JP2013011867A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition having high sensitivity at the time of pattern formation.SOLUTION: A colored photosensitive resin composition contains a colorant, a resin, a polymerizable compound and a polymerization initiator, in which the colorant contains a halogenated zinc phthalocyanine pigment and a quinophthalone pigment, and the polymerization initiator contains an O-acyloxime compound and an alkylphenone compound.

Description

  The present invention relates to a colored photosensitive resin composition.

  The colored photosensitive resin composition is used for manufacturing a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. As such a colored photosensitive resin composition, only N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine is used as a polymerization initiator. The composition containing this is known (patent document 1).

JP 2009-223288 A

  Conventionally known colored photosensitive resin compositions described above may not always have sufficient sensitivity during pattern formation.

The present invention includes the following inventions.
[1] including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
The colorant comprises a zinc halide phthalocyanine pigment and a quinophthalone pigment;
A colored photosensitive resin composition, wherein the polymerization initiator includes an O-acyloxime compound and an alkylphenone compound.
[2] The colored photosensitive resin composition according to [1], wherein the polymerization initiator further includes a biimidazole compound.
[3] The colored photosensitive resin composition according to [1] or [2], further comprising a thiol compound.
[4] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].

  According to the present invention, it is possible to provide a colored photosensitive resin composition having high sensitivity during pattern formation.

  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), and the colorant (A) is a halogenated zinc phthalocyanine pigment. And a quinophthalone pigment, and the polymerization initiator (D) is a colored photosensitive resin composition that is a polymerization initiator containing an O-acyloxime compound and an alkylphenone compound.

  The colored photosensitive resin composition of the present invention contains a halogenated zinc phthalocyanine pigment (A1) and a quinophthalone pigment (A2) as a colorant (A).

The halogenated zinc phthalocyanine pigment (A1) is a pigment containing a halogenated zinc phthalocyanine compound. The halogenated zinc phthalocyanine compound is a compound having a phthalocyanine compound having a halogen atom as a ligand and having zinc as a central metal, and is preferably a compound represented by the formula (P).
The content of the halogenated zinc phthalocyanine compound in the halogenated zinc phthalocyanine pigment (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, the halogenated zinc phthalocyanine pigment (A1) is preferably composed only of a halogenated zinc phthalocyanine compound.

[In Formula (P), A ^{1 to} A ¹⁶ independently represent a hydrogen atom, a chlorine atom, or a bromine atom, and at least one represents a chlorine atom or a bromine atom. ]

Among A ^{1 to} A ¹⁶ , 0 to 6 are preferably chlorine atoms, 10 to 16 are bromine atoms, and the sum of the number of chlorine atoms and the number of bromine atoms is preferably 10 to 16 More preferably, 0-3 are chlorine atoms, 13-16 are bromine atoms, and the sum of the number of chlorine atoms and the number of bromine atoms is 13-16, More preferably, 13 to 15 chlorine atoms are bromine atoms, and the sum of the number of chlorine atoms and the number of bromine atoms is 14 to 16.

When the number of substituents is in the above range, the hue becomes yellowish, and the brightness becomes high without lowering the color reproduction range when a color filter is formed.
Preferred examples of the halogenated zinc phthalocyanine pigment include C.I. I. And CI Pigment Green 58.

  Examples of the halogenated zinc phthalocyanine pigment (A1) include those disclosed in JP 2007-284589, JP 2007-284592, JP 2007-291232, JP 2007-320986, and JP 2008-19383. It can be produced by the method described.

The quinophthalone pigment (A2) is a pigment containing a quinophthalone compound. The quinophthalone compound is preferably a compound represented by the formula (Q).
The content of the quinophthalone compound in the quinophthalone pigment (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, the quinophthalone pigment (A2) is preferably composed only of a quinophthalone compound.

［式（Ｑ２）中、Ｘ^１〜Ｘ^８は、互いに独立に、水素原子、ハロゲン原子又は炭素数１〜６のアルキル基を表す。］
ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子及びヨウ素原子等が挙げられる。
炭素数１〜６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基及びヘキシル基等が挙げられる。
顔料の入手が容易である点及び得られるカラーフィルタの明度の点で、Ｘ^１〜Ｘ^８は、互いに独立に、塩素原子又は臭素原子であることが好ましく、全て塩素原子であることがより好ましい。
好ましいキノフタロン顔料（Ａ２）としては、例えば、Ｃ．Ｉ．ピグメントイエロー１３８が挙げられる。

[In Formula (Q2), X ^{1 to} X ⁸ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. ]
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group.
X ^{1 to} X ⁸ are each independently a chlorine atom or a bromine atom, more preferably a chlorine atom, from the viewpoint of easy availability of the pigment and the brightness of the obtained color filter. .
Preferred examples of the quinophthalone pigment (A2) include C.I. I. And CI Pigment Yellow 138.

The halogenated zinc phthalocyanine pigment (A1) and the quinophthalone pigment (A2) are optionally treated with 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 halogenated zinc phthalocyanine pigment (A1) and the quinophthalone pigment (A2) preferably have uniform particle sizes.

  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 halogenated zinc phthalocyanine pigment (A1) and the quinophthalone pigment (A2) may be dispersed separately, or both 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. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), and 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.

  The colorant (A) contained in the colored photosensitive resin composition of the present invention may further contain a pigment (A3) different from the halogenated zinc phthalocyanine pigment (A1) and the quinophthalone pigment (A2). It is preferable not to include.

As the pigment (A3), specifically, the color index (The Society of Dyers and Colouri
compounds classified as pigments by sts publication). Specifically, for example, 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, 139, 147, Yellow pigments such as 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7 and 36;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

Among them, C.I. I. Pigment yellow 139, 150, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Green 7 and 36 are preferable. These pigments may be used alone or in combination of two or more.
The pigment (A3) is preferably subjected to a dispersion treatment in the same manner as the halogenated zinc phthalocyanine pigment (A1) and the quinophthalone pigment (A2).

The content of the halogenated zinc phthalocyanine pigment (A1) is preferably 20 to 95% by mass and more preferably 30 to 90% by mass with respect to the colorant (A).
5-80 mass% is preferable with respect to a coloring agent (A), and, as for content of a quinophthalone pigment (A2), 10-70 mass% is more preferable.
When the content of the halogenated zinc phthalocyanine pigment (A1) and the quinophthalone pigment (A2) is in the above range, the resulting color filter tends to be excellent in contrast, brightness, heat resistance, and chemical resistance.

  The total amount of the colorant (A) is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, based on the solid content of the colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention contains a resin (B). Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1] At least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a monomer (b) (hereinafter sometimes referred to as “(b)”) having an ethylenically unsaturated bond.
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) Copolymer with Resin [K3] (a) and (c) Resin [K4] Obtained by reacting (b) with copolymer of (a) and (c) Resin.
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 with a carboxylic acid anhydride.

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 (hymic acid 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.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

(B) has, for example, 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 (oxolane ring)) and an ethylenically unsaturated bond. It refers to a polymerizable compound. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  (B1) is, for example, a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as “(b1-1)”), an unsaturated alicyclic hydrocarbon And a monomer (b1-2) (hereinafter sometimes referred to as “(b1-2)”) having an epoxidized structure.

  As (b1-1), 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 2,4-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- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

[In Formula (I) and Formula (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ^a and ^{X b} are each independently a single ^{bond, -R c -, * - R} c -O -, * - R c -S -, * - represents the 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 alkanediyl groups 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— (* represents a bond to O) group, or * —CH ₂ CH ₂ —O— group. More preferably, a single bond and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) Is mentioned. More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

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

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, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (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;

  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. .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 Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, 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, benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2. 2.1] hept-2-ene and the like are preferable. Moreover, since it is excellent in the developability at the time of pattern formation, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable.

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%)
Structural unit derived from (b); 50 to 98 mol% (more preferably 55 to 90 mol%)
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and stirred, heated, and kept warm in a deoxygenated atmosphere. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of 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.) As the solvent, any solvent capable of dissolving each monomer may be used, and a solvent (E) described later can be used as a solvent for the colored photosensitive resin composition.

  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 a solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
Structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%)
Structural unit derived from (b); 2-95 mol% (more preferably 5-80 mol%)
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%)
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, heat resistance, and mechanical strength tend to be excellent.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].
Specifically, a predetermined amount of (a), (b) and (c), a polymerization initiator, and a solvent are charged into a reaction vessel, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
(A) 2 to 55 mol%, more preferably 10 to 50 mol%
(C) 45-98 mol%, more preferably 50-90 mol%
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
(A) 5 to 50 mol%, more preferably 10 to 45 mol%
(C) 50 to 95 mol%, more preferably 55 to 90 mol%

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( (Dimethylaminomethyl) phenol and the like) and a polymerization inhibitor (for example, hydroquinone and the like) are placed in a flask and reacted at, for example, 60 to 130 ° C. for 1 to 10 hours to obtain a resin [K4]. .
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c).
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.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. 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.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
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). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. 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 (highmic acid anhydride) and the like. It is done.

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. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Resin [K3] such as (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; benzyl Resin obtained by adding glycidyl (meth) acrylate to (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Added resin, resin [K4] such as resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; tricyclodecyl (meta ) Acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid Reacted resin, resin such as resin obtained by reacting (meth) acrylic acid with tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer [K5]; tricyclodecyl (meth) acrylate / Examples thereof include a resin [K6] such as a resin obtained by further reacting a copolymer of glycidyl (meth) acrylate with (meth) acrylic acid and further reacting with tetrahydrophthalic anhydride.
These resins may be used alone or in combination of two or more.

  Among them, as the resin (B), the resin [K3] is preferable and has at least one selected from the group consisting of a structural unit derived from benzyl (meth) acrylate and a structural unit derived from tricyclodecyl (meth) acrylate. Resin [K3] is more preferable, and resin [K3] having both a structural unit derived from benzyl (meth) acrylate and a structural unit derived from tricyclodecyl (meth) acrylate is more preferable. These resins can form a pattern with high sensitivity and have a high dissolution rate during development.

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 solubility of the unexposed portion in the developer tends to be high, and the remaining film ratio and hardness of the resulting pattern tend to be high.
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 180 mg-KOH / g, more preferably 60 to 150 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, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

  The content of the resin (B) 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 solid content of the colored photosensitive resin composition. %. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

  The colored photosensitive resin composition of the present invention contains a polymerizable compound (C), and the polymerizable compound (C) preferably has a weight average molecular weight of 3,000 or less. The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical or the like generated from the polymerization initiator (D) by being irradiated with light, for example, polymerizable ethylenically unsaturated Examples thereof include a compound having a bond.

Among these, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, such as 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 (meta ) 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 And caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like can be given.
The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass with respect to 100 parts by mass of the resin (B) in the colored photosensitive resin composition.

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−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。 The colored photosensitive resin composition of the present invention contains an O-acyloxime compound and an alkylphenone compound as the polymerization initiator (D).
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, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 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 It is done. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used.

Among these, a compound having a partial structure represented by the formula (d2) is preferable, and a compound represented by the formula (d3) is more preferable.

［式（ｄ３）中、Ｒ^１は、炭素数１〜８の飽和炭化水素基を表す。Ｒ^２は、炭素数１〜４のアルキル基又はフェニル基を表す。］

[In the formula (d3), R ¹ represents a saturated hydrocarbon group having 1 to 8 carbon atoms. R ² represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. ]

Examples of the saturated hydrocarbon group having 1 to 8 carbon atoms include an alkyl group having 1 to 8 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 8 carbon atoms, and a group in which these are combined.
Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Especially, a C2-C6 alkyl group is preferable and a hexyl group is more preferable.
Examples of the cyclic saturated hydrocarbon group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a norbornyl group. Of these, a cyclopentyl group is preferred.

  Examples of O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-2-imine is preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

The alkylphenone compound is a compound having a partial structure represented by the formula (d4) or a partial structure represented by the formula (d5). In the partial structure represented by the formula (d4) or the partial structure represented by the formula (d5), the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d4) 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] -1-butanone, etc. Is mentioned. 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 (d5) 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 (d4).

［式（ｄ６）中、Ｒ^４〜Ｒ^９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 polymerization initiator (D) preferably further contains a biimidazole compound. As the biimidazole compound, a compound represented by the formula (d6) is preferable.

[In Formula (d6), R ^{4 to} R ⁹ 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.

  The polymerization initiator (D) may include a polymerization initiator (D ′) other than the O-acyloxime compound, the alkylphenone compound, and the biimidazole compound, but is preferably not included in terms of sensitivity. The polymerization initiator (D ′) is not particularly limited as long as it is a compound that generates an active radical by the action of light and initiates polymerization of the polymerizable compound (C), and a known polymerization initiator may be used. it can. Examples of the polymerization initiator (D ′) include triazine compounds and acylphosphine oxide compounds. These polymerization initiators may be used alone or in combination of two or more.

  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- Methoxystyryl) -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-Methylfe Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like. .

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

  Furthermore, 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; 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.

When the polymerization initiator (D) does not contain a biimidazole compound,
The content of the O-acyloxime compound is preferably 10 to 80% by mass and more preferably 30 to 75% by mass with respect to the polymerization initiator (D).
The content of the alkylphenone compound is preferably 20 to 90% by mass and more preferably 25 to 70% by mass with respect to the polymerization initiator (D).
When the polymerization initiator (D) contains a biimidazole compound,
The content of the O-acyl oxime compound is preferably 10 to 80% by mass and more preferably 30 to 60% by mass with respect to the polymerization initiator (D).
The content of the alkylphenone compound is preferably 15 to 85% by mass and more preferably 20 to 60% by mass with respect to the polymerization initiator (D).
The content of the biimidazole compound is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, and further preferably 2 to 30% by mass with respect to the polymerization initiator (D). Even more preferably, it is 2 to 20% by mass.

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 solid content of the colored photosensitive resin composition.
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 10-30 mass parts.

The colored photosensitive resin composition of the present invention may contain a polymerization initiation assistant (D1). When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D). The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D).
Examples of the polymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. These polymerization initiation assistants may be used alone or in combination of two or more.
Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl 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, and 4,4′-bis (diethylamino) benzophenone is preferred. 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, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When using the polymerization initiation assistant (D1), the content thereof is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, relative to 1 mol of the polymerization initiator (D).
Moreover, the total content of the polymerization initiator (D) and the polymerization initiation assistant (D1) is preferably 1 to 35% by mass, more preferably 5 to 25%, based on the solid content of the colored photosensitive resin composition. It is 10 mass%, More preferably, it is 10-20 mass%.

  The colored photosensitive resin composition of the present invention preferably further contains a 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, the sensitivity tends to be high and the developability tends to be good.

  The colored photosensitive resin composition of the present invention preferably contains a solvent (E). A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), ketones other than ester solvents A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, or the like can be selected and used.

  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, and the like methyl anisole.

  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.

  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, and glycerin.
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, 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, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, More preferred are 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like.

  The content of the solvent (E) is preferably 70 to 95% by mass and more preferably 75 to 92% by mass with respect to the colored photosensitive resin composition. 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.

  The colored photosensitive resin composition of the present invention contains additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc., as necessary. But you can.

Examples of the method for forming a pattern using 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, exposed through a photomask, and developed to obtain a pattern. In this method, a coating film having no pattern can be obtained by not performing exposure and / or development through a photomask.

Examples of the substrate include glass, metal, plastic, and the like, and may be plate-shaped or film-shaped. In addition, structures such as a color filter, various insulating or conductive films, and a driving circuit may be formed on these substrates.
Application to the substrate can be performed using a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater, a curtain flow coater, or a spinless coater) or an inkjet.

Examples of the method for drying the film applied to the substrate include methods such as heat drying, natural drying, ventilation drying, and vacuum drying. A plurality of methods may be combined. As drying temperature, 10-120 degreeC is preferable and 25-100 degreeC is more preferable. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. The vacuum drying is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa.
The film thickness of the coating film after drying is not particularly limited and can be appropriately adjusted depending on the material used, application, and the like, and is, for example, 0.1 to 20 μm, preferably 1 to 6 μm.

The dried coating film is exposed through a photomask for forming a target pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended application 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.
It is preferable to use an apparatus such as a mask aligner or a stepper because the entire exposed surface can be irradiated with parallel rays uniformly and accurate alignment between the mask and the substrate can be performed.

After exposure, a pattern can be obtained by contacting a developing solution to dissolve a predetermined portion, for example, an unexposed portion, and developing. As the developer, an organic solvent can be used, but an aqueous solution of a basic compound is preferable because the developer does not easily dissolve or swell the exposed portion of the coating film, and a pattern having a good shape is obtained.
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.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, and sodium carbonate. Inorganic basic compounds such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine Organic basic compounds such as monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Of these, potassium hydroxide, sodium hydrogen carbonate and tetramethylammonium hydroxide are preferable.
The density | concentration in the aqueous solution of these inorganic and organic basic compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The aqueous solution of the basic compound may contain a surfactant.
Surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters , Nonionic surfactants such as polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine;
Anionic surfactants such as sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate;
And cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
The concentration of the surfactant in the aqueous solution of the basic compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and particularly preferably 0.1 to 5% by mass.

  Furthermore, you may post-bake as needed. Post baking is preferably performed, for example, in the range of 150 to 250 ° C. for 1 to 240 minutes.

  The pattern obtained as described above by the colored photosensitive resin composition of the present invention is useful as a color filter. The color filter can be used in a known manner for devices related to various colored images such as a display device (for example, a liquid crystal display device, an organic EL device, etc.), a solid-state imaging device, and electronic paper.

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

Synthesis example 1
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 kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw was 10.3 × 10 ³ , solid content 33.6%, solid content. A resin B1 solution having an acid value of 110.4 mg-KOH / g was obtained.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 2.5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts of ethylene glycol monomethyl ether acetate, followed by 15 parts of methacrylic acid and ω-carboxyl. 10 parts of dicaprolactone monoacrylate, 15 parts of N-phenylmaleimide, 33 parts of 2-ethylhexyl methacrylate, 12 parts of styrene, 15 parts of glycerol monomethacrylate and 5.0 parts by weight of α-methylstyrene dimer (chain transfer agent) After substituting with nitrogen, the reaction solution was heated to 80 ° C. with gentle stirring and polymerized for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was further continued for 1 hour, whereby resin B2 solution (Solid concentration = 30%) was obtained. Resin B2 had Mw = 14,000 and Mn = 5,700.

About the measurement of polystyrene conversion weight average molecular weight Mw and number average molecular weight Mn of resin obtained by said synthesis example, it carried out on condition of the following using GPC method.
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)

[Preparation of pigment dispersion 1]
C. I. Pigment Green 58 10.8 parts Acrylic pigment dispersant 2.8 parts Propylene glycol monomethyl ether acetate 76.3 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, whereby a pigment dispersion (A-1) Got.

[Preparation of pigment dispersion 2]
C. I. Pigment Yellow 138 15.1 parts Acrylic pigment dispersant 4.5 parts Propylene glycol monomethyl ether acetate 75.9 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, whereby a pigment dispersion (A-2) Got.

[Preparation of pigment dispersion 3]
C. I. Pigment Green 58 24 parts C.I. I. Pigment Yellow 138 16 parts Dispersbyk-2001 (manufactured by Big Chemie) 24 parts Propylene glycol monomethyl ether acetate 136 parts were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-3).

Examples 1 to 12 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 addition, it mixed with propylene glycol monomethyl ether acetate so that solid content of a coloring photosensitive resin composition might be "solid content (%)" of Table 1.

重合開始剤（Ｄ）；Ｄ１−１；ジエチルチオキサントン
チオール化合物（Ｔ）；Ｔ−１；２−スルファニルベンゾチアゾール（Soxinol M；住友化学（株）製製；下記式で表される化合物）

In Table 1, each component is as follows.
Colorant (A); A-1; Pigment dispersion (A-1) obtained above
Colorant (A); A-2; Pigment dispersion (A-2) obtained above
Colorant (A); A-3; Pigment dispersion (A-3) obtained above
Resin (B); B-1; Resin B1 solution Resin (B); B-2; Resin B2 solution Polymerizable compound (C); C-1; Dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Made)
Polymerization initiator (D); D-1; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; O-acyloxime compound)
Polymerization initiator (D); D-2; N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine (Irgacure OXE 02; BASF (O-acyl oxime compound)
Polymerization initiator (D); D-3; 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF; alkylphenone compound)
Polymerization initiator (D); D-4; Mixture of compounds represented by the following formula (CHEMCURE-TCDM; manufactured by Cambridge; biimidazole compound)

Polymerization initiator (D); D1-1; Diethylthioxanthone thiol compound (T); T-1; 2-sulfanylbenzothiazole (Soxinol M; manufactured by Sumitomo Chemical Co., Ltd .; compound represented by the following formula)

[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. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the photomask made of quartz glass having a pattern is set to 100 μm, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) , And was irradiated with light at an exposure dose of 150 mJ / cm ² (based on 365 nm). As a photomask, a mask on which a 50 μm line and space pattern was formed was used. After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and 220 ° C. in an oven. Was post-baked for 20 minutes to obtain a pattern.

[Sensitivity evaluation]
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. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the photomask made of quartz glass having a pattern is set to 100 μm, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) , And was irradiated with light at an exposure dose of 50 mJ / cm ² (based on 365 nm). In addition, as a photomask, the gray scale mask which has a translucent part with the transmittance | permeability of 1 to 100% with respect to the transmittance | permeability of quartz glass was used. The size of each translucent part is 5 × 8 mm. After the light irradiation, the coating film was developed by immersing it in an aqueous developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 24 ° C. for 60 seconds, and washed with water. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a pattern. The board | substrate with which the pattern was formed was observed visually, and the sensitivity was calculated | required from the following formula. The results are shown in Table 2.
Sensitivity (mJ / cm ² ) = T _M (%) × 50 (mJ / cm ² )
Wherein, T _M, of the pattern formed from the transparent portion remaining on the substrate, representing the transmittance of the transparent portion corresponding to the pattern formed from the lowest transmittance transparent portion. ]

[Evaluation of dissolution time]
A colored photosensitive resin composition was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) in the same manner as described above, and then pre-baked at 100 ° C. for 3 minutes. After cooling, an aqueous developer containing 0.12% nonionic surfactant and 2% sodium carbonate was sprayed at 0.05 hPa with a spin developing machine (SD-408R; manufactured by Oshibe) The time until all of the film applied on the surface was dissolved was measured. The results are shown in Table 2.

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

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

According to the present invention, it is possible to provide a colored photosensitive resin composition having high sensitivity during pattern formation.
The pattern obtained as described above by the colored photosensitive resin composition of the present invention is useful as a color filter. The color filter can be used in a known manner for devices related to various colored images such as a display device (for example, a liquid crystal display device, an organic EL device, etc.), a solid-state imaging device, and electronic paper.

Claims (5)

Including a colorant, a resin, a polymerizable compound and a polymerization initiator,
The colorant comprises a zinc halide phthalocyanine pigment and a quinophthalone pigment;
A colored photosensitive resin composition, wherein the polymerization initiator includes an O-acyloxime compound and an alkylphenone compound.   The colored photosensitive resin composition according to claim 1, wherein the polymerization initiator further contains a biimidazole compound.   Furthermore, the coloring photosensitive resin composition of Claim 1 or 2 containing a thiol compound.   The color filter formed with the coloring photosensitive resin composition as described in any one of Claims 1-3.   A display device comprising the color filter according to claim 4.