JP2013242554A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition having excellent developability in forming a coloring pattern by a photo-lithographic method.SOLUTION: A colored photosensitive resin composition includes colorant, resin, polymerizable compound and polymerization initiator. The colorant includes C. I. pigment green 36, yellow pigment, and at least one kind selected from the group consisting of blue pigment, red pigment, purple pigment and orange pigment. The resin is a copolymer including a structural unit derived from at least one kind selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and a structural unit having alicyclic hydrocarbon structure.

Description

  The present invention relates to a colored photosensitive resin composition.

  Colored photosensitive resin compositions are used in the production of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a colored photosensitive resin composition, a composition containing a copolymer of methacrylic acid, methyl methacrylate, n-butyl methacrylate and 2-hydroxyethyl methacrylate as a resin is known (Patent Document 1).

JP 2004-309537 A

  In the above-described colored photosensitive resin composition known from the past, when forming a colored pattern by a photolithographic method, the unexposed portion could not be sufficiently removed by development, and a residue or a film residue sometimes occurred. .

The present invention includes the following inventions.
[1] A colored photosensitive resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
The colorant (A) is C.I. I. Pigment Green 36,
Yellow pigment,
Selected from the group consisting of blue pigments, red pigments, purple pigments and orange pigments
Including at least one kind,
The resin (B) is a copolymer containing a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit having an alicyclic hydrocarbon structure. Colored photosensitive resin composition.
[2] The structure derived from the monomer which has a C3-C18 alicyclic hydrocarbon group in which the structural unit which has an alicyclic hydrocarbon structure of resin (B) may have a substituent. The colored photosensitive resin composition according to [1], which is a unit.
[3] The colored photosensitive resin composition according to [1] or [2], wherein the polymerization initiator (D) includes an O-acyloxime compound.
[4] At least one selected from the group consisting of a blue pigment, a red pigment, a purple pigment and an orange pigment of the colorant (A) is C.I. I. The colored photosensitive resin composition according to any one of [1] to [3], which is CI Pigment Red 177.
[5] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [4].
[6] A display device including the color filter according to [5].

  According to the colored photosensitive resin composition of this invention, it is excellent in the developability at the time of forming a colored pattern by the photolithographic method.

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
The colored photosensitive resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E), a thiol compound (T), a leveling agent (F), and an adhesion promoter (G).
The colored photosensitive resin composition of the present invention may further contain a polymerization initiation assistant (D1).

<Colorant (A)>
The colorant (A) is C.I. I. Pigment Green 36, a yellow pigment, and at least one selected from the group consisting of a blue pigment, a red pigment, a purple pigment, and an orange pigment.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc., preferably C.I. I. Pigment yellow 138 and 150.
Examples of the blue pigment include C.I. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60, 80, and the like.
Examples of red pigments include C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Preferably, C.I. I. Pigment Red 177.
Examples of purple pigments include C.I. I. Pigment violet 1, 19, 23, 29, 32, 36, 38, etc., preferably C.I. I. Pigment Violet 23.
Examples of the orange pigment include C.I. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc., preferably C.I. I. Pigment Orange 38.
Among at least one selected from the group consisting of blue pigments, red pigments, purple pigments and orange pigments, C.I. I. Pigment Red 177 is preferable in that the contrast of the obtained color filter is improved.

The pigment used in the colored photosensitive resin composition of the present invention is, as necessary, a rosin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced, a pigment surface with a polymer compound, etc. May be subjected to a grafting process, an atomization process using a sulfuric acid atomization method, or a cleaning process using an organic solvent or water for removing impurities, an ion exchange method for removing ionic impurities, or the like. . The pigments preferably have a uniform particle size.
These pigments can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniform dispersion state tends to be obtained.

C. I. 20-99 mass% is preferable with respect to the total amount of a coloring agent (A), and, as for content of pigment green 36, 30-95 mass% is more preferable.
0.1-79.9 mass% is preferable with respect to the total amount of a coloring agent (A), and, as for content of a yellow pigment, 4.9-60 mass% is more preferable.
The content of at least one selected from the group consisting of a blue pigment, a red pigment, a violet pigment and an orange pigment is preferably 0.1 to 5% by mass, preferably 0.1 to 3%, based on the total amount of the colorant (A). The mass% is more preferable.

  The content of the colorant (A) is preferably 20% by mass or more and 50% by mass or less, and more preferably 28-45% by mass with respect to the total amount of the solid content. In the present specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored photosensitive resin composition of the present invention.

<Resin (B)>
The resin (B) includes a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and an alicyclic hydrocarbon structure. It is a copolymer containing the structural unit which has.
The structural unit having an alicyclic hydrocarbon structure is derived from a monomer having an alicyclic hydrocarbon structure (hereinafter sometimes referred to as “(x)”).
Examples of the resin (B) include the following copolymers [K1] to [K5].
Copolymer [K1]; copolymer of (a) and (x);
Copolymer [K2]; (a), (x), and monomer (c) copolymerizable with (a) (however, different from (a) and (x)) (hereinafter referred to as “( c) ”); copolymer [K3]; copolymer [K1] or copolymer [K2] with a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond A resin obtained by reacting a monomer (b) (hereinafter sometimes referred to as “(b)”) having
A resin obtained by reacting (a) with a copolymer of copolymer [K4] (b) and (x);
Copolymer [K5] A resin obtained by further reacting a carboxylic acid anhydride with a resin obtained by reacting (a) with a copolymer of (b) and (x).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(X) is, for example, a monomer having an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.
Examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a tricyclodecyl group, a decahydronaphthyl group, and an adamantyl group. And a polycyclic alicyclic hydrocarbon group such as a norbornyl group, preferably a polycyclic alicyclic hydrocarbon group, and more preferably a tricyclodecyl group.
Examples of the substituent that they may have include an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a hydroxy group, a halogen atom, and an epoxy group.
Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. .
Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl group, naphthyl group, anthryl group, toluyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The monomer having an alicyclic hydrocarbon structure is, for example, a monomer having an alicyclic hydrocarbon structure and an ethylenically unsaturated bond, and preferably an alicyclic hydrocarbon structure and (meth) acryloyl. It is a monomer having an oxy group.
In the present specification, “(meth) acryloyl” represents at least one selected from the group consisting of acryloyl and methacryloyl. Notations such as “(meth) acrylic acid” and “(meth) acrylate” have the same meaning.

Examples of (x) include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth). Acrylate (in this technical field, it is referred to as “dicyclopentanyl (meth) acrylate” as a common name. It may also be referred to as “tricyclodecyl (meth) acrylate”), tricyclo [5.2.1 .0 ^2,6] (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) decene-8-yl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate , Cycloaliphatic hydrocarbon structures such as isobornyl (meth) acrylate and adamantyl (meth) acrylate (Meth) acrylic esters having a structure;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclo unsaturated compounds; N-substituted maleimides having an alicyclic hydrocarbon structure such as N-cyclohexylmaleimide; and the like.

In addition, (x) is a monomer having a structure in which two hydrogen atoms bonded to two adjacent carbon atoms of the alicyclic hydrocarbon are each substituted with an epoxy group as an alicyclic hydrocarbon structure (hereinafter referred to as “alicyclic hydrocarbon structure”). It may be “(x ′)”).
As such (x), for example, vinyl cyclohexylene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I) and Formula (II) And the like.

[In Formula (I) and Formula (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ^a and ^{X b} is a single ^{bond, -R c -, * - R} c -O -, * - represents the R c -S- or ^* -R c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

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

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, more preferably a single bond, * —CH _2. CH ₂ —O— (* represents a bond with O).

  Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I-15) A compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferred.

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) A compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

  The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination with the compound represented by formula (I) and the compound represented by formula (II). May be. When these are used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

(C) is not particularly limited as long as it is copolymerizable with (a) and is a monomer different from (a) and (x).
Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate , Dicarbonylimide derivatives such as N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene, benzyl (meth) acrylate, N-phenylmaleimide, N-benzylmaleimide and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

Further, among (c), a monomer having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) (hereinafter referred to as “(c ′)”) For example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether P-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) )styrene, , 4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2 , 3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyl) A monomer having an oxiranyl group such as oxymethyl) styrene and an ethylenically unsaturated bond;
3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3 An oxetanyl group such as methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and an ethylenically unsaturated bond; Having a monomer;
A monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond such as tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

In the copolymer [K1], the ratio of the structural units derived from each is the total structural unit constituting the copolymer [K1].
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (x); 40 to 98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (x); 50 to 90 mol%
It is more preferable that
When the ratio of the structural unit of the copolymer [K1] is in the above range, the developability when forming a colored pattern and the solvent resistance of the resulting color filter tend to be excellent.

  The copolymer [K1] can be prepared by, for example, a method described in the document “Experimental Method for Polymer Synthesis” (published by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.

  Specifically, a predetermined amount of (a) and (x), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to obtain a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer. Examples of the solvent (E) for the colored photosensitive resin composition of the present invention include the solvents described later.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored photosensitive resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored photosensitive resin composition of the present invention. Therefore, the manufacturing process of the colored photosensitive resin composition of the present invention can be simplified.

In the copolymer [K2], the ratio of the structural unit derived from each is the total structural unit constituting the copolymer [K2],
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (x); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (x); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the copolymer [K2] is in the above range, the developability when forming a colored pattern, and the solvent filter, heat resistance and mechanical strength of the resulting color filter tend to be excellent. is there.

  The copolymer [K3] can be produced by adding (b) to the copolymer [K1] or the copolymer [K2]. Examples of (b) include the above (c ′) and (x ′). The copolymer [K1] and the copolymer [K2] used for the production of the copolymer [K3] have no structural unit derived from (x ′) and no structural unit derived from (c ′). preferable.

In the copolymer [K1] or copolymer [K2] produced as described above, a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer, (b) Is reacted with a cyclic ether having 2 to 4 carbon atoms.
Subsequent to the production of the copolymer [K1] or the copolymer [K2], the atmosphere in the flask is changed from nitrogen to air, and (b) a reaction catalyst (for example, tris) of carboxylic acid or carboxylic anhydride and cyclic ether is used. (Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce a copolymer [K3]. can do.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making it within this range, the storage stability of the colored photosensitive resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the pattern obtained are improved. Tend. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b) used in the production of the copolymer [K3] is a monomer having an oxiranyl group and an ethylenically unsaturated bond. The body is preferred.
The amount of the reaction catalyst used is 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of all monomers and (b) used in the production of the copolymer [K1] or copolymer [K2]. Is preferred. The amount of the polymerization inhibitor used is 0.001 to 5 mass relative to 100 mass parts of the total amount of all monomers and (b) used in the production of the copolymer [K1] or the copolymer [K2]. Part is preferred.
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

As the first step, the copolymer [K4] is obtained in the same manner as in the above-described production method of the copolymer [K1] to obtain a copolymer of (b) and (x). Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as. As (b) used for the production of the copolymer [K4], a monomer having an oxiranyl group and an ethylenically unsaturated bond is preferable.
The ratio of the structural units derived from (b) and (x) is the total number of moles of all structural units constituting the copolymer, respectively.
Structural unit derived from (b); 5-95 mol%
Structural unit derived from (x); 5-95 mol%
It is preferable that
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (x); 10 to 90 mol%
It is more preferable that

Further, the cyclic ether derived from (b) of the copolymer of (b) and (x) under the same conditions as in the method for producing the copolymer [K4], the carboxylic acid or carboxylic acid of (a) A copolymer [K4] can be obtained by reacting the acid anhydride.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b).

Copolymer [K5] is a resin obtained by further reacting copolymer [K4] with a carboxylic acid anhydride. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Decyl (meth) acrylate / (meth) acrylic acid copolymer, tricyclo [5.2.1.0 ^2.6 ] copolymer such as decyl (meth) acrylate / (meth) acrylic acid copolymer [K1 ];
3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, tricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid Copolymer / copolymer such as benzyl (meth) acrylate [K2];
Resin of glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer Copolymer [K3] such as a resin obtained by adding glycidyl (meth) acrylate to a polymer; resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate , A copolymer such as a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate with (meth) acrylic acid [K4]; tricyclodecyl (meth) acrylate / glycidyl ( To a resin obtained by reacting a (meth) acrylate copolymer with (meth) acrylic acid Et copolymer resin obtained by reacting tetrahydrophthalic anhydride [K5], and the like in.

  The resin (B) is preferably a kind selected from the group consisting of a copolymer [K1] and a copolymer [K2]. When these resins are used, the colored photosensitive resin composition is excellent in developability. From the viewpoint of adhesion between the colored pattern and the substrate, the copolymer [K2] is more preferable.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

  Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the resin (B) is in the above range, the resolution of the coloring pattern and the remaining film ratio tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned.
Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there.
Further, the content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 35: 65-80: 20, more preferably 50: 50-75: 25, and particularly preferably 55: 50-70: 30.
When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

前記Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュアＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。中でも、Ｏ−アシルオキシム化合物は、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン及びＮ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミンからなる群から選ばれる少なくとも１種が好ましく、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミンがより好ましい。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-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-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

［式（ｄ５）中、Ｒ^３〜Ｒ^８は、置換基を有していてもよい炭素数６〜１０のアリール基を表す。］ The biimidazole compound is, for example, a compound represented by the formula (d5).

[In Formula (d5), R ^{3 to} R ⁸ represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group and a naphthyl group, and a phenyl group is preferable.
Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example, Preferably it is a methoxy group.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazo (See, for example, JP-B-48-38403, JP-A-62-174204, etc.), Imidazole compounds in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group (for example, And JP-A-7-10913). Among these, compounds represented by the following formula and mixtures thereof are preferable.

  Examples of the triazine compound 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-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Commercial products such as Lucirin (registered trademark) TPO (manufactured by BASF) and Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

The content of the polymerization initiator (D) is preferably 1 to 30% by mass and more preferably 5 to 20% by mass with respect to the total amount of the solid content.
Moreover, the content of the polymerization initiator (D) is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part, More preferably, it is 20-40 mass parts.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may 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-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

  Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

  When using these polymerization initiation assistants (D1), the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Thiol compound (T)>
The thiol compound (T) is a compound having —SH in the molecule.
Examples of the compound having one —SH in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2 -Sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4- Amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamidine -6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6 -Propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2- Sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2- Methyl-4H-1,2,4-triazo Lu-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1 , 3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2- Sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2 -Sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2 Sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4-triazole, 4- Examples include amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine and the like.

  Compounds having two or more —SH in the molecule include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl). Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), tri Methylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyl Echirutorisu (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

As the thiol compound (T), a compound having one —SH in the molecule is preferable.
The content of the thiol compound (T) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within this range, sensitivity tends to be high and developability tends to be good.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

  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, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 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, dipropylene glycol methyl ether acetate and the like.

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

These solvents may be used alone or in combination of two or more.
Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate , Ethyl lactate, 3-methoxybutyl acetate, 3- Butoxy-1-butanol, ethyl 3-ethoxypropionate, and the like are more preferable.

Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of a coloring photosensitive resin composition, More preferably, it is 75-92 mass%. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass.
When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

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

  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, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  The content of the leveling agent (F) is preferably 0.001% by mass to 0.2% by mass, preferably 0.002% by mass to 0.1%, based on the total amount of the colored photosensitive resin composition. It is not more than mass%, more preferably not less than 0.005 mass% and not more than 0.05 mass%. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Adhesion promoter (G)>
Examples of the adhesion promoter (G) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxyxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxy Silane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (amino ester Til) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (Aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Examples include triethoxysilane.

  The content of the adhesion promoter (G) is preferably 0.1% by mass or more and 5% by mass or less, and preferably 0.2% by mass or more and 2% by mass or less with respect to the total amount of the solid content. When the content of the adhesion promoter (G) is within the above range, the adhesion with the substrate can be improved.

<Other ingredients>
The colored photosensitive resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. , A thiol compound (T), a leveling agent (F), a polymerization initiation assistant (D1), an adhesion promoter (G), and other components can be mixed.
The pigment is preferably mixed in advance with part or all of the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored photosensitive resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The colored photosensitive resin composition after mixing is preferably filtered with a filter having a pore size of about 0.1 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored photosensitive resin composition of the present invention include a photolithographic method, an ink jet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored photosensitive resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5. ~ 6 μm.

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored photosensitive resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum 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 the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask to form a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

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

  According to the colored photosensitive resin composition of the present invention, a color filter with few defects can be produced, particularly because there are few residues and film residues. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  Next, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel to form a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added and stirred to 70 ° C. Heated. Then 8 parts acrylic acid, 70 parts N-cyclohexylmaleimide, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5. 2.1.0 ^2,6 ] Decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) 32 parts by weight is dissolved in propylene glycol monomethyl ether acetate 140 parts by weight to prepare a solution, The solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.
On the other hand, a solution obtained by dissolving 15 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of propylene glycol monomethyl ether acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a resin B1 solution having a solid content of 26.7% by mass. The weight average molecular weight of Resin B1 was 6.8 × 10 ³ , the molecular weight distribution was 2.23, and the acid value in terms of solid content was 114 mg-KOH / g. Resin B1 has the following structural units.

Synthesis example 2
A suitable amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Then 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution prepared by dissolving 225 parts of a mixture of decan-9-yl acrylate (content ratio is 50:50 in molar ratio) and 81 parts of vinyl toluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate. Was dropped into the flask over 4 hours.
On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition of the initiator solution, the mixture was kept at 85 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer solution. This copolymer is referred to as "resin B2." The solid content of the resin B2 solution was 37.5%, and the viscosity measured with a B-type viscometer (23 ° C.) was 246 mPa · s. Resin B2 had a weight average molecular weight of 1.06 × 10 ⁴ , a molecular weight distribution of 2.01, and an acid value in terms of solid content of 115 mg-KOH / g. Resin B2 has the following structural units.

Synthesis example 3
200 parts of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. After raising the temperature of the solution in the flask to 70 ° C., 144 parts of benzyl methacrylate, 30 parts of tricyclo [5.2.1.0 ^2.6 ] decyl methacrylate, 35 parts of methacrylic acid, 5.2 azobisisobutyronitrile. The mixture consisting of 213 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over 2 hours using a dropping funnel, and further stirred at 100 ° C. for 5 hours after completion of the addition. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a resin B3 solution having a solid content of 33.6%. Resin B3 had a weight average molecular weight of 1.03 × 10 ⁴ , a molecular weight distribution of 2.16, and an acid value in terms of solid content of 110.4 mg-KOH / g. Resin B3 has the following structural units.

Synthesis example 4
200 parts of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. After raising the temperature of the solution in the flask to 70 ° C., 144 parts of benzyl methacrylate, 30 parts of tricyclo [5.2.1.0 ^2.6 ] decyl methacrylate, 42 parts of acrylic acid, 5.2 azobisisobutyronitrile. The mixture consisting of 213 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over 2 hours using a dropping funnel, and further stirred at 100 ° C. for 5 hours after completion of the addition. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a resin B4 solution having a solid content of 34.1%. Resin B4 had a weight average molecular weight of 1.13 × 10 ⁴ , a molecular weight distribution of 2.18, and an acid value in terms of solid content of 108.5 mg-KOH / g. Resin B4 has the following structural units.

The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

[Preparation of pigment dispersion A1]
C. I. Pigment Green 36 15.0 parts Acrylic Pigment Dispersant 3.0 parts Propylene glycol monomethyl ether acetate 78.0 parts were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain Pigment Dispersion Liquid A1.

[Preparation of pigment dispersion A2]
C. I. Pigment Yellow 150 11.9 parts Acrylic pigment dispersant 5.4 parts Propylene glycol monomethyl ether acetate 77.3 parts were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion A2.

[Preparation of pigment dispersion A3]
C. I. Pigment Yellow 139 15.0 parts Acrylic Pigment Dispersant 4.5 parts Propylene Glycol Monomethyl Ether Acetate 80.6 parts was mixed, and the pigment was sufficiently dispersed using a bead mill to obtain Pigment Dispersion Liquid A3.

[Preparation of pigment dispersion A4]
C. I. Pigment Red 177 14.2 parts Acrylic Pigment Dispersant 2.8 parts Propylene glycol monomethyl ether acetate 77.3 parts were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain Pigment Dispersion Liquid A4.

[Preparation of pigment dispersion A5]
C. I. Pigment Red 254 11.1 parts Acrylic pigment dispersant 6.4 parts Propylene glycol monomethyl ether acetate 80.0 parts were mixed, and pigment dispersion A5 was obtained by sufficiently dispersing the pigment using a bead mill.

Examples 1-7 and Comparative Example 1
[Preparation of colored photosensitive resin composition]
The components shown in Table 1 were mixed to obtain a colored photosensitive resin composition.

In Table 1, the “resin (B)” column represents the content (parts) in terms of solid content.
For the colorant (A), pigment dispersions A1 to A5 were prepared in advance and used for mixing. The column “Colorant (A)” in Table 1 represents the content (parts) of the colorant contained in the used pigment dispersion.
The “acrylic dispersant” column represents the total amount (parts) of the acrylic dispersant contained in the used pigment dispersion.
The “solvent (E)” column represents the total amount (parts) of each solvent contained in the colored photosensitive resin composition.

重合開始助剤（Ｄ１）；４，４’−ビス（ジエチルアミノ）ベンゾフェノン（ＥＡＢ−Ｆ；保土ヶ谷化学工業（株）製）
チオール化合物（Ｔ）；Ｄ１a；２−スルファニルベンゾチアゾール（ソクシノール（登録商標）Ｍ；住友化学（株）製：下記式で表される化合物）

密着促進剤（Ｇ）；Ｄ１b；３-メタクリロイルオキシプロピルトリメトキシシラン（ＫＢＭ−５０３；信越化学工業（株）製）
溶剤（Ｅ）；Ｅ１；プロピレングリコールモノメチルエーテルアセテート
溶剤（Ｅ）；Ｅ２；乳酸エチル
溶剤（Ｅ）；Ｅ３；シクロヘキサノン
界面活性剤（Ｆ）；ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製；ＳＨ８４００） In Table 1, each component is as follows.
Colorant (A); A1; C.I. I. Pigment Green 36 (Pigment dispersion A1)
Colorant (A); A2; C.I. I. Pigment Yellow 150 (Pigment dispersion A2)
Colorant (A); A3; C.I. I. Pigment Yellow 139 (Pigment Dispersion A3)
Colorant (A); A4; C.I. I. Pigment Red 177 (Pigment Dispersion A4)
Colorant (A); A5; C.I. I. Pigment Red 254 (Pigment Dispersion A5)
Resin (B); B1; Resin B1
Resin (B); B2; Resin B2
Resin (B); B3; Resin B3
Resin (B); B4; Resin B4
Resin (B); B5; methacrylic acid / methyl methacrylate / n-butyl methacrylate / 2-hydroxymethacrylate copolymer (copolymerization ratio is 20/10/55/15 on a mass basis, weight average molecular weight: about 40000, JP, Synthesizing according to examples of 2004-309537
Polymerizable compound (C); C1; dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable compound (C); C2; trimethylolpropane acrylate (NK ester ATMPT; manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerization initiator (D); D1; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF; O-acyloxime compound )
Polymerization initiator (D); D2; 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF; alkylphenone compound)
Polymerization initiator (D); D3; mixture of compounds represented by the following formula (CHEMCURE-TCDM; manufactured by Cambridge; biimidazole compound)

Polymerization initiation aid (D1); 4,4′-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
Thiol compound (T); D1a; 2-sulfanylbenzothiazole (Soccinol (registered trademark) M; manufactured by Sumitomo Chemical Co., Ltd .: compound represented by the following formula)

Adhesion promoter (G); D1b; 3-methacryloyloxypropyltrimethoxysilane (KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.)
Solvent (E); E1; Propylene glycol monomethyl ether acetate Solvent (E); E2; Ethyl lactate Solvent (E); E3; Cyclohexanone Surfactant (F); Polyether-modified silicone oil (manufactured by Dow Corning Toray) SH8400)

[Preparation of pattern]
A colored photosensitive resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 30 mJ / Light irradiation was performed with an exposure amount of cm ² (based on 365 nm). A photomask having a 50 μm line and space pattern was used. After the light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 24 ° C. for 60 seconds, washed with water, and then in an oven at 230 ° C. for 30 minutes. Post-baking was performed to obtain a colored pattern.

(Developability evaluation)
The glass substrate on which the colored pattern was formed was observed with an optical microscope. If no residue or film residue was observed in the unexposed area, it was rated as “◯”. The results are shown in Table 2.

[Adhesion evaluation]
The colored pattern was observed with an optical microscope. If no peeling was observed, it was evaluated as “◯”. If peeling was observed in a part of the colored pattern, “Δ” was indicated. The results are shown in Table 2.

[Film thickness measurement]
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 2.

[Chromaticity evaluation]
About the obtained coloring pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE using the characteristic function of C light source (X, y) and tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

[Contrast evaluation]
Except not using a photomask at the time of exposure, the same operation as the pattern preparation was performed to obtain a colored pattern. About the obtained colored pattern, a contrast meter (CT-1; manufactured by Osaka Co., Ltd., color difference meter BM-5A; manufactured by Topcon Co., Ltd., light source: F-10, polarizing film; manufactured by Osaka Co., Ltd.) was used. The contrast was measured with a blank value of 30000. The results are shown in Table 2. When the colorant A1 and the colorant A4 are used in combination, the contrast of the color pattern tends to increase.

  According to the colored photosensitive resin composition of this invention, it is excellent in the developability at the time of colored pattern formation.

Claims (6)

A colored photosensitive resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
The colorant (A) is C.I. I. Pigment Green 36,
Yellow pigment,
Selected from the group consisting of blue pigments, red pigments, purple pigments and orange pigments
Including at least one kind,
The resin (B) is a copolymer containing a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit having an alicyclic hydrocarbon structure. Colored photosensitive resin composition.   The structural unit having an alicyclic hydrocarbon structure of the resin (B) is a structural unit derived from a monomer having an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. The colored photosensitive resin composition according to claim 1.   The colored photosensitive resin composition according to claim 1 or 2, wherein the polymerization initiator (D) contains an O-acyloxime compound.   At least one selected from the group consisting of a blue pigment, a red pigment, a purple pigment, and an orange pigment is C.I. I. The colored photosensitive resin composition according to any one of claims 1 to 3, which is CI Pigment Red 177.   The color filter formed with the coloring photosensitive resin composition as described in any one of Claims 1-4.   A display device comprising the color filter according to claim 5.