CN107092165A - Colored curable resin composition, colour filter and the display device comprising the colour filter - Google Patents

Abstract

The present invention provides a colored curable resin composition comprising a colorant (A), a resin (B), and a polymerizable compound, and a color filter and a display device using the colored curable resin composition. (C) and polymerization initiator (D), coloring agent (A) contains C.I. The (meth)acrylate (c1) of at least 1 sort(s) among the group which consists of an alkane-modified dipentaerythritol hexa(meth)acrylate.

Description

Colored curable resin composition, color filter and display device comprising same

technical field

The present invention relates to a colored curable resin composition, a color filter, and a display device including the color filter.

Background technique

In recent years, liquid crystal display devices have been developed to widen the displayable color gamut, and as part of this, darker color filters are required. As a method of darkening a color filter, a method of increasing the concentration of a colorant in a color filter is mentioned. However, when the concentration of the coloring agent is increased, the performance of the colored curable resin composition, such as deterioration of the pattern shape, deteriorates. On the other hand, there is a method of obtaining a dark color filter by using a colorant with high tinting strength. However, when the coloring agent with high coloring power is used, the brightness|luminance of the color filter obtained will fall. In addition, a method of expressing a dark color by making a color filter into a thick film is also mentioned. However, when a thickened color filter is applied to a liquid crystal display device, color mixing of light occurs between the color filter and adjacent pixels (adjacent pixels).

Japanese Patent Application Laid-Open No. 2011-084726 describes the coloring and curability of color filters including C.I. Pigment Green 58 as a polyhalogenated zinc phthalocyanine pigment and a polymerizable compound containing an ethylenically unsaturated compound modified with ethylene oxide. combination.

Contents of the invention

The present invention provides a colored curable resin composition, a color filter, and a display device shown below.

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),

The above-mentioned colorant (A) contains C.I. Pigment Green 59,

The polymerizable compound (C) contains at least one selected from the group consisting of ethylene oxide-modified dipentaerythritol penta(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate ( Meth)acrylate (c1).

[2] The colored curable resin composition according to [1], wherein the polymerizable compound (C) further contains a (meth)acryloyl group-containing compound ( c2).

[3] The colored curable resin composition according to [1] or [2], wherein the (meth)acryloyl group-containing compound (c2) is selected from trimethylolpropane tri(meth)acrylate , Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, three Pentaerythritol hepta(meth)acrylate, tetraerythritol deca(meth)acrylate, tetraerythritol nona(meth)acrylate, tris(2-(meth)acryloxyethyl)isocyanurate, Ethylene glycol modified pentaerythritol tetra(meth)acrylate, propylene oxide modified pentaerythritol tetra(meth)acrylate, propylene oxide modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate A compound in the group consisting of (meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the content of the (meth)acrylate (c1) is 100% by mass of the polymerizable compound (C). Medium is 20% by mass or more.

[5] A color filter formed of the colored curable resin composition according to any one of [1] to [4].

[6] A display device including the color filter described in [5].

Description of drawings

FIG. 1 is a schematic cross-sectional view showing a colored pattern having a forward tapered shape.

Fig. 2 is a schematic cross-sectional view showing a colored pattern having an inverted tapered shape.

detailed description

＜Colored curable resin composition＞

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), the colorant (A) contains C.I. Pigment Green 59, and the polymerizable compound ( C) (meth)acrylic acid containing at least one selected from the group consisting of ethylene oxide-modified dipentaerythritol penta(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate Esters (c1). The colored curable resin composition of this invention can form the color filter compatible with high brightness and excellent pattern shape.

Hereinafter, each component will be described in detail, and the compounds exemplified as each component in the present specification can be used alone or in combination of two or more unless otherwise specified.

[1] Colorant (A)

The colored curable resin composition of the present invention contains C.I. Pigment Green 59 as a colorant (A).

The content of C.I. Pigment Green 59 in the colorant (A) is usually 10 to 100% by mass in 100% by mass of the colorant (A), and is preferably 30% by mass or more from the viewpoint of effectively achieving both high brightness and excellent pattern shape , more preferably 40% by mass or more, still more preferably 45% by mass or more.

The colored curable resin composition of the present invention may further contain other colorants other than C.I. Pigment Green 59 as the colorant (A). In this case, the content of C.I. Pigment Green 59 may be 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less in 100% by mass of the colorant (A). .

The other colorants other than C.I. Pigment Green 59 may be pigments other than C.I. Pigment Green 59, or may be dyes. Also available for both.

Other colorants may be used alone or in combination of two or more. Examples of other pigments include organic pigments and inorganic pigments, and examples include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

Pigments other than C.I. Pigment Green 59 include:

C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 16, 60 and other blue pigments;

C.I. Pigment Green 7, 36, 58 and other green pigments other than C.I. Pigment Green 59;

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments;

C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments;

wait.

Among them, the other pigments other than C.I. Pigment Green 59 are preferably yellow pigments. Among the yellow pigments, C.I. Pigment Yellow 138, 139, 150, 185 and the like are preferably contained, and C.I. Pigment Yellow 138 is more preferably contained.

When the colored curable resin composition of the present invention contains the above-mentioned preferred yellow pigment and C.I. Pigment Green 59, a color filter showing better brightness can be obtained.

From the viewpoint of effectively achieving both high brightness and excellent pattern shape, it is preferable to increase the content of C.I. Pigment Green 59 in the green colorant. The content of C.I. Pigment Green 59 in the green colorant is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more in 100% by mass of the green colorant. , most preferably 100% by mass.

The above-mentioned other colorants may be dyes. Known dyes can be used as the dye, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Dyes include, for example, compounds classified as substances having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (色红ノート) (色滑社) . In addition, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azo Methine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, etc. Among these, organic solvent-soluble dyes are preferable.

When the colorant (A) contains other colorants than C.I. Pigment Green 59, the content of the other colorants in 100% by mass of the colorant (A) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, 40% by mass or more.

The total content of the colorant (A) in the colored curable resin composition is usually 10 to 60% by mass in 100% by mass of the solid content of the colored curable resin composition, from the viewpoint of achieving both high brightness and excellent pattern shape , in 100 mass % of solid content of a colored curable resin composition, Preferably it is 15-50 mass %, More preferably, it is 20-50 mass %.

In addition, in this specification, "the solid content of a colored curable resin composition" means all components other than a solvent (E) among the components contained in a colored curable resin composition.

The various pigments used in the preparation of the colored curable resin composition are preferably in the state of a dispersion liquid uniformly dispersed in a solvent. In addition, the pigment preferably has a uniform particle diameter. The above-mentioned dispersion liquid can be obtained by mixing a pigment and a solvent. A pigment dispersant can be mixed as needed. A pigment dispersion in which the pigment is uniformly dispersed in a solvent can be obtained by carrying out a dispersion treatment containing a pigment dispersant.

Pigment dispersants can use commercially available surfactants, silicone, fluorine, ester (including polyester), cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic and other surfactants.

Specific examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, poly In addition to ethyleneimine, etc., as indicated by trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOREN (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Ajisper (registered trademark) (Ajinomoto Fine-Techno Co., Inc.), Disperbyk (BYK-CHEMIE Corporation), etc. Pigment dispersants may be used alone or in combination of two or more.

When using a pigment dispersant, the usage-amount is preferably 100 mass parts or less with respect to 100 mass parts of pigments, More preferably, it is 5-50 mass parts. When the usage-amount of a pigment dispersant exists in the said range, the pigment dispersion liquid of a uniform dispersion state tends to be obtained easily.

It does not specifically limit as a solvent which comprises a pigment dispersion liquid, The thing similar to the solvent (E) mentioned later which may be contained in a colored curable resin composition is mentioned.

Among them, the solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc., more Preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3- Ethoxy ethyl propionate etc. Two or more solvents may be used in combination.

The amount of the solvent used is not particularly limited, but is preferably an amount such that the solid content in the pigment dispersion liquid is 3 to 20% by mass, more preferably 5 to 18% by mass.

The various pigments used in the preparation of the colored curable resin composition may be subjected to rosin treatment, surface treatment using pigment derivatives for introducing acidic groups or basic groups, pigment dispersants, etc. Grafting treatment on the surface of pigments, micronization treatment by sulfuric acid micronization method, etc., or cleaning treatment using organic solvents, water, etc. for removing impurities, removal treatment of ionic impurities by ion exchange method, etc. .

[2] Resin (B)

The colored curable resin composition of this invention contains resin (B). The colored curable resin composition may contain 1 type, or 2 or more types of resins as resin (B). The resin (B) is preferably an alkali-soluble resin. Alkali solubility refers to the property of being soluble in a developing solution which is an aqueous solution of an alkali compound. The resin (B) includes the following resins [K1] to [K6] and the like.

Resin [K1]: At least one kind selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (a) [hereinafter sometimes referred to as "(a)"] and a cyclic ether structure having 2 to 4 carbon atoms A copolymer with an ethylenically unsaturated bond monomer (b) [hereinafter sometimes referred to as "(b)"].

Resin [K2]: (a) and (b) and monomer (c) copolymerizable with (a) (it should be noted that it is different from (a) and (b)) [hereinafter sometimes referred to as "(c) ”) of copolymers.

Resin [K3]: a copolymer of (a) and (c).

Resin [K4]: a resin obtained by reacting (b) with a copolymer of (a) and (c).

Resin [K5]: a resin obtained by reacting (a) with a copolymer of (b) and (c).

Resin [K6]: a resin obtained by reacting (a) with a copolymer of (b) and (c), and further reacting a carboxylic anhydride.

(a) Specifically, it may include:

(Meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid and other unsaturated monocarboxylic acids;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid Dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[ 2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1] hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1, 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (nadic anhydride), etc. Unsaturated dicarboxylic anhydrides;

Unsaturation of polyhydric carboxylic acids with more than two valences such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate Mono[(meth)acryloyloxyalkyl]esters;

Unsaturated (meth)acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid, and the like.

Among them, (a) is preferably (meth)acrylic acid, maleic anhydride, or the like from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution.

In addition, in this specification, "(meth)acrylic acid" means at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. The same applies to expressions such as "(meth)acryloyl" and "(meth)acrylate".

(b) means a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring). species) and polymerizable compounds with ethylenically unsaturated bonds. (b) Preferably, it is a monomer which has a C2-C4 cyclic ether structure and a (meth)acryloyloxy group.

(b) For example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as "(b1)"], a monomer having an oxetanyl group and an ethylenically unsaturated bond Body (b2) [hereinafter sometimes referred to as "(b2)"], monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as "(b3)"], and the like.

Examples of (b1) include a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter sometimes referred to as "(b1-1)"], a monomer having an unsaturated alicyclic hydrocarbon ring Monomer (b1-2) of the oxidized structure [hereinafter may be referred to as "(b1-2)"].

(b1-1) Examples of glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl Base ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl o-vinyl benzyl glycidyl ether, α-methyl 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyl 2,5-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tri (glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Chemical Industry Co., Ltd.), (meth)acrylic acid 3 , 4-epoxycyclohexyl methyl ester (such as CYCLOMERA400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl methyl (meth)acrylate (such as CYCLOMER M100; manufactured by Daicel Chemical Industry Co., Ltd.), formula Compounds represented by (I), compounds represented by formula (II), and the like.

In formula (I) and formula (II), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X ¹ and X ² independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * Indicates the connection bit with O.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.

Alkyl groups whose hydrogen atoms are substituted by hydroxyl groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1 -Methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group constituting R ^c include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1 , 5-dibasic. X ¹ and X ² are preferably single bonds, methylene, ethylene, *-CH ₂ -O- (* represents the connection position with O), *-CH ₂ CH ₂ -O-, more preferably Single bond, *-CH ₂ CH ₂ -O- group.

Specific examples of the compound represented by formula (I) include compounds represented by formula (I-1) to formula (I-15). Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) and formula (I-11) to formula (I-15) The compounds shown are more preferably compounds represented by formula (I-1), formula (I-7), formula (I-9) and formula (I-15).

Examples thereof include hexane-1,6-diyl and the like.

Specific examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15). Preferred are formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11) ~ formula (II-15) The compounds shown are more preferably compounds represented by formula (II-1), formula (II-7), formula (II-9) and formula (II-15).

Each of the compound represented by formula (I) and the compound represented by formula (II) can be used alone. In addition, they can also be mixed in any ratio. When mixing, the mixing ratio is preferably 5:95 to 95:5, more preferably 10:90 to 90 in terms of the compound represented by formula (I): the compound represented by formula (II) [molar ratio]. :10, more preferably 20:80 to 80:20.

The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Preferable examples of (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, Butane, 3-methyl-3-(meth)acryloyloxyethyl oxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetane.

The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group.

Preferable examples of (b3) include tetrahydrofurfuryl acrylate (for example, VISCOAT V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Specific examples of (c) include:

Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylate-2 -Ethylhexyl, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate ester, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate [in this technical field, known as "Dicyclopentyl (meth)acrylate". In addition, it is also sometimes called "tricyclodecanyl (meth)acrylate"], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate [in this technical field, as a customary The name is called "dicyclopentenyl (meth)acrylate"], dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate (meth)acrylates such as ester, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc. ;

Hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2 .1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5- Methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6 -Dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1 ]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5 - tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2 -ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, etc. unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleimide Imide propionate, N-(9-acridyl)maleimide and other dicarbonyl imide derivatives;

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

Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) is preferably benzyl (meth)acrylate, tricyclodecanyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. Moreover, since (c) is excellent in developability at the time of pattern formation, benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable.

In resin [K1], it is preferable that the ratio derived from each structural unit exists in the following range among all the structural units which comprise resin [K1].

Structural unit derived from (a): 2 to 50 mol% (more preferably 10 to 45 mol%),

Structural unit derived from (b), especially structural unit derived from (b1): 50 to 98 mol% (more preferably 55 to 90 mol%).

When the ratio of the structural unit of resin [K1] exists in the said range, it exists in the tendency which is excellent in storage stability, developability, and the solvent resistance of the pattern obtained.

Resin [K1] can refer to the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin First Edition, First Printing, March 1, 1972) and the method described in this document. citations for manufacturing.

Specifically, a method is mentioned in which a predetermined amount of (a) and (b) (especially (b1)), a polymerization initiator, a solvent, etc. are charged into a reaction vessel, and stirred, heated, and kept warm in a deoxygenated atmosphere. In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, The polymerization initiator, solvent, etc. commonly used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxides (peroxide benzoyl oxide, etc.). What is necessary is just to dissolve each monomer as a solvent, and the solvent (E) etc. which are described below can be used as a solvent of a colored curable resin composition.

It should be noted that the obtained copolymer may be used as it is after the reaction, or as a concentrated or diluted solution, or as a solid (powder) taken out by reprecipitation or the like. In particular, at the time of this polymerization, by using the solvent (E) mentioned later as a solvent, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

In resin [K2], it is preferable that the ratio derived from each structural unit exists in the following range among all the structural units which comprise resin [K2].

Structural unit derived from (a): 4 to 45 mol% (more preferably 10 to 30 mol%),

Structural unit derived from (b), especially structural unit derived from (b1): 2 to 95 mol% (more preferably 5 to 80 mol%),

Structural unit derived from (c): 1 to 65 mol% (more preferably 5 to 60 mol%).

When the ratio of the structural unit of resin [K2] exists in the said range, it exists in the tendency which is excellent in storage stability, developability, the solvent resistance of the obtained pattern, heat resistance, and mechanical strength.

Resin [K2] can be produced in the same manner as the method described as the production method of resin [K1]. Concretely, the following method can be mentioned: a predetermined amount of (a), (b) (especially (b1)) and (c), a polymerization initiator, and a solvent are put into a reaction container, and stirring and heating are carried out under a deoxidizing atmosphere. , insulation. The resulting copolymer may be used as it is after the reaction, or as a concentrated or diluted solution, or as a solid (powder) taken out by reprecipitation or the like.

In resin [K3], it is preferable that the ratio derived from each structural unit exists in the following range among all the structural units which comprise resin [K3].

Structural unit derived from (a): 2 to 55 mol% (more preferably 10 to 50 mol%),

Structural unit derived from (c): 45 to 98 mol% (more preferably 50 to 90 mol%).

Resin [K3] can be produced in the same manner as the method described as the production method of resin [K1].

Resin [K4] can be produced by obtaining a copolymer of (a) and (c), by cycloadding the cyclic ether structure having 2 to 4 carbon atoms in (b), especially the ethylene oxide in (b1) Carboxylic acid and/or carboxylic acid anhydride possessed in (a), thus produced. Specifically, first, the copolymer of (a) and (c) is manufactured similarly to the method described as the manufacturing method of resin [K1]. In this case, the ratios derived from the respective structural units are preferably in the following ranges among all the structural units constituting the copolymer of (a) and (c).

Structural unit derived from (a): 5 to 50 mol% (more preferably 10 to 45 mol%),

Structural unit derived from (c): 50 to 95 mol% (more preferably 55 to 90 mol%).

Next, the cyclic ether structure having 2 to 4 carbon atoms in (b), especially the oxirane ring in (b1), is combined with the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer. part of the reaction. Specifically, following the manufacture of the copolymer of (a) and (c), the atmosphere in the flask is replaced by nitrogen to air, and (b) (especially (b1)), carboxylic acid or carboxylic anhydride and cyclic ether structure The reaction catalyst (such as three (dimethylaminomethyl) phenol, etc.) and the polymerization inhibitor (such as hydroquinone, etc.) are added in the flask, and the reaction can be carried out at 60 ~ 130 ° C for 1 ~ 10 hours, so that Resin [K4] was obtained.

The usage-amount of (b), especially the usage-amount of (b1), is preferably 5-80 mol with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to be favorable. Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for resin [K4], and (b1-1) is more preferable.

It is preferable that the usage-amount of the said reaction catalyst is 0.001-5 mass % with respect to the total amount of (a), (b) (especially (b1)), and (c). It is preferable that the usage-amount of the said polymerization inhibitor is 0.001-5 mass % with respect to the total amount of (a), (b) and (c).

Reaction conditions such as a feeding method, reaction temperature, and time can be appropriately adjusted in consideration of production equipment, heat generation by polymerization, and the like. In the same manner as the polymerization conditions, the method of feeding and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value obtained by polymerization, and the like.

About resin [K5], as a 1st stage, it carries out similarly to the manufacturing method of above-mentioned resin [K1], and obtains the copolymer of (b) (especially (b1)) and (c). Similar to the above, the obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution may be used, or a solid (powder) taken out by reprecipitation or the like may be used.

It is preferable that the ratio of the structural unit derived from (b) (especially (b1)) and (c) exists in the following range with respect to the total molar amount of all the structural units which comprise the said copolymer.

Structural unit derived from (b), especially structural unit derived from (b1): 5 to 95 mol% (more preferably 10 to 90 mol%),

Structural unit derived from (c): 5 to 95 mol% (more preferably 10 to 90 mol%).

In addition, under the same conditions as the production method of resin [K4], the carboxylic acid or carboxylic anhydride contained in (a) and the copolymer of (b) (especially (b1)) and (c) have ) to react with a cyclic ether structure to obtain the resin [K5]. It is preferable that the usage-amount of the above-mentioned (a) which reacts with a copolymer is 5-80 mol with respect to 100 mol of (b) (especially (b1)). Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for resin [K5], and (b1-1) is more preferable.

Resin [K6] is resin obtained by further reacting carboxylic anhydride and resin [K5].

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

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Formic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride ( Nadic anhydride), etc.

Among the resins [K1] to [K6], the resin preferable as the resin (B) is [K1] or [K2]. Resin (B) may consist of 1 type of resin, and may contain 2 or more types of resins.

The polystyrene conversion weight average molecular weight of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight exists in the said range, the solubility to the developing solution of an unexposed part becomes high, and there exists a tendency for the remaining film rate and hardness of the obtained pattern to become high. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

The solution acid value of the resin (B) is preferably 5 to 180 mg-KOH/g, more preferably 10 to 100 mg-KOH/g, and still more preferably 12 to 50 mg-KOH/g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass in 100% by mass of solid content of the colored curable resin composition. When content of resin (B) exists in the said range, there exists a tendency for the solubility to the developing solution of an unexposed part to become high.

[3] Polymerizable compound (C)

The polymerizable compound (C) is a compound that can be polymerized by active radicals or the like generated from the polymerization initiator (D) by light irradiation or the like.

In the colored curable resin composition of the present invention, the polymerizable compound (C) contains a compound selected from the group consisting of ethylene oxide-modified dipentaerythritol penta(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate. (meth)acrylate (c1) of at least 1 sort(s) in the group which consists of esters.

(Meth)acrylate (c1) is a (meth)acrylate compound represented by the following formula.

In the above formula, X each independently represents an acryloyl group or a methacryloyl group. Y represents a hydrogen atom, an acryloyl group or a methacryloyl group. a to f are integers of 1 or more, and the total of a to f, that is, a+b+c+d+e+f+g (hereinafter the total amount may be referred to as "EO modification amount") is an integer of 6 to 24 . The total of a to f is preferably 6-18.

Ethylene oxide modified dipentaerythritol penta(meth)acrylate is a compound in which Y is a hydrogen atom in the above formula, and ethylene oxide modified dipentaerythritol hexa(meth)acrylate is Y in the above formula for acryloyl or Methacryloyl compounds.

In the polymerizable compound (C), it is possible to contain only a compound in which Y is a hydrogen atom in the above formula as (meth)acrylic acid ester (c1), and it is also possible to contain only a compound in which Y is an acryloyl or methacryloyl group as (meth) ) acrylate (c1), and both may be included as (meth)acrylate (c1).

With the colored curable resin composition of the present invention that contains C.I. Pigment Green 59 as the colorant (A) and the polymerizable compound (C) contains (meth)acrylate (c1), it is possible to form a pattern that achieves both high brightness and excellent pattern shape. color filter.

(Meth)acrylate (c1) can be produced by a method including the step of ring-opening addition of ethylene oxide to dipentaerythritol, and (meth)acryloyl chloride, (meth)acrylic acid and The method of the step of introducing (meth)acryloyl group by reacting the terminal hydroxyl group of ethylene oxide introduced by ring-opening addition; ring-opening addition of ethylene oxide to (meth)acrylic acid to synthesize ethylene oxide modification After (meth)acrylic acid, the method of carrying out esterification reaction with dipentaerythritol; Etc.

As the ethylene oxide-modified dipentaerythritol penta(meth)acrylate, a commercially available product (eg, brand name "M-DPH-6E" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)) can also be used.

The colored curable resin composition of this invention may contain other polymeric compounds other than (meth)acrylate (c1) further.

In this specification, (meth)acrylate (c1) and other polymeric compounds are collectively called "polymeric compound (C)".

The weight average molecular weight of other polymerizable compounds is preferably 3,000 or less.

The colored curable resin composition of this invention may contain 1 type, or 2 or more types of other polymeric compounds other than a (meth)acrylate (c1).

The other polymerizable compound is preferably a compound containing a polymerizable ethylenically unsaturated bond, more preferably a compound containing a (meth)acryloyl group (eg (meth)acryloyloxy group) as a polymerizable ethylenically unsaturated bond (meth)acryloyl-containing compound (c2).

Among them, the (meth)acryloyl group-containing compound (c2) is preferably a polymerizable compound having three or more (meth)acryloyl groups in the molecule. Specific examples thereof include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tri( 2-(meth)acryloyloxyethyl)isocyanurate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, propylene oxide modified pentaerythritol tetra(meth)acrylate, epoxy Propane-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

Among these, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferable.

The content of the polymerizable compound (C) is preferably 10 to 150 parts by mass, more preferably 50 to 120 parts by mass relative to 100 parts by mass of the resin (B) in the colored curable resin composition.

It is preferable that content of the (meth)acrylate (c1) in a polymeric compound (C) is high from a viewpoint of making both high brightness|luminance and an excellent pattern shape effective. Specifically, the content of (meth)acrylate (c1) in 100% by mass of the polymerizable compound (C) is usually 20% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably It is 80% by mass or more, and it should be noted that it is more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

[4] Polymerization initiator (D)

The colored curable resin composition of this invention contains a polymerization initiator (D). The colored curable resin composition may contain 1 type, or 2 or more types of polymerization initiators as a polymerization initiator (D).

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat to initiate polymerization, and known polymerization initiators can be used.

Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, alkyl phenone compounds, biimidazole compounds, triazine compounds, acyl phosphine oxide compounds, and the like. The polymerization initiator (D) may be used in combination of two or more in consideration of sensitivity, formation of a precise pattern shape, and the like.

The polymerization initiator (D) preferably contains an oxime compound such as an O-acyl oxime compound, from the viewpoints of sensitivity and precise preparation of a pattern shape having a desired line width.

When the colored curable resin composition of this invention contains an oxime compound, it is preferable to further contain a biimidazole compound.

The O-acyloxime compound is a compound having a structure represented by formula (d). Hereinafter, * indicates a connection bit.

The O-acyl oxime compound is, for example, preferably selected from a compound represented by formula (d1) (hereinafter sometimes referred to as "compound (d1)"), a compound represented by formula (d2) (hereinafter sometimes referred to as "compound (d2)") ) and a compound represented by formula (d3) (hereinafter sometimes referred to as "compound (d3)").

In formula (d1)～(d3),

R ^d1 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have a substituent, a heterocyclic group with 3 to 36 carbon atoms that may have a substituent, an alkyl group with 1 to 15 carbon atoms that may have a substituent, or an aromatic A group that may have substituents that are a combination of a hydrocarbon group and an alkanediyl group derived from the alkyl group. The methylene group (-CH ₂ -) contained in the above-mentioned alkyl group can be replaced by -O-, -CO-, -S -, -SO ₂ -or -NR ^d5 -,

R ^d2 represents an aromatic hydrocarbon group with 6 to 18 carbons, a heterocyclic group with 3 to 36 carbons or an alkyl group with 1 to 10 carbons,

R ^d3 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms,

R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, and the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be Replaced by -O-, -CO- or -S-, the methine group (-CH<) contained in the above-mentioned aliphatic hydrocarbon group can be replaced by -PO ₃ <, the hydrogen atom contained in the above-mentioned aliphatic hydrocarbon group can be replaced by OH group replace,

R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the alkyl group may be substituted with —O— or —CO—.

The number of carbon atoms in the aromatic hydrocarbon group represented by R ^d1 is preferably 6-15, more preferably 6-12, even more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, etc., preferably phenyl and naphthyl, and more preferably phenyl.

The aromatic hydrocarbon group represented by R ^d1 may have one or two or more substituents.

The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, and more preferably substituted at the γ-position. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, C1-15 alkyl groups such as tetradecyl and pentadecyl; halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atom; etc.

The number of carbon atoms in the alkyl group as the substituent is preferably 1-10, more preferably 1-7. The alkyl group as the substituent may be linear, branched or cyclic, or may be a combination of a chain group and a cyclic group. The methylene group (—CH ₂ —) contained in the alkyl group as the substituent may be substituted with —O— or —S—. The hydrogen atoms contained in the alkyl group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, iodine atoms, bromine atoms, and are preferably substituted with fluorine atoms.

In the aromatic hydrocarbon group represented by ^Rd1 , the alkyl group as a substituent includes a group represented by the following formula, and the like. In the formula, * represents the connection position.

As the aromatic hydrocarbon group which may have a substituent represented by ^Rd1 , the group represented by the following formula etc. are mentioned. In the formula, * represents the connection position.

The optionally substituted aromatic hydrocarbon group represented by R ^d1 is preferably a group represented by the following formula.

In the formula, R ^d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, and the hydrogen atoms included in R ^d6 may be substituted by a halogen atom. m2 represents the integer of 1-5.

Examples of the alkyl group represented by R ^d6 include the same groups as the alkyl groups exemplified as substituents of the aromatic hydrocarbon group represented by R ^d1 .

The carbon number of R ^d6 is preferably 2-7, more preferably 2-5. In addition, the alkyl group represented by R ^d6 may be any of linear, branched and cyclic, and is preferably chain.

The halogen atom which can replace the hydrogen atom contained in R ^d6 includes a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and fluorine atom is especially preferable. In addition, preferably 2 or more and 10 or less hydrogen atoms included in R ^d6 are substituted with halogen atoms, more preferably 3 or more and 6 or less are substituted with halogen atoms. The substitution position of the R ^d6 O-group is preferably the ortho-position or the para-position, particularly preferably the para-position. In addition, m2 is preferably 1-2, particularly preferably 1.

The carbon number of the heterocyclic group represented by R ^d1 is preferably 3-20, more preferably 3-10, even more preferably 3-5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, carbazolyl and the like.

The heterocyclic group represented by R ^d1 may have one or two or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent that the aromatic hydrocarbon group represented by R ^d1 may have.

The carbon number of the alkyl group represented by R ^d1 is preferably 1-12. The alkyl groups represented by R ^d1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, deca Trialkyl, tetradecyl and pentadecyl, etc. These alkyl groups may be linear, branched, or cyclic, or may be a combination of a chained group and a cyclic group. In addition, in the alkyl group represented by R ^d1 , the methylene group (-CH ₂ -) can be replaced by -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 -, and the hydrogen atom can be replaced by OH Substituted by group or SH group.

R ^d5 represents an alkyl group having 1 to 10 carbons, preferably an alkyl group having 1 to 5 carbons, more preferably an alkyl group having 1 to 3 carbons. The alkyl group may be chain (straight chain or branched), may be cyclic, may be any one of straight chain, branched and cyclic, or may be a chain-like group. A combination of a group and a cyclic group. In the alkyl group of R ^d5 , the methylene group (-CH ₂ -) may be substituted with -O- or -CO-.

In the group represented by R ^d1 , the alkyl group which may have a substituent specifically includes the group represented by the following formula, etc. * Indicates a connected bit.

In addition, the carbon number of the group that combines the aromatic hydrocarbon group represented by ^Rd1 and the ^alkanediyl group derived from the alkyl group represented by Rd1 is preferably 7 to 33, more preferably 7 to 18, and even more preferably 7. ~12. The combined group may have one or two or more substituents, and examples of the substituents are the same as those exemplified as substituents that the aromatic hydrocarbon group and the alkyl group may have. The group represented by R ^d1 which is a combination of an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group represented by R ^d1 includes an aralkyl group, specifically, a group represented by the following formula. In the formula, * represents the connection position.

Among them, R ^d1 is preferably an optionally substituted aromatic hydrocarbon group or an optionally substituted alkyl group, more preferably an optionally substituted aromatic hydrocarbon group.

The number of carbon atoms in the aromatic hydrocarbon group represented by R ^d2 is preferably 6-15, more preferably 6-12, even more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and terphenyl.

The carbon number of the heterocyclic group represented by R ^d2 is preferably 3-20, more preferably 3-10, even more preferably 3-5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, carbazolyl and the like.

The carbon number of the alkyl group represented by R ^d2 is preferably 1-7, more preferably 1-5, and still more preferably 1-3. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group may be linear, branched or cyclic, and may be a combination of a chain group and a cyclic group.

R ^d2 is preferably a chained alkyl group, more preferably a chained alkyl group having 1 to 5 carbons, still more preferably a chained alkyl group having 1 to 3 carbons, and particularly preferably a methyl group.

The number of carbon atoms in the aromatic hydrocarbon group represented by R ^d3 is preferably 6-15, more preferably 6-12, even more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl and the like, more preferably phenyl and naphthyl.

The aromatic hydrocarbon group represented by R ^d3 may have one or two or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl Alkyl groups with 1 to 15 carbons; alkenyls with 1 to 15 carbons such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl and decenyl; etc. .

As for the substituent in the aromatic hydrocarbon group represented by ^Rd3 , the carbon number of the aliphatic hydrocarbon group is more preferably 1-7. The aliphatic hydrocarbon group may be any of linear, branched and cyclic, and may be a combination of a chain group and a cyclic group. The methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group may be replaced by —O—, —CO— or —S—, and the methine group (—CH<) may be replaced by —N<.

Among the groups represented by R ^d3 , the aliphatic hydrocarbon group that the aromatic hydrocarbon group may have includes groups represented by the following formula, and the like. In the formula, * represents the connection position.

Among the groups represented by R ^d3 , the aromatic hydrocarbon group which may have a substituent includes a group represented by the following formula and the like. In the formula, * represents the connection position.

The carbon number of the heterocyclic group represented by R ^d3 is preferably 3-20, more preferably 3-10, even more preferably 3-5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, carbazolyl and the like. In addition, the heterocyclic group represented by ^Rd3 may have one or two or more substituents, and examples of the substituents are the same as those exemplified as substituents that the aromatic hydrocarbon group represented by ^Rd1 may have. group.

Among them, R ^d3 is preferably an aromatic hydrocarbon group with a substituent, the substituent is preferably a chain alkyl group with 1 to 7 carbons (more preferably 1 to 3 carbons), and the number of substituents is preferably 2 or more , less than 5.

The number of carbon atoms in the aromatic hydrocarbon group represented by R ^d4 is preferably 6-15, more preferably 6-12, even more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and terphenyl, more preferably phenyl and naphthyl, and still more preferably phenyl. In addition, the aromatic hydrocarbon group represented by R ^d4 may have one or two or more substituents. Examples of the substituent include the same substituents that the aromatic hydrocarbon group of R ^d1 may have.

The number of carbon atoms in the aliphatic hydrocarbon group represented by R ^d4 is preferably 1-13, more preferably 2-10, even more preferably 4-9. The aliphatic hydrocarbon group represented by R ^d4 includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Alkyl groups such as tridecyl, tetradecyl and pentadecyl; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene Alkenyl groups such as undecenyl, dodecenyl, tridecenyl, tetradecenyl and pentadecenyl; etc. These aliphatic hydrocarbon groups may be chain (linear or branched), cyclic, or a combination of a chain group and a cyclic group. In the aliphatic hydrocarbon group of R ^d4 , methylene (-CH ₂ -) can be replaced by -O-, -CO- or -S-, methine (-CH<) can be replaced by -PO ₃ <, the above fatty Hydrogen atoms contained in the hydrocarbon group may be substituted with OH groups.

Among the groups represented by R ^d4 , the aliphatic hydrocarbon group which may have a substituent includes a group represented by the following formula and the like. In the formula, * represents the connection position.

R ^d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and still more preferably a branched chain alkyl group having no substituent.

Compound (d1) includes compounds represented by formula (d1), specifically, compounds having each substituent described in column (d1-1) to compounds having each substituent described in column (d1-67) base compound. In Tables 1 to 7, * indicates a connection bit.

Table 1

Table 2

table 3

Table 4

table 5

Table 6

Table 7

Among them, compounds having the substituents described in the column (d1-3) to compounds having the substituents described in the column (d1-6) and compounds having the substituents described in the column (d1-18) are preferred. Compounds to compounds having the substituents described in the column (d1-52), compounds having the substituents described in the column (d1-55), compounds having the substituents described in the column (d1-56), A compound having each substituent described in the column of (d1-60), a compound having each substituent described in the column of formula (d1-61),

More preferably, it is a compound having each substituent described in column (d1-3) to a compound having each substituent described in column (d1-6), or a compound having each substituent described in column (d1-18) ~ Compounds having the substituents described in the column (d1-41),

More preferably, it is a compound having each substituent described in column (d1-24), a compound having each substituent described in column (d1-36) to a compound having each substituent described in column (d1-40) , particularly preferably a compound having each of the substituents described in the column (d1-24).

Compound (d1) can be produced, for example, by the production method described in JP 2014-500852 A.

Compound (d2) is preferably:

R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent,

R ^d2 is an alkyl group with 1 to 10 carbon atoms,

R ^d3 is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent,

R ^d4 is a compound having an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent,

More preferably:

R ^d1 represents methyl, ethyl or propyl,

R ^d2 represents methyl, ethyl or propyl,

R ^d3 represents phenyl substituted by methyl,

Compounds in which R ^d4 is methyl, ethyl or propyl,

Further preferred are:

A compound wherein ^{Rd1 and Rd2 are methyl, Rd3 is o} -tolyl and ^Rd4 is ethyl.

Compound (d3) is preferably:

R ^d1 is an alkyl group having 1 to 15 carbon atoms which may have a substituent,

R ^d2 is a compound having an aromatic hydrocarbon group with 6 to 18 carbon atoms,

More preferably:

A compound wherein ^Rd1 is hexyl and ^Rd2 is phenyl.

Examples of such O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylmercaptophenyl)butane-1-one-2-imine, N-benzoyloxy-1 -(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropane-1 -Keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine , N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy)benzyl Acyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-3-cyclopentylpropane-1-one-2-imine, etc. Commercially available items such as IRGACURE OXE01, OXE02, and OXE03 (the above are manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Corporation) can be used. These O-acyl oxime compounds tend to provide a color filter excellent in photolithography performance.

The alkyl phenyl ketone compound is a compound having a structure represented by formula (d4) or a structure represented by formula (d5). In these structures, the benzene ring may have a substituent.

Compounds having a structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylmercaptophenyl)propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( 4-morpholino)phenyl]butane-1-one, etc. Commercial items such as IRGACURE 369, 907, and 379 (the above are manufactured by BASF Corporation) can be used.

Compounds having a structure represented by formula (d5) include 2-hydroxyl-2-methyl-1-phenylpropane-1-one, 2-hydroxyl-2-methyl-1-[4-(2- Low levels of hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one polymer, α, α-diethoxyacetophenone, benzoin dimethyl ether, etc.

From the viewpoint of sensitivity, the alkyl phenyl ketone compound is preferably a compound having a structure represented by formula (d4).

Biimidazole compounds can include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) base)-4,4',5,5'-tetraphenylbiimidazole (see Japanese Patent Application Publication No. 6-75372, Japanese Patent Application Publication No. 6-75373, etc.), 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene base) 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 (see Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), 4 , 4', 5, and 5'-positions of phenyl groups are substituted with alkoxycarbonyl imidazole compounds (see Japanese Patent Application Laid-Open No. 7-10913, etc.), etc.

Among them, compounds represented by the following formulas or mixtures thereof are preferred.

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

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

In addition, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butyl peroxide) oxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10 -Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiation adjuvant (D1) (especially amines) described later.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and even more preferably 10 to 20 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). parts by mass. When content of a polymerization initiator (D) exists in the said range, since there exists a tendency for sensitivity to become high and exposure time shortened, it exists in the tendency for the productivity of a color filter to improve.

[5] Polymerization initiation aid (D1)

The polymerization initiation adjuvant (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound (C) whose polymerization is initiated by a polymerization initiator. When a polymerization initiation adjuvant (D1) is included, it can be used in combination with a polymerization initiator (D).

Examples of the polymerization initiation adjuvant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among them, thioxanthone compounds are preferable. Two or more polymerization initiation adjuvants (D1) may be used in combination.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 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'-bis(ethylmethylamino)benzophenone, etc., among them, 4,4'- Bis(diethylamino)benzophenone. Commercial items such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include phenylthioglycolic acid, methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylthioglycolic acid, methoxyphenylthioglycolic acid, Dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc. .

The content of the polymerization initiation adjuvant (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When content of a polymerization start adjuvant (D1) exists in the said range, a colored pattern can be formed with high sensitivity, and there exists a tendency for the productivity of a color filter to improve.

[6] Thiol compound (T)

The colored curable resin composition of the present invention may contain a thiol compound (T). The colored curable resin composition of this invention may contain 1 type, or 2 or more types of thiol compounds as a thiol compound (T). The thiol compound (T) is particularly preferably used when the polymerization initiator (D) is an oxime compound such as an O-acyl oxime compound and/or a biimidazole compound. The thiol compound (T) is a compound having at least one mercapto group (—SH) in the molecule. The thiol compound (T) is preferably a compound having one mercapto group in the molecule.

Compounds having one mercapto group in the molecule include 2-mercaptooxazole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptonicotinic acid , 2-mercaptopyridine, 2-mercaptopyridine-3-ol, 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-6-hydroxy-2-mercaptopyrimidine , 4-amino-2-mercaptopyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 4,6-diamino- 2-mercaptopyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4-hydroxy-2-mercapto- 6-methylpyrimidine, 4-hydroxy-2-mercapto-6-propylpyrimidine, 2-mercapto-4-methylpyrimidine, 2-mercaptopyrimidine, 2-thiouracil, 3,4,5,6- Tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, 4-amino-3-hydrazino-5-mercapto -1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4- Methyl-4H-1,2,4-triazole-3-thiol, 3-mercapto 1H-1,2,4-triazole-3-thiol, 2-amino-5-mercapto-1,3, 4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dimercapto-1,3,4-thiadiazole, (furan-2-yl)methane Thiol, 2-mercapto-5-thiazolidinone, 2-mercaptothiazoline, 2-mercapto-4(3H)-quinazolone, 1-phenyl-1H-tetrazole-5-thiol, 2- Quinolinethiol, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 6-amino-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole , 6-ethoxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptonaphthimidazole, 2-mercaptonaphthoxazole, 3-mercapto-1,2,4 -triazole, 4-amino-6-mercaptopyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-mercaptopurine and 4-mercapto-1H-pyrazolo[2, 4-d] pyrimidine etc.

Compounds having two or more mercapto groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylmercapto)benzene, butanediol bis(3-mercaptopropionate), butanediol Alcohol bis(3-mercaptoacetate), Ethylene glycol bis(3-mercaptoacetate), Trimethylolpropane tris(3-mercaptoacetate), Butylene glycol bis(3-mercaptopropionate) ), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptoethylene ester), trihydroxyethyl tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate) and 1,4-bis(3-mercaptobutoxy)butane, etc.

The content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass relative to 100 parts by mass of the polymerization initiator (D). When content of a thiol compound (T) exists in the said range, sensitivity improves and developability also tends to become favorable.

[7] Solvent (E)

The colored curable resin composition of the present invention preferably contains a solvent (E). The colored curable resin composition may contain 1 type, or 2 or more types of solvents as a solvent (E). Examples of the solvent (E) include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), ester Other than solvents are ketone solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, propyl Butyl Butyrate, Isopropyl Butyrate, Ethyl Butyrate, Butyl Butyrate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetoacetate, Ethyl Acetoacetate, Cyclohexanolacetic Acid Esters and γ-butyrolactone, etc.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Alcohol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, Tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methyl anisole, etc.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2-ethoxy Ethyl-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol Methyl ether acetate, etc.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone , cyclopentanone, cyclohexanone and isophorone, etc.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene. Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

The solvent (E) preferably contains an organic solvent having a boiling point of 120° C. to 180° C. at 1 atm from the viewpoint of coating properties and drying properties. Among them, the solvent (E) preferably contains propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethyl At least one of the group consisting of formamides, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate , 3-methoxy-1-butanol and 3-ethoxy ethyl propionate at least one of the group consisting of.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass in the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 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 favorable, and the color density does not become insufficient when forming a color filter, so the display characteristics tend to become favorable.

[8] Leveling agent (F)

The colored curable resin composition of this invention may contain a leveling agent (F). The colored curable resin composition may contain 1 type, or 2 or more types of leveling agents as a leveling agent (F). Examples of the leveling agent (F) include silicone-based surfactants (which do not have fluorine), fluorine-based surfactants, silicone-based surfactants having a fluorine atom, and the like. These may have a polymerizable group in a side chain.

Examples of silicone-based surfactants (which do not contain fluorine) include surfactants having a siloxane bond in the molecule, and the like. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray SiliconeDC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Toray Dow Corning Corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan) and the like.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Corporation), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Corporation), F top (registered trademark) EF301, F top EF303, F top EF351, F top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC Corporation) etc. are mentioned.

The content of the leveling agent (F) in the colored curable resin composition is usually not less than 0.001% by mass and not more than 0.2% by mass, preferably not less than 0.002% by mass and not more than 0.1% by mass, more preferably not less than 0.005% by mass and not more than 0.05% by mass %the following. It should be noted that this content is not included in the above-mentioned content of the pigment dispersant.

[9] Antioxidant (G)

From the viewpoint of improving the heat resistance and light resistance of the colorant (A), it is preferable that the colored curable resin composition contains an antioxidant. The antioxidant is not particularly limited as long as it is an antioxidant generally used in industry, and phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like can be used. Two or more types of antioxidants can be used.

Examples of phenolic antioxidants include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox 1076 ( Irganox 1076: 3-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, manufactured by BASF Corporation), Ilganox 1330 (Irganox 1330: 3, 3', 3", 5 , 5', 5"-hexa-tert-butyl-a, a', a"-(trimethylbenzene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corporation), Irganox 3114 (Irganox 3114 : 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, BASF Co., Ltd.), Iruganox 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5- Triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), Irganox 1035 (Irganox 1035: thiodiethylenebis[3-(3,5-di-tert-butyl Irganox 1135 (Irganox 1135: phenylpropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy C7 - C9 side chain alkyl ester, manufactured by BASF Corporation), Iluganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), Iluganox 3125 (Irganox 3125, BASF Co., Ltd.), Iruganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3, 5-triazine, manufactured by BASF Corporation), ADEKA STAB AO-80 (ADEKA STAB AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl )propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA Corporation), Sumilizer BHT (SumilizerBHT, Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, Cytec Co., Ltd.), vitamin E (manufactured by Eisai Co., Ltd.) and the like.

Examples of phosphorus antioxidants include Irgafos 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corporation), and Ilugafos 12 (Irgafos 12: tris[2-[[2, 4,8,10-Tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, manufactured by BASF Corporation), Ilugafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl) ethyl phosphorous acid, manufactured by BASF Corporation), ADEKA STAB 329K (manufactured by ADEKA Corporation) ), ADEKA STAB PEP36 (manufactured by ADEKA Co., Ltd.), ADEKA STAB PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G , manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE), and Sumilizer GP (Sumilizer GP: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy ]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphapine) (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, or distearyl thiodipropionate, and tetrakis[ethylene oxide]. β-alkylmercaptopropionate compounds of polyhydric alcohols such as methyl(3-dodecylthio)propionate]methane, etc.

[10] Other ingredients

The colored curable resin composition of the present invention may contain one or more fillers, polymer compounds other than the resin (B), adhesion promoters, ultraviolet absorbers, anti-aggregating agents, organic acids, Organic amine compounds, curing agents and other additives.

Examples of fillers include glass, silica, alumina and the like. Examples of polymer compounds other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like.

Adhesion accelerators include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethylsilane Oxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, etc.

Examples of UV absorbers include benzotriazole compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2-hydroxy-4-octyloxy Benzophenone compounds such as benzophenone; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-(4 , 6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol and other triazine compounds; etc.

Sodium polyacrylate etc. are mentioned as an anti-agglomeration agent.

Organic acids are used for the adjustment of developability, specifically, the following can be cited:

Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, hexanoic acid, diethylacetic acid, heptanoic acid, octanoic acid and other aliphatic monocarboxylic acids;

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid , Dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid and other aliphatic dicarboxylic acids ;

Aliphatic tricarboxylic acids such as glyceric acid, aconitic acid, and camphoric acid;

Benzoic acid, methylbenzoic acid, isopropylbenzoic acid, 2,3-dimethylbenzoic acid (hemellitic acid), trimethylbenzoic acid and other aromatic monocarboxylic acids;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid;

Trimellitic acid, trimellitic acid, trimellitic acid, pyromellitic acid and other aromatic polycarboxylic acids; etc.

Examples of organic amine compounds include:

N-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-decylamine Monoalkylamines such as diamines;

Cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine and other monocycloalkylamines;

Methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di-n-pentylamine, Dialkylamines such as di-n-hexylamine;

Monoalkyl monocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;

Dicycloalkylamines such as dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyl-di-n-propylamine, ethyl-di-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-propylamine Butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine and other trialkylamines;

Dimethylcyclohexylamine, diethylcyclohexylamine and other dialkyl monocycloalkylamines;

Methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine and other monoalkyldicyclohexylamines;

2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, etc. Monoalkanolamine;

4-amino-1-cyclohexanol and other monocycloalkanolamines;

Diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine and other dialkanolamines;

Bicycloalkanolamines such as bis(4-cyclohexanol)amine;

Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, and tri-n-hexanolamine;

Tricycloalkanolamines such as tris(4-cyclohexanol)amine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino- 1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol and other aminoalkanediols;

4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol and other amino cycloalkane diols;

1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol and other cycloalkanone methanol containing amino groups;

1-Aminocyclohexanone Methanol, 4-Aminocyclohexanone Methanol, 4-Dimethylaminocyclopentane Methanol, 4-Diethylaminocyclopentane Methanol, 4-Dimethylaminocyclohexane Methanol, 4-Diethyl Amino cyclohexane methanol and other amino cycloalkane methanol;

β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid and other aminocarboxylic acids;

Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-propylaniline, p-isopropylaniline, p-n-butylaniline, p-tert-butylaniline, 1-naphthyl Amine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, p-methyl-N,N-dimethylaniline and other aromatic amines;

o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol and other aminobenzyl alcohols;

Aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;

Aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid; etc.

Examples of the curing agent include compounds capable of crosslinking the resin (B) by reacting with carboxyl groups in the resin (B) by heating, compounds capable of curing a colored pattern by polymerization alone, and the like. Specific examples thereof include epoxy compounds, oxetane compounds, and the like. A curing agent may be used alone or in combination of two or more.

Examples of epoxy compounds include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, and other aromatic Epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxidized oils and other epoxy resins; brominated derivatives of these epoxy resins , aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, epoxides of (co)polymers of butadiene, (co)polymers of isoprene epoxy, (co)polymer of glycidyl (meth)acrylate, triglycidyl isocyanurate, etc. Examples of commercially available epoxy resins include o-cresol novolak-type epoxy resins, "SUMI EPOXY (registered trademark) ESCN-195XL-80" (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

Examples of the oxetane compound include bisoxetane carbonate, bisoxetane xylylene, bisoxetane adipate, bisoxetane terephthalate, cyclo Hexane dicarboxylic acid dioxetane, etc.

In the colored curable resin composition of the present invention, when an epoxy compound, an oxetane compound, etc. are contained as a curing agent, an epoxy group capable of making the epoxy compound, an oxetane compound A compound in which an oxetane skeleton undergoes ring-opening polymerization. Examples of this compound include polyvalent carboxylic acids, polycarboxylic acid anhydrides, and acid generators.

Polycarboxylic acids can be cited:

3,4-Dimethylphthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid Other aromatic polycarboxylic acids;

1,2,3,4-butane tetracarboxylic acid and other aliphatic polycarboxylic acids;

Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2 , 4-cyclohexanetricarboxylic acid, cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid and other alicyclic polycarboxylic acids; etc.

Polycarboxylic acid anhydrides can be cited:

Aromatic polycarboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride;

Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, glyceric anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride and other aliphatic polycarboxylic anhydrides;

Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentane Alicyclic polyhydric carboxylic acid such as tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-bicycloheptene-2,3-dicarboxylic anhydride (anhydrous haimic acid), nadic anhydride, etc. anhydride;

Carboxylic anhydrides containing ester groups such as ethylene glycol ditrimellitic acid and glycerin tritrimellitic anhydride; etc.

As the carboxylic acid anhydride, a commercially available epoxy resin curing agent can be used. Examples of the epoxy resin curing agent include the product name "ADEKA Hardener (registered trademark) EH-700" (manufactured by ADEKA Co., Ltd.), the product name "Rikacid (registered trademark) HH" (manufactured by Shin Nippon Chemical Co., Ltd.), the product name " MH-700" (manufactured by Nippon Chemical Co., Ltd.), etc.

Acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate salt, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonic acid salt, onium salts such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

<Manufacturing method of colored curable resin composition>

The colored curable resin composition of the present invention can be obtained by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and if necessary, a solvent (E), a thiol compound ( T), a leveling agent (F), a polymerization initiation adjuvant (D1), an antioxidant (G), and other components were mixed and prepared.

<Color filter, manufacturing method thereof, color filter, and display device>

The colored curable resin composition of the present invention is useful as a material of a color filter. A color filter formed from the colored curable resin composition of the present invention is also included in the scope of the present invention. The color filter may be formed with a coloring pattern.

As a method for producing a colored pattern from the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, and the like are exemplified. Among them, photolithography is preferable. The photolithography method is a method of applying a colored curable resin composition to a substrate, drying it to form a colored composition layer, exposing the colored composition layer through a photomask, and developing. In photolithography, a colored coating film that is a cured product of the above-mentioned colored composition layer can be formed by not using a photomask and/or not performing development at the time of exposure. The colored pattern and colored coating film formed in this way are the color filter of this invention.

The color filters of the present invention are typically used as green pixels.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with a silica coating on the surface; polycarbonate, polymethyl methacrylate, polyparaphenylene, etc. Resin boards such as ethylene diformate; silicon; substrates in which aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the above substrates. Other color filter layers, resin layers, transistors, circuits, and the like may also be formed on these substrates.

Formation of pixels of various colors by photolithography can be performed using known or commonly used devices and conditions, and can be produced, for example, as follows. First, a colored curable resin composition is applied on a substrate, and dried by heat drying (prebaking) and/or reduced pressure drying to remove volatile components such as solvents to obtain a smooth colored composition layer. As a coating method, a spin coating method, a slit coating method, a slit spin coating method, etc. are mentioned.

The temperature at the time of heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When performing reduced-pressure drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa. The film thickness of a coloring composition layer is not specifically limited, It can select suitably according to the film thickness of the objective color filter.

Next, the colored composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use can be used. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, light less than 350nm can be cut with a filter that cuts off this wavelength band, and light around 436nm, 408nm, and 365nm can be selectively extracted using a bandpass filter that extracts these wavelength bands.

Specifically, examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.

It is preferable to use a mask aligner and a stepper ( stepper) and other exposure devices.

A colored pattern is formed on a board|substrate by making the exposed coloring composition layer contact a developing solution, and developing. By image development, the unexposed part of a coloring composition layer is dissolved in a developing solution, and removed.

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

The image development method may be any one of spin-on immersion method, dipping method, spraying method and the like. In addition, the substrate can be tilted at any angle during development. Water washing is preferably performed after image development.

In addition, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

The film thickness of the obtained color filter is preferably as thin as possible because it affects adjacent pixels. In particular, when forming a thick film, light from a light source may leak through pixels of two or more colors when producing a liquid crystal panel, and the vividness of the color may be lost when the panel is viewed from an oblique direction. The film thickness of the color filter is usually preferably 3 μm or less, more preferably 2.8 μm or less. The lower limit of the film thickness of the color filter is not particularly limited, but it is usually 1 μm or more, and may be 1.5 μm or more.

The color filter of the present invention is useful as a color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Example

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to these examples. In the examples, % and parts indicating the content or usage amount are the quality standard unless otherwise stated.

<Synthesis Example 1: Preparation of Resin Solution (B1)>

An appropriate amount of nitrogen was flowed through a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^{2 , 6} ] A mixed solution of 289 parts of a mixture of decane-9-yl ester and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, after keeping at the same temperature for 4 hours, it was cooled to room temperature to obtain a resin solution ( B1). The weight-average molecular weight Mw of the resin contained in the resin solution (B1) was 9200, and the molecular weight distribution was 2.08.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin contained in a resin solution (B1) was performed on the following conditions using the GPC method. The ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained under the following conditions was made molecular weight distribution.

Device: HLC-8120GPC (manufactured by Tosoh Corporation),

Column: TSK-GELG2000HXL,

Column temperature: 40°C,

Solvent: THF,

Flow rate: 1.0mL/min,

Detected liquid solid content concentration: 0.001 ~ 0.01% by mass,

Injection volume: 50μL,

Detector: RI,

Standard material for calibration: TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500

(manufactured by Tosoh Corporation).

<Synthesis Example 2: Preparation of Pigment Dispersion (A1)>

C.I. Pigment Green 59 14.0 parts

Acrylic pigment dispersant 1.9 parts

Propylene glycol monomethyl ether acetate 84.1 parts

The mixture was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A1).

<Synthesis Example 3: Preparation of Pigment Dispersion (A2)>

C.I. Pigment Green 58 14.0 parts

Acrylic pigment dispersant 1.9 parts

Propylene glycol monomethyl ether acetate 84.1 parts

The mixture was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A2).

<Synthesis Example 4: Preparation of Pigment Dispersion Liquid (A3)>

C.I. Pigment Yellow 138 15.0 parts

Acrylic pigment dispersant 4.5 parts

Propylene glycol monomethyl ether acetate 80.5 parts

The mixture was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A3).

<Examples 1 to 5 and Comparative Examples 1 to 5>

(1) Preparation of colored curable resin composition

The components described in Table 8 were mixed in the compounding quantities described in Table 8 to obtain a colored curable resin composition. The unit of the compounding quantity of each component in Table 8 is "mass part". The details of each component are as follows.

[1] Pigment dispersion (A1): the pigment dispersion (A1) obtained in Synthesis Example 2,

[2] Pigment dispersion (A2): the pigment dispersion (A2) obtained in Synthesis Example 3,

[3] Pigment dispersion (A3): the pigment dispersion (A3) obtained in Synthesis Example 4,

[4] Resin solution (B1): the resin solution (B1) obtained in Synthesis Example 1,

[5] Polymerizable compound (C1): ethylene oxide-modified dipentaerythritol hexamethacrylate (EO modification amount 6) (trade name "M-DPH-6E" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.),

[6] Polymerizable compound (C2): dipentaerythritol hexaacrylate (trade name "A-9550" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.),

[7] Polymerization initiator (D1): a compound represented by the following formula

[8] Polymerization initiator (D2): 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1 , 1'-biimidazole (trade name "TCDM" manufactured by CHEMBRIDGE INTERNATIONAL CORPORATION),

[9] Thiol compound (T1): 2-Mercaptobenzothiazole (trade name "Sanceler M" manufactured by Sanshin Chemical Industry Co., Ltd.),

[10] Additive: 3-acryloxypropyltrimethoxysilane (trade name "KBM-503" manufactured by Shin-Etsu Silicone Co., Ltd.)

[11] Leveling agent (F1): polyether modified silicone oil (trade name "Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.),

[12] Solvent (E1): Propylene glycol monomethyl ether acetate.

Table 8

(2) Preparation of colored coating film

After coating the colored curable resin composition on a 2-inch-square glass substrate (Eagle XG: manufactured by Corning Incorporated) by a spin coating method, prebaking was performed at 100° C. for 3 minutes. After cooling, the substrate coated with the colored curable resin composition was irradiated with light at an exposure dose of 80 mJ/cm ² (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK: manufactured by TOPCON Co., Ltd.) . Thereafter, post-baking was performed at 230° C. for 30 minutes in an oven to obtain a colored coating film.

(3) Film thickness measurement

The film thickness of the colored coating film obtained in the above (2) was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 9.

(4) Chromaticity evaluation

The spectrum of the colored coating film obtained in (2) above was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and xy in the XYZ colorimetric system of CIE was calculated using the characteristic function of the C light source. Chromaticity coordinates (x, y) and stimulus value (Y). The larger (Y) is, the higher the brightness is. The results are shown in Table 9.

(5) Preparation of colored patterns and shape evaluation of colored patterns

A colored curable resin composition was applied by spin coating on a 2-inch square glass substrate (EagleXG; manufactured by Corning Corporation) so that the film thickness after post-baking was 2.7 μm, and then pre-baked at 100° C. for 3 minutes. Bake to form layers of composition. After cooling, set the distance between the substrate on which the composition layer was formed and the photomask made of quartz glass to 80 μm, and use an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) with an exposure amount of 50 mJ/cm ² in the air atmosphere. (365 nm standard) light irradiation was performed. In addition, the photomask which formed the line width and space pattern of 50 micrometers was used for the photomask. The composition layer after light irradiation was immersed in an aqueous solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 60 seconds to develop, washed with water, and then dried in an oven at 230°C for 30 minutes. The post-bake, thereby obtaining the coloring pattern. As a result of measuring the film thickness of the obtained colored pattern using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), it was confirmed that it was 2.7 μm.

The shape of the obtained colored pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Tech Co., Ltd.), and evaluated according to the following evaluation criteria. The results are shown in Table 9.

A: The shape of the coloring pattern is a forward tapered shape as shown in FIG. 1 .

B: The shape of the coloring pattern is an inverted tapered shape as shown in FIG. 2 .

Table 9

In Examples 1 to 5 and Comparative Examples 1 to 5, the chromaticity coordinates (x, y) of the colored coating film were unified. In Examples 1 to 5, both high luminance and a good shape of the colored pattern can be achieved. On the other hand, in Comparative Examples 1 to 2, the luminance was insufficient, and in Comparative Examples 1 to 5, the coloring pattern had an inverted tapered shape.

Industrial availability

According to the colored curable resin composition of the present invention, a color filter having high brightness and an excellent pattern shape, and a display device including the color filter can be provided.

Claims (6)

1. A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), The colorant (A) contains C.I. Pigment Green 59, The polymerizable compound (C) contains at least one selected from the group consisting of ethylene oxide-modified dipentaerythritol penta(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate. (meth)acrylate (c1). 2. The colored curable resin composition according to claim 1, wherein the polymerizable compound (C) further contains a (meth)acryloyl group-containing compound other than the (meth)acrylate (c1) (c2). 3. The colored curable resin composition according to claim 2, wherein the (meth)acryloyl group-containing compound (c2) is selected from trimethylolpropane tri(meth)acrylate, pentaerythritol tri(methyl) base) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol seven(meth)acrylate ) acrylate, tetraerythritol deca(meth)acrylate, tetraerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, modified ethylene oxide Pentaerythritol tetra(meth)acrylate, propylene oxide modified pentaerythritol tetra(meth)acrylate, propylene oxide modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate Compounds in the group consisting of acrylates and caprolactone-modified dipentaerythritol hexa(meth)acrylate. 4. The colored curable resin composition according to claim 1 or 2, wherein the content of the (meth)acrylate (c1) is 20% by mass in 100% by mass of the polymerizable compound (C) above. The color filter formed from the colored curable resin composition in any one of Claims 1-3. 6. A display device comprising the color filter of claim 5.