, not containing -O-, -CO-, and -COO- Solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent 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 acetate, ethyl acetate, cyclohexane Alcohol acetate and γ-butyrolactone.

Examples of the ether solvent 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, and diethyl ether. 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-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and Methyl anisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Ester and the like.

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone, isophorone, and the like.

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 mesylene.

The guanamine solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

Among the above solvents, an organic solvent having a boiling point of 1 atm of 120 ° C or more and 210 ° C or less is preferred because of coating properties and drying properties. As a solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N-dimethyl More preferably, decylamine, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are preferred.

The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of the solid content of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and when a color filter is formed, the color density is not insufficient, so that the color density is not insufficient. The display characteristics tend to become better.

<Colorless metal complex (G)>

The colorless metal complex (G) may, for example, be a zinc complex represented by the formula (10).

[In the formula (10), R ⁸¹ to R ⁸⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a hydroxyl group]

Examples of the alkyl group having 1 to 4 carbon atoms in the formula (10) 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.

Specific examples of the zinc complex represented by the formula (10) include a substituent having a substituent shown in Table 4. Among them, based on the improvement of heat resistance, (10)-18 is preferred.

The content of the colorless metal complex is preferably 0.1% by mass or more and 30% by mass or less based on the coloring agent (A), and more preferably 0.5% by mass or more and 15% by mass or less.

<Other ingredients>

The colored curable resin composition of the present invention may contain other dyes and pigments in the colorant (A).

Examples of other dyes include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, and may be classified as dyes in the Colour Index (published by The Society of Dyens and Colourists). Compound or dyed notebook (color dyeing agency) Know the dye. These dyes may be used singly or in combination of two or more.

Specific examples of other dyes include CI Solvent Orange 2, 7, 11, 15, 26, 56; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63 , 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Direct Dye Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96 , 97, 106, 107; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43 47, 48 and other orange dyes.

The pigment is not particularly limited, and conventional pigments can be used, and examples thereof include pigments classified as pigments in the Colour Index (published by The Society of Dyens and Colourists).

Specific examples of the pigment include orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73.

The colored curable resin composition of the present invention may further contain a polymerization initiation aid, a leveling agent, a filler, another polymer compound, an adhesion promoter, an antioxidant, a photostabilizer, and a chain transfer agent, as needed. Such additives are well known in the art.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can be obtained by using a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a colorless metal complex. (G) and, as needed, the leveling agent (F) and polymerization initiation Other ingredients such as auxiliaries are mixed and formulated.

The dye may also be partially or completely dissolved in a solvent (E) in advance to prepare a solution.

It is preferred that the solution be filtered by a filter having a pore diameter of about 0.01 to 1 μm.

The pigment is preferably mixed with a part or all of the solvent (E) in advance, and is dispersed by a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, a part or all of the pigment dispersant and the resin (B) may be added as needed. In the pigment dispersion liquid thus obtained, the remaining components are mixed so as to have a predetermined concentration, whereby the intended color-curable resin composition is prepared.

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

<Method of Manufacturing Color Filter>

A coating film formed of the colored curable resin composition of the present invention and a color filter formed of the colored curable resin composition are all within the scope of the present invention.

This coating film can be obtained by hardening the said colored curable resin composition. The coating film may also have a coloring pattern.

The film thickness of the coating film is not particularly limited, and can be appropriately adjusted depending on the purpose, use, etc., and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

A method of producing a coloring pattern from the colored curable resin composition of the present invention includes a lithography method, an inkjet method, a printing method, and the like. Whisper The law is better. The lithography method is a method in which the colored curable resin composition is applied onto a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the lithography method, a colored coating film of a cured product of the colored composition layer can be formed by using no mask and/or no development at the time of exposure. The color pattern or colored coating film thus formed 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 preferably 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 cerium oxide, polycarbonate, polymethyl methacrylate or polyethylene terephthalate can be used. A resin plate such as an ester 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 each color pixel by the lithography method can be performed by conventional or conventional devices and conditions. For example, it can be produced as follows.

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

Examples of the coating method include a spin coating method, a slit coating method, a slit, and a spin coating method.

The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Also, as the heating time, from 10 seconds to 60 minutes Preferably, it is better to use 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.

The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the intended color filter.

Next, the colored composition layer is exposed through a photomask for forming a color pattern of interest. The pattern on the reticle is not particularly limited, and a pattern corresponding to the purpose of the purpose can be used.

As the light source for exposure, a light source for generating light having a wavelength of 250 to 450 nm is preferred. For example, light that is less than 350 nm can be blocked by a filter that blocks the wavelength region, and light near 436 nm, near 408 nm, and around 365 nm can be selectively used by using a band pass filter that takes out the wavelength regions. take out. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to use an exposure apparatus such as a photomask alignment machine or a stepper because the uniform parallel light can be irradiated on the entire exposed surface, and the mask and the substrate on which the colored composition layer are formed can be accurately aligned.

The coloring composition layer after exposure is developed in contact with the developing solution, and a color pattern is formed on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed.

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

The development method may be any one of a puddle method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at any angle during development.

After development, it is preferred to perform water washing.

Furthermore, it is preferred to obtain a color pattern for post-baking. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 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 which is particularly excellent in heat resistance can be produced.

The color filter is a color filter used as a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image sensor. A display device including the color filter is also one of the inventions.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited. In the examples, the content and the % and the amount of the use amount are, unless otherwise specified, the basis of the mass.

In the following synthesis examples, the compounds were identified by NMR (JNM-EX-270; (manufactured by JEOL Ltd.)).

Synthesis Example 1: Synthesis of a compound represented by the formula (AII-23)

5.4 parts of N,N-dibutyl-3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 3,4-dihydroxy-3-cyclobutene-1,2-dione (Tokyo Chemical Industry Co., Ltd. ( 1.7 parts, 20-0.7 parts of 1-butanol and 134.1 parts of toluene were mixed. The resulting mixture was stirred at 125 ° C for 5 hours while removing the generated water using a Dean-Stark tube.

After completion of the reaction, the solvent was distilled off, and a small amount of toluene was added thereto, and then 100 parts of water was added to discard the aqueous layer. After repeating the washing operation twice, 50 parts of hexane was added, and the precipitated solid was obtained by filtration. The solid obtained by filtration was dispersed in 5 parts of tetrahydrofuran, and after filtration, the solid was washed with 10 parts of tetrahydrofuran, followed by 25 parts of hexane. The obtained solid was dried under reduced pressure at 60 ° C for 24 hours to obtain 3.23 parts of a compound represented by formula (AII-23).

¹ H-NMR (270 MHz, δ value (ppm, TMS basis), CDCl ₃ ) δ 0.96 (t, 12H), 1.35 (m, 8H), 1.61 (m, 8H) of the compound represented by the formula (AII-23) ), 3.37 (t, 8H), 6.10 (D, 2H), 6.30 (DD, 2H), 7.86 (D, 2H), 12.07 (s, 2H)

Synthesis Example 2

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a gas introduction tube, nitrogen gas was introduced at 0.02 L/min to form a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated while stirring. Up to 70 ° C. Next, 36 parts of acrylic acid, 4,5-epoxytricyclo[5.2.1.0 ^2,6 ]dec-8-ester {i.e., monomer (BI-1)} and 3,4-epoxy 3 of acrylic acid were used. Ring [5.2.1.0 ^2,6 ]癸-8-ester {ie monomer (BII-1)} mixture {monomer (BI-1) in the mixture: monomer (BII-1) molar ratio is 50:50} 264 parts, dissolved in 140 parts of propylene glycol monomethyl ether acetate, and the monomer solution was formulated. The monomer solution was dropped into a 70 ° C-incubated flask using a dropping funnel over 4 hours. On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of a polymerization initiator solution of propylene glycol monomethyl ether acetate, and other drops were used. The funnel took 4 hours and was dropped into the flask. After the completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw: 9000, a molecular weight distribution: 2.0, a solid content of 33%, and a solid content of an acid value of 90 mg-KOH/ g resin B1 solution.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was carried out under the following conditions using a GPC method.

Device; K2479 (made by Shimadzu Corporation)

Pipe string; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

Detector; RI

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

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

Example 1 and Example 2, Comparative Example 1

<Preparation of coloring photosensitive resin composition> Example 1

The following components were mixed to obtain a colored curable resin composition.

Example 2

The following components were mixed to obtain a colored curable resin composition.

Comparative example 1

The following components were mixed to obtain a colored curable resin composition.

[Production of color filter]

The colored curable resin composition was applied by a spin coating method on a glass substrate (#1737; manufactured by Corning Incorporated), and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, it was exposed to an exposure amount (365 nm basis) at 150 mJ/cm ² in an atmosphere using an exposure machine (TME-150RSK; TOPCON). Furthermore, no reticle is used. The exposed color composition layer was placed in an oven and post-baked at 180 ° C for 20 minutes to prepare a color filter (film thickness: 2.8 μm).

[Heat resistance evaluation]

The coating film of the coloring photosensitive resin composition was heated at 230 ° C for 20 minutes, and the color difference (ΔEAB*) before and after heating of the coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS).

The color difference (?EAB*) is such that the smaller the value, the more excellent the heat resistance.

The coating films obtained in Examples 1 and 2 were subjected to the above evaluation of heat resistance, and as a result, the color difference (ΔEAB*) was 8.1 and 10.2, respectively. In the same manner as in Comparative Example 1, the heat resistance was evaluated. As a result, the color difference (ΔEAB*) was 25.1, and it was found that the color filter containing the colored curable resin composition of the present invention was excellent in heat resistance.

[Industry use possibility]

When the colored curable resin composition of the present invention is used, a color filter excellent in heat resistance can be provided. The color filter is a color filter used as a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, or the like) and a solid-state image sensor.

Claims (9)

A colored curable resin composition comprising a green dye-containing color former (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a colorless metal complex. (G). The colored curable resin composition according to claim 1, wherein the green dye is at least one selected from the group consisting of a squarylium dye, an anthraquinone dye, and a triarylmethane dye. The colored curable resin composition according to claim 2, wherein the green dye is a squaric acid dye. The colored curable resin composition according to the first or second aspect of the invention, wherein the colorant (A) further comprises at least one selected from the group consisting of a green pigment, a yellow pigment, and a yellow dye. The colored curable resin composition according to claim 1 or 2, wherein the colorant (A) further contains a yellow pigment. The colored curable resin composition according to claim 5, wherein the yellow pigment is C.I. Pigment Yellow 138. A coating film formed of the color-curable resin composition as described in claim 1 or 2. A color filter formed of the color-curable resin composition as described in claim 1 or 2. A display device comprising the color filter of claim 8 of the patent application.