JP6787436B2 - Color curable resin composition - Google Patents

Description

The present invention relates to a colored curable resin composition.

Color filters formed from color-curable resin compositions are used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels, and color filters having good brightness, good contrast, and good resolution are required. Was being done.
In order to realize a color filter having good brightness, good contrast, and good resolution, a color curable resin composition containing a dye as a colorant has been studied, but heat resistance due to the inclusion of the dye, There has been a problem that chemical resistance and the like are lowered.
In Patent Document 1, C.I. I. Pigment Blue 15: 6 and C.I. I. A colored curable resin composition containing Acid Red 52 and a dye represented by the following formula, wherein C.I. I. The content of Acid Red 52 is C.I. I. Pigment Blue 15: 6 A colored curable resin composition having 14.7 parts by mass with respect to 100 parts by mass is described.

Japanese Unexamined Patent Publication No. 2013-144724

The color filter formed from the above-mentioned color curable resin composition did not always sufficiently satisfy both heat resistance and lightness.

［式（Ａ７）中、
ｇは、任意の自然数を表す。
Ｇ^ｇ−は、ｇ価のアニオンを表す。
Ｄは、置換基を有していてもよいヘテロ芳香族炭化水素基を表す。
Ｒ^１Ａ、Ｒ^２Ａ、Ｒ^３Ａ、Ｒ^４Ａ、Ｒ^５Ａ、Ｒ^６Ａ、Ｒ^７Ａ及びＲ^８Ａは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基又はアルキル基を表し、該アルキル基に含まれる−ＣＨ_２−は、−Ｏ−に置き換わっていてもよい。
Ｒ^２１Ａ及びＲ^２２Ａは、それぞれ独立して、置換されていてもよいアミノ基を表す。
］
［１２］青色顔料（Ａ１）が、Ｃ．Ｉ．ピグメントブルー１５：６を含む［１１］に記載の着色剤。
［１３］青色顔料（Ａ１）が、Ｃ．Ｉ．ピグメントブルー１５：６のみからなる［１１］に記載の着色剤。
［１４］［１１］〜［１３］のいずれかに記載の着色剤、樹脂（Ｂ）、重合性化合物（Ｃ）及び重合開始剤（Ｄ）を含む着色硬化性樹脂組成物。
［１５］［１］〜［６］、［１０］及び［１４］のいずれかに記載の着色硬化性樹脂組成物により形成されるカラーフィルタ。
［１６］［１５］に記載のカラーフィルタを含む表示装置。 The present invention includes the following inventions.
[1] A color curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the colorant (A) is a blue pigment (A1). ) And C.I. I. Including Acid Red 52, C.I. I. A colored curable resin composition in which the content of acid red 52 is 0.1 to 10 parts by mass with respect to 100 parts by mass of the blue pigment (A1).
[2] The color curable resin composition according to [1], wherein the colorant (A) further contains a blue or purple dye (A2).
[3] The content of the blue or purple dye (A2) is C.I. I. The colored curable resin composition according to [2], which is 80 to 10000 parts by mass with respect to 100 parts by mass of Acid Red 52.
[4] The content of the blue or purple dye (A2) is C.I. I. The colored curable resin composition according to [3], which is 80 to 1000 parts by mass with respect to 100 parts by mass of Acid Red 52.
[5] The blue pigment (A1) is C.I. I. The colored curable resin composition according to any one of [1] to [4], which comprises Pigment Blue 15: 6.
[6] The blue pigment (A1) is C.I. I. The colored curable resin composition according to any one of [1] to [4], which comprises only Pigment Blue 15: 6.
[7] Triarylmethane dye, blue pigment (A1) and C.I. I. A colorant containing Acid Red 52, wherein the triarylmethane dye is a polymer.
[8] The blue pigment (A1) is C.I. I. The colorant according to [7], which comprises Pigment Blue 15: 6.
[9] The blue pigment (A1) is C.I. I. The colorant according to [7], which comprises only Pigment Blue 15: 6.
[10] A color curable resin composition containing the colorant, resin (B), polymerizable compound (C) and polymerization initiator (D) according to any one of [7] to [9].
[11] Polymers containing structural units derived from the dye represented by the formula (A7) or the dye represented by the formula (A7), the blue pigment (A1) and C.I. I. A colorant containing Acid Red 52.

[In formula (A7),
g represents an arbitrary natural number.
G ^g- represents a g-valent anion.
D represents a heteroaromatic hydrocarbon group which may have a substituent.
R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group or an alkyl group, and the alkyl group. -CH _2- contained in may be replaced with -O-.
R ^21A and R ^22A each independently represent an ^optionally substituted amino group.
]
[12] The blue pigment (A1) is C.I. I. The colorant according to [11], which comprises Pigment Blue 15: 6.
[13] The blue pigment (A1) is C.I. I. The colorant according to [11], which comprises only Pigment Blue 15: 6.
[14] A color curable resin composition containing the colorant, resin (B), polymerizable compound (C) and polymerization initiator (D) according to any one of [11] to [13].
[15] A color filter formed by the color curable resin composition according to any one of [1] to [6], [10] and [14].
[16] A display device including the color filter according to [15].

According to the color curable resin composition of the present invention, a color filter having good heat resistance and good brightness can be produced.

The color-curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
The color curable resin composition of the present invention preferably contains at least one selected from the solvent (E) and the leveling agent (F).
The color curable resin composition of the present invention may contain a polymerization initiation aid (D1).

<Colorant (A)>
The colorant (A) is a blue pigment (A1) and C.I. I. Includes Acid Red 52.
C. I. The content of acid red 52 is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and 1 to 8 parts by mass with respect to 100 parts by mass of the blue pigment (A1). It is more preferably parts by mass.
The colorant (A) may contain a blue or purple dye (A2) (hereinafter, may be referred to as "dye (A2)"). The colorant (A) is a pigment different from the blue pigment (A1) (hereinafter, may be referred to as "pigment (Ad)"), or a dye (Ac) different from the blue or purple dye (A2) (hereinafter,). , "Dye (Ac)" may be included.).
In the present application, "CI" means a color index (CI).

<Blue pigment (A1)>
Examples of the blue pigment (A1) include C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, preferably C.I. I. Pigment Blue 15: 3 and 15: 6, more preferably C.I. I. Pigment Blue 15: 6.
Two or more kinds of blue pigments (A1) may be contained.
The blue pigment (A1) is C.I. I. Pigment Blue 15: 6 is preferably included, and C.I. I. More preferably, it consists only of Pigment Blue 15: 6.

<Dye (A2)>
The blue or purple dye means a dye having a maximum absorption wavelength in the range of 560 nm or more and 650 nm or less in a chloroform solution. The blue or purple dye is preferably a dye having a maximum absorption wavelength in the range of 580 nm or more and 650 nm or less, and more preferably a dye having a maximum absorption wavelength in the range of 600 nm or more and 645 nm or less.
The blue or purple dye (A2) is a dye represented by a xanthene dye (A3), a triarylmethane dye (A4), a tetraazaporphyrin dye (A5), an anthraquinone dye (A6) and a formula (A7) (hereinafter, dye). It is preferably at least one selected from the group consisting of (A7).
More preferably, it is at least one selected from the group consisting of xanthene dye (A3), triarylmethane dye (A4) and dye (A7).
More preferably, it is at least one selected from the group consisting of the triarylmethane dye (A4) and the dye (A7).
Two or more kinds of dyes (A2) may be contained.

The xanthene dye (A3) is a dye containing a compound having a xanthene skeleton in the molecule.
Examples of the xanthene dye (A3) include the compounds described below. In the formula below, R ²⁶ and R ⁴⁰ each represent a 2-ethylhexyl group.

Examples of the xanthene dye (A3) include commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugai Pharmaceutical Co., Ltd. and "Rhodamin 6G" manufactured by Taoka Chemical Co., Ltd.). .. Further, it is also possible to synthesize using a commercially available xanthene dye as a starting material with reference to Japanese Patent Application Laid-Open No. 2010-32999.

The triarylmethane dye (A4) is a dye containing a compound having a triarylmethane skeleton in the molecule. Examples of the triarylmethane dye (A4) include, for example.
C. I. Acid Violet (Hereinafter, the description of CI acid violet is omitted and only the number is described.) 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72,
C. I. Acid Blue 1,3,5,7,9,11,13,15,17,22,24,26,34,38,48,75,83,84,86,88,90,90: 1,91, 93, 93: 1, 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269,
C. I. Basic Blue 7, 81, 83, 88, 89,
C. I. Basic Violet 2,
C. I. Direct Blue 1, 3, 28, 29, 41, 42, 47, 52, 55,
C. I. Food Violet 3,
C. I. Modant Violet 1, 1: 1, 3, 6, 8, 10, 11, 15, 16, 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, 49,
And so on.

Examples of the triarylmethane dye (A4) include the compounds described below.

The tetraazaporphyrin dye (A5) is a dye containing a compound having a tetraazaporphyrin skeleton in the molecule. When the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.
Examples of the tetraazaporphyrin dye include the compounds described below.

The anthraquinone dye (A6) is a dye containing a compound having an anthraquinone skeleton in the molecule.
Examples of the anthraquinone dye (A6) include, for example.
C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112
C. I. Disperse Violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct Blue 40,
C. I. Modant Blue 8
And so on.

Examples of the anthraquinone dye (A6) include the compounds described below.

［式（Ａ７）中、
ｇは、任意の自然数を表す。
Ｇ^ｇ−は、ｇ価のアニオンを表す。
Ｄは、置換基を有していてもよいヘテロ芳香族炭化水素基を表す。
Ｒ^１Ａ、Ｒ^２Ａ、Ｒ^３Ａ、Ｒ^４Ａ、Ｒ^５Ａ、Ｒ^６Ａ、Ｒ^７Ａ及びＲ^８Ａは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基又はアルキル基を表し、該アルキル基に含まれる−ＣＨ_２−は、−Ｏ−に置き換わっていてもよい。
Ｒ^２１Ａ及びＲ^２２Ａは、それぞれ独立して、置換されていてもよいアミノ基を表す。
］ Examples of the dye (A7) include a compound represented by the formula (A7) and a tautomer thereof.

[In formula (A7),
g represents an arbitrary natural number.
G ^g- represents a g-valent anion.
D represents a heteroaromatic hydrocarbon group which may have a substituent.
R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group or an alkyl group, and the alkyl group. -CH _2- contained in may be replaced with -O-.
R ^21A and R ^22A each independently represent an ^optionally substituted amino group.
]

Alkyl groups represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. , Se-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, Cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl group) Il) Alkane-1-yl groups, norbornyl groups, methylnorbornyl groups, isobornyl groups and other alkyl groups having 1 to 20 carbon atoms can be mentioned. It is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
-CH _2- contained in the alkyl group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A may be replaced with -O-.
Specific examples of the group in which -CH _2- contained in the alkyl groups represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A are replaced with -O- Examples include the following groups. Preferably, −CH ₂ − contained in the alkyl group having 1 to 10 carbon atoms is replaced with −O −, and more preferably −CH ₂ − contained in the alkyl group having 1 to 6 carbon atoms is −. It is a group that replaces O-.

Examples of the halogen atom represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A include fluorine atom, chlorine atom, bromine atom and iodine atom, and fluorine atom is preferable. It is an atom or a chlorine atom.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. It is more preferably a methyl group and even more preferably a hydrogen atom.

The hydrogen atom contained in the amino group represented by R ^21A and R ^22A is an aryl group which may have a substituent, an alkyl group which may have a substituent, or an acryloyl group or a methacryloyl group. It may be substituted with a containing group.

Among the aryl groups which may have a substituent, examples of the aryl group include an aryl group having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group and an anthracenyl group, and the aryl group may have an aryl group. Examples of the substituent include a halogen atom and an alkyl group having 1 to 8 carbon atoms.

Among the alkyl groups which may have a substituent, the alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a pentyl group. Hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group , Cyclooctyl group, Cyclononyl group, Cyclodecyl group, Decahydronaphthyl group, Adamanthyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, norbornyl group, methylnor Examples thereof include alkyl groups having 1 to 20 carbon atoms such as a boronyl group and an isobornyl group. Other -CH 2 _{- -} -CH 2 adjacent to a nitrogen atom contained in the alkyl group may be replaced by -O-, Examples of the substituent that the said alkyl group optionally having an amino group , Substituent amino groups, groups containing halogen atoms and silicon atoms.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the substituted amino group, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, sec-butylamino group, tert-butylamino group, dimethylamino group, diethylamino group, dipropylamino group, Examples thereof include an alkylamino group having 1 to 8 carbon atoms such as an ethylmethylamino group and a dialkylamino group having 1 to 8 carbon atoms.

［式（Ａ７−１）中、Ｒ^１５Ａはアクリロイル基又はメタクリロイル基を表す。
Ｒ^１４Ａは、炭素数１〜８のアルカンジイル基を表し、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−に置き換わっていてもよい。
＊は窒素原子との結合手を表す。］ The group containing an acryloyl group or a methacryloyl group means a group having at least one acryloyl group or a methacryloyl group as a constituent unit of the group.
The carbon number of a group containing an acryloyl group or a methacryloyl group is usually 3 to 30, preferably 3 to 20.
The group containing an acryloyl group or a methacryloyl group is preferably a group containing an acryloyloxy group or a methacryloyloxy group.
The group containing an acryloyl group or a methacryloyl group is preferably a group represented by the formula (A7-1).

[In formula (A7-1), R ^15A represents an acryloyl group or a methacryloyl group.
R ^14A represents an alkanediyl group having 1 to 8 carbon atoms, and −CH ₂ − contained in the alkanediyl group may be replaced with −O−.
* Represents a bond with a nitrogen atom. ]

Examples of the alkanediyl group having 1 to 8 carbon atoms represented by R ^14A include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , Hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1, 2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1 , 4-Diyl group, 2-methylbutane-1,4-Diyl group, preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, and further preferably a methylene group. Is.

Examples of the group containing an acryloyl group or a methacryloyl group include the groups described below. (* Indicates the bond with the nitrogen atom.)

The ^optionally substituted amino groups represented by R ^21A and R ^22A include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, sec-butylamino group, and the like. tert-butylamino group, pentylamino group, neopentylamino group, hexylamino group, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, ethylmethylamino group, ethylisopropylamino group, ethylpropylamino group, Isopropylmethylamino group, isopropylpropylamino group, methylpropylamino group, phenylamino group, naphthylamino group, 2-methylphenylamino group, 4-methylphenylamino group, 3-methylphenylamino group, 3,5-dimethylphenyl Amino group, 4-ethylphenylamino group, N-methyl-N-phenylamino group, acryloyloxymethylamino group, N- (acryloyloxymethyl) -N-methylamino group, N- (acryloyloxyethyl) -N- Ethylamino group, N- (methacryloyloxyethyl) -N-ethylamino group, N- (acryloyloxyethyl) -N-phenylamino group, N- (acryloyloxyethyl) -N- (methacryloyloxymethyl) amino group, Examples thereof include N- (acryloyloxyethyloxymethyl) -N-ethylamino group and N- (methacryloyloxyethyloxymethyl) -N-ethylamino group.

The heteroaromatic hydrocarbon group represented by D may have at least one heteroatom, and examples of the heteroatom include a nitrogen atom, an oxygen atom and a sulfur atom.
The heteroaromatic hydrocarbon group represented by D may be monocyclic or polycyclic.
The heteroaromatic hydrocarbon group represented by D includes a pyridyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, a benzothiazolyl group, a benzoisothiazolyl group, a thienyl group and a benzothienyl group. Examples thereof include a heteroaromatic hydrocarbon group having 2 to 8 carbon atoms, and a heteroaromatic hydrocarbon group having 2 to 8 carbon atoms containing at least one nitrogen atom or sulfur atom as a ring component is preferable.
The substituent which the heteroaromatic hydrocarbon group represented by D may have may have an amino group which may be substituted, an alkyl group having 1 to 20 carbon atoms, and a substituent. Aryl groups are mentioned, and an amino group which may be substituted and an aryl group which may have a substituent are preferable.

^Examples of the optionally substituted amino group include the same ^optionally substituted amino groups represented by R ^21A and R ^22A .
The alkyl groups having 1 to 20 carbon atoms are the same as the alkyl groups having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A. Can be mentioned.
Examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group and an anthrasenyl group, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; having 1 to 20 carbon atoms. Alkyl groups can be mentioned.

［式（ＩＩＩ）中、Ｘは、酸素原子又は硫黄原子を示す。
Ｒ^５５は、水素原子、炭素数１〜２０のアルキル基又は置換基を有していてもよいアリール基を表す。
Ｒ^５６は、置換されていてもよいアミノ基を表す。
＊は、炭素原子との結合手を表す。］ The heteroaromatic hydrocarbon group represented by D is preferably a group represented by the formula (III).

[In formula (III), X represents an oxygen atom or a sulfur atom.
R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent.
R ⁵⁶ represents an optionally substituted amino group.
* Represents a bond with a carbon atom. ]

Alkyl groups having 1 to 20 carbon atoms represented by R ⁵⁵ include R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A having 1 to 20 carbon atoms. The same as the alkyl group can be mentioned.
^Examples of the aryl group which may have a substituent represented by R ⁵⁵ include a phenyl group.
^Examples of the optionally substituted amino group represented by R ⁵⁶ include the same as the ^optionally substituted amino group represented by R ^21A and R ^22A .

R ⁵⁵ is preferably an aryl group having no substituent or a substituent, and more preferably an aryl group which is unsubstituted or substituted with a halogen atom.
R ⁵⁶ is preferably an ^optionally substituted amino group.

Examples of the heteroaromatic hydrocarbon group represented by D include groups represented by formula (III-1) to groups represented by formula (III-8), preferably formula (III-1) or. It is a group represented by the formula (III-2).

［式（ｙ１）において、Ｒ^Ｂ１は、ハロゲン原子を有していてもよい炭化水素基を表す。
式（ｙ２）において、Ｒ^Ｂ２及びＲ^Ｂ３は、それぞれ独立して、ハロゲン原子又はハロゲン化炭化水素基を表すか、又はＲ^Ｂ２とＲ^Ｂ３とが互いに結合して−ＳＯ_２−Ｎ⁻−ＳＯ_２−を含む環を形成する。
式（ｙ３）において、Ｍはアルミニウム原子又はホウ素原子を表し、Ｒ^Ｂ４及びＲ^Ｂ５は、それぞれ独立に、置換基を有していてもよいフェニル基を表す。］ g is an arbitrary natural number, preferably a natural number of 1 to 2, and more preferably 1.
G ^{g −} represents a g-valent anion, and is not limited as long as it forms a salt with a cation and a g-valent anion. For example, when g is a natural number of 2 or more, it may have one g-valent anion, or may have g monovalent anion or monovalent anion moiety.
G ^g- is preferably a monovalent anion, for example, a halide ion such as a fluoride ion, a chloride ion, a bromide ion and an iodide ion, an anion represented by the formula (y1), and a formula (y2). ) And the anion represented by the formula (y3).

[In the formula (y1), R ^B1 represents a hydrocarbon group which may have a halogen atom.
In the formula ^{(y2), R B2} and ^{R B3} each independently, represent a halogen atom or a halogenated hydrocarbon group, or ^{R B2} and ^{R B3} are bonded to _-SO 2 ^-N together - -SO Form a ring containing _2- .
In the formula (y3), M represents an aluminum atom or a boron atom, and ^RB4 and ^RB5 each independently represent a phenyl group which may have a substituent. ]

The hydrocarbon group represented by R ^B1, include alkyl groups and aromatic hydrocarbon group having 6 to 14 carbon atoms having 1 to 8 carbon atoms.
As alkyl groups having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2 -Ethylhexyl group, octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group can be mentioned.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Examples of the alkyl halide group having 1 to 8 carbon atoms include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group and a perfluoro. Ethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2, 2,2-Tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2 , 3, 3, 4,4-Octafluorobutyl group, perfluorobutyl group, dibromomethyl group, tribromomethyl group, and preferably an alkyl fluoride group having 1 to 8 carbon atoms.
Examples of the aromatic hydrocarbon group having a halogen atom having 6 to 14 carbon atoms include a phenyl group having a halogen atom and a naphthyl group having a halogen atom. Specific examples thereof include a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a difluorophenyl group, a 1-fluoro-4-chlorophenyl group, a trifluorophenyl group and a fluoronaphthyl group.

^RB1 is preferably an alkyl halide group having 1 to 8 carbon atoms, and more preferably an alkyl fluoride group having 1 to 8 carbon atoms.

Examples of the halogen atom represented by ^RB2 and ^RB3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
Examples of the halogenated hydrocarbon group represented by R ^B2 and R ^B3, and an aromatic hydrocarbon group having 6 to 14 carbon atoms having a halogenated alkyl group having 1 to 8 carbon atoms, a halogen atom.
Examples of the alkyl halide group having 1 to 8 carbon atoms include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group and a perfluoro. Ethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2, 2,2-Tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2 , 3, 3, 4,4-Octafluorobutyl group, perfluorobutyl group, dibromomethyl group, tribromomethyl group, and preferably an alkyl fluoride group having 1 to 8 carbon atoms.
Examples of the aromatic hydrocarbon group having a halogen atom having 6 to 14 carbon atoms include a phenyl group having a halogen atom and a naphthyl group having a halogen atom. Specific examples thereof include a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a difluorophenyl group, a 1-fluoro-4-chlorophenyl group, a trifluorophenyl group and a fluoronaphthyl group.

R ^B2 and R ^B3 are preferably the same group.
R ^B2 and R ^B3 are each independently preferably an alkyl fluoride group having 1 to 8 carbon atoms, and more preferably a trifluoromethyl group.

As the substituent that the phenyl group represented by R ^B4 and R ^B5 may have, a hydroxyl group is preferable.
R ^B4 and R ^B5 are preferably the same group.

Examples of the anion represented by the formula (y1) include methanesulfonic acid anion, toluenesulfonic acid anion, dodecylbenzenesulfonic acid anion, trifluoromethanesulfonic acid anion, perfluorobutanesulfonic acid anion, phenylsulfonic acid anion, and fluorophenylsulfonic acid anion. And so on.

Examples of the anion represented by the formula (y2) include the anions described below.

Examples of the anion represented by the formula (y3) include the anions described below.

Examples of the dye (A7) include compounds represented by the formulas (AI-a1) to (AI-a15). Compounds represented by the formula (AI-a5) to compounds represented by the formula (AI-a12) are preferable.

The dye (A7) can be produced, for example, by the method described in Korean Patent Publication No. 2014-0026284.

The blue or violet dye may be a monomer or a polymer. The polymer which is a blue or purple dye is a polymer containing structural units derived from the blue or purple dye, and may be a polymer consisting only of structural units derived from the blue or purple dye, or the blue or purple dye. It may be a copolymer containing a structural unit derived from the above and another structural unit (hereinafter, may be referred to as a copolymer (a)). The structural unit derived from the blue or purple dye may be a divalent or higher valent group produced by the polymerization of the polymerizable blue or purple dye, or the blue or purple dye excluding one or more hydrogen atoms. It may be a group having a valence of 1 or more. As the copolymer (a), in addition to the structural unit derived from the blue or purple dye, the structural unit derived from the monomer having an ethylenically unsaturated bond and the formulas (1) to (1) to (1) to be described below. Examples thereof include copolymers containing at least one selected from the group consisting of the structural unit represented by 3).
Further, the copolymer (a) may be a copolymer containing a structural unit derived from a monomer leading to the resin (B) described later and a structural unit derived from a blue or purple dye.

［式（１）中、Ｒ^９及びＲ^１０は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜３０のアルキル基、置換基を有していてもよい炭素数６〜３０のアリール基、置換基を有していてもよいアルキルアリール基又はこれらの組み合わせを表す。
ｍ’は、０〜５の整数を表す。］

[In the formula (1), R ⁹ and R ¹⁰ independently have a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, and a carbon which may have a substituent. Represents an aryl group of number 6 to 30, an alkylaryl group which may have a substituent, or a combination thereof.
m'represents an integer from 0 to 5. ]

［式（２）中、Ｒ^１１は、水素原子、置換基を有していてもよい炭素数１〜３０のアルキル基、置換基を有していてもよい炭素数６〜３０のアリール基、置換基を有していてもよいアルキルアリール基又はこれらの組み合わせを表す。
Ｒ^１２は、置換基を有していてもよい炭素数１〜３０のアルキル基、置換基を有していてもよい炭素数６〜３０のアリール基、−ＣＯ−Ｒ^１７−ＣＯＯＨ又はこれらの組み合わせを表す。
Ｒ^１７は、置換基を有していてもよい炭素数１〜３０のアルキレン基又は置換基を有していてもよい炭素数１〜３０のアルコキシレン基を表す。］

[In the formula (2), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent. Represents an alkylaryl group which may have a substituent or a combination thereof.
R ¹² is an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, -CO-R ^17- COOH or these. Represents a combination.
R ¹⁷ represents an alkylene group having 1 to 30 carbon atoms which may have a substituent or an alkoxylen group having 1 to 30 carbon atoms which may have a substituent. ]

［式（３）中、Ｒ^１３及びＲ^１４は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜３０のアルキル基、置換基を有していてもよい炭素数６〜３０のアリール基、置換基を有していてもよいアルキルアリール基又はこれらの組み合わせを表す。
Ｒ^１５は、−ＣＯＯＨ又は−ＣＯＮＨＲ^１８を表す。
Ｒ^１８は、置換基を有していてもよい炭素数１〜３０のアルキル基又は置換基を有していてもよい炭素数６〜３０のアリール基を表す。
Ｒ^１６は、−ＣＯＯＨを表し、Ｒ^１５及びＲ^１６は、互いに結合して環を形成する。］

[In the formula (3), R ¹³ and R ¹⁴ independently have a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, and a carbon which may have a substituent. Represents an aryl group of number 6 to 30, an alkylaryl group which may have a substituent, or a combination thereof.
R ¹⁵ represents −COOH or −CONHR ¹⁸ .
R ¹⁸ represents an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent.
R ¹⁶ represents −COOH, and R ¹⁵ and R ¹⁶ combine with each other to form a ring. ]

The monomer having an ethylenically unsaturated bond is an ethylenically unsaturated monomer containing one or more carboxy groups, and specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid. Can be mentioned.
The weight ratio of the monomer having an ethylenically unsaturated bond is usually 1 to 50% by weight, preferably 3 to 40% by weight, based on the total weight of the monomer forming the copolymer (a). It is more preferably 5 to 30% by weight.

Further, it may contain a structural unit derived from a monomer having an ethylenically unsaturated bond and a structural unit derived from a copolymerizable monomer, and specifically,
Alkenyl aromatic monomers such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate. , Cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate and other unsaturated carboxylic acid ester compounds;
Unsaturated carboxylic acid aminoalkyl esters compounds such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate;
Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate;
Unsaturated carboxylic acid glycidyl esters compounds such as glycidyl acrylate and glycidyl methacrylate;
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Examples include unsaturated amide compounds such as acrylamide and methacrylamide, and combinations thereof.

The structural units derived from the blue or purple dye contained in the copolymer (a) are the structural units derived from the triarylmethane dye (A4) and the structural units derived from the dye represented by the formula (A7). It is preferably at least one selected from the group consisting of.
As the structural unit derived from the triarylmethane dye (A4), each structure derived from the compound represented by the above formula (2b-1) to the compound represented by the formula (2b-13). The unit is preferred.
As the structural unit derived from the dye represented by the formula (A7), the structural unit derived from the compound represented by the above-mentioned formula (AI-a15) is preferable.

The content of the dye (A2) is C.I. I. Acid Red 52 is usually 80 to 10000 parts by mass, preferably 80 to 7500 parts by mass, more preferably 80 to 1000 parts by mass, and further preferably 80 to 600 parts by mass with respect to 100 parts by mass. is there.

<Dye (Ac) and Pigment (Ad)>
The dye (Ac) is not particularly limited, and a known dye can be used.
As the pigment (Ad), a known pigment can be used without particular limitation, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
As the pigment, C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments and the like.

The colorant (A) is preferably a colorant containing the combinations described below.
(1) Blue pigment (A1), C.I. I. Acid Red 52 and blue or purple dye (A2)
(2) Blue pigment (A1), C.I. I. Acid Red 52, Blue or Purple Dye (A2) and Violet Color Pigment (Ad)

The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and further preferably 10 to 50% by mass with respect to the total amount of solids. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in the composition in a required amount. Therefore, it is possible to form a pattern having sufficient mechanical strength. Here, the "total amount of solid content" in the present specification means an amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1] At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (a) (hereinafter sometimes referred to as "(a)") and a cyclic ether structure having 2 to 4 carbon atoms. Copolymer with a monomer (b) having an ethylenically unsaturated bond (hereinafter, may be referred to as "(b)");
Resins [K2] (a) and (b) and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as "(c)" Copolymer with);
Copolymer of resin [K3] (a) and (c);
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.

Specifically, as (a), 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, 1,4-cyclohexendicarboxylic 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 and 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 divalent or higher valent carboxylic acids such as monosuccinate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. 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 obtained resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. In (b), a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group is preferable.
In addition, in this specification, "(meth) acrylic acid" represents at least one kind 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 oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a simple monomer having an oxetanyl group and an ethylenically unsaturated bond. A metric (b2) (hereinafter sometimes referred to as "(b2)"), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)"), etc. Can be mentioned.

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”). ), Monomers (b1-2) having an alicyclic unsaturated hydrocarbon epoxidized structure (hereinafter, may be referred to as “(b1-2)”).

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and 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-tris (Glysidyloxymethyl) styrene and the like can be mentioned.

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

[In formulas (I) and (II), ^Ra 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. You may.
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, a tert-butyl group and the like.
The alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.
Examples of R ^a and R ^b include ^a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-. Examples include 1,6-diyl group.
Examples of 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-, and more preferably a single bond, * -CH ₂ CH _2- O-can be mentioned (* represents a bond with O).

Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15). Preferably, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formulas (I-11) to (I-15). Examples thereof include compounds represented by. More preferably, a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15) can be mentioned.

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). Preferably, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15). Examples thereof include compounds represented by. More preferably, a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15) can be mentioned.

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

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 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 (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscort V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

As (b), (b1) is preferable in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further improved. Further, (b1-2) is more preferable in that the color-curable resin composition has excellent storage stability.

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 ] Decane-8-yl (meth) acrylate (In the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate", and when it is referred to as "tricyclodecyl (meth) acrylate". ), Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate". ), Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meta) acrylic acid esters such as (meth) acrylate;
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, and diethyl itaconic acid;
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 (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylnitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are selected from the viewpoint of copolymerization reactivity and heat resistance. preferable.

In the resin [K1], the ratio of the structural units derived from each is determined in the total structural units constituting the resin [K1].
Structural unit derived from (a); 2-60 mol%
Structural unit derived from (b); 40-98 mol%
Is preferable,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
Is more preferable.
When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the color curable resin composition, the developability when forming a color pattern, and the solvent resistance of the obtained color filter are excellent. Tend.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Kagaku-Dojin Co., Ltd., 1st edition, 1st print, published on March 1, 1972) and the document. It can be manufactured with reference to the cited references described in.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples thereof include a method of heating and keeping warm. The polymerization initiator, solvent, and the like used here are not particularly limited, and those usually used in the art can be used. For example, as the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) The solvent may be any solvent that dissolves each monomer, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later.

As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the copolymer is taken out as a solid (powder) by a method such as reprecipitation. You may use the one. In particular, by using the solvent contained in the color curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the color curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each is determined in the total structural units constituting the resin [K2].
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2-95 mol%
Structural unit derived from (c); 1-65 mol%
Is preferable,
Structural unit derived from (a); 5-40 mol%
Structural unit derived from (b); 5-80 mol%
Structural unit derived from (c); 5-60 mol%
Is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the color curable resin composition, the developability when forming a color pattern, and the solvent resistance of the obtained color filter, It tends to have excellent heat resistance and mechanical strength.

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

In the resin [K3], the ratio of the structural units derived from each is determined in the total structural units constituting the resin [K3].
Structural unit derived from (a); 2-60 mol%
Structural unit derived from (c); 40-98 mol%
Is preferable,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50-90 mol%
Is more preferable.
The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

The resin [K4] is a carboxylic acid and / or a carboxylic acid anhydride having the cyclic ether having 2 to 4 carbon atoms of (b) obtained by obtaining a copolymer of (a) and (c). It can be manufactured by adding to.
First, the copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that mentioned in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms of (b) is reacted with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.
Following the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen, and (b) a reaction catalyst of carboxylic acid or carboxylic acid anhydride and cyclic ether (for example, Tris (for example, Tris) Resin [K4] can be produced by putting (dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours. it can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, based on 100 mol of (a). Within this range, the balance between the storage stability of the colored curable resin composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern is improved. Tend. Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K4], and (b1-1) is further preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization and the like. As with 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 resin [K5] obtains a copolymer of (b) and (c) in the same manner as in the above-mentioned production method of the resin [K1]. In the same manner as above, the obtained copolymer may be a solution after the reaction as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. You may use the one taken out as.
The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
Is preferable,
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c); 10-90 mol%
Is more preferable.

Further, under the same conditions as the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) has the carboxylic acid or carboxylic acid anhydride of (a). The resin [K5] can be obtained by reacting an object.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K5], and (b1-1) is further preferable.

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride.
The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic acid 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 (hymic acid anhydride) and the like. Be done. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mol with respect to 1 mol of the amount used in (a).

The resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymers, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] Resins such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) ) acrylic acid copolymers, 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- ( Resins such as meta) acrylic loyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer Resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer to which glycidyl (meth) acrylate is added, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid co-weight Resins with glycidyl (meth) acrylate added to the coalescence, resins such as tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer with glycidyl (meth) acrylate added [ K4]; Co-weight of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid. Resin such as resin in which (meth) acrylic acid is reacted with coalescence [K5]; Tetrahydro is further added to resin in which (meth) acrylic acid is reacted with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate. Examples thereof include a resin [K6] such as a resin obtained by reacting an phthalic acid anhydride.
Among them, as the resin (B), the resin [K1] and the resin [K2] are 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 even more 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 portion in the developing solution is good, and the resolution 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, and even more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titrating with 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 total amount of solids.

<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 compounds having a polymerizable ethylenically unsaturated bond, which is preferable. Is a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethritol propanthritol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa. Meta) 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, Examples thereof include caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.
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 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

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

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. by the action of light or heat, and a known polymerization initiator can be used.
As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound is preferable, and an O-acyloxy compound is preferable. A polymerization initiator containing a compound compound is more preferable.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-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- (9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) −Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-Il] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1 -On-2-imine and the like. Commercially available products such as Irgacure OXE01, OXE02 (all manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. The O-acyloxym compounds are N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one. At least one selected from the group consisting of -2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy-1 is preferable. -(4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. With these O-acyloxime compounds, a high-brightness color filter tends to be obtained.

The alkylphenone compound is 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-. On, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one, 2-hydroxy-2-methyl-1-phenyl Propane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- Examples thereof include an oligomer of (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone, benzyldimethylketal and the like. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF) may be used.

Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like can be mentioned. ..

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

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, JP-A-6-75373, etc.), 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) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), the phenyl group at the 4,4'5,5'-position is substituted with a carboalkoxy group. Examples thereof include an imidazole compound (see, for example, Japanese Patent Application Laid-Open No. 7-10913).

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoin compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrene quinone, Kinone compounds such as 2-ethylanthraquinone and benzoin; 10-butyl-2-chloroacrydone, benzyl, methylphenylglycoxylate, titanosen compounds and the like can be mentioned. These are preferably used in combination with the polymerization initiator (D1) (particularly amines) described later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonium, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonium, and 4-acetoxyphenylmethylbenzylsulfonium. Onium salts such as hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylates, benzointoshi Examples include rates.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Polymerization initiator (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiator (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-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 can be mentioned, with 4,4′-bis (diethylamino) benzophenone being preferred. Commercially available products such as EAB-F (manufactured by 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. Examples thereof include anthracene 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 phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanic acetic acid, dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl sulfany acetic acid, and N. -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

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

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , Propropylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol and methyl anisole.

Examples of the ether ester solvent 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 Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

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. And so on.

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 and mesitylene.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone And N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

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

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: 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, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like. ..

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

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.1, based on the total amount of the colored curable resin composition. It is mass% or less, more preferably 0.01 mass% or more and 0.05 mass% or less. When the content of the leveling agent (F) is in the above range, the flatness of the color filter can be improved.

<Other ingredients>
The color curable resin composition of the present invention is an additive known in the art, such as a filler, other polymer compounds, an adhesion accelerator, an antioxidant, a light stabilizer, and a chain transfer agent, if necessary. May include.

<Manufacturing method of colored curable resin composition>
The color curable 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. It can be prepared by mixing a leveling agent (F), a polymerization initiator (D1) and other components.
The dye (A2) and the dye (Ac) used as needed may be dissolved in a part or all of the solvent (E) in advance to prepare a solution. It is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 μm.
It is preferable that the blue pigment (A1) is mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size of the pigment becomes about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. The desired color-curable resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.
It is preferable to filter the colored curable resin composition after mixing with a filter having a pore size of about 0.01 to 10 μm.

According to the color curable resin composition of the present invention, a color filter having particularly excellent heat resistance can be produced. 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.

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.
Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.
In the following synthetic examples, the compounds were identified by mass analysis (LC; Agilent 1200, MASS; Agilent LC / MSD) or elemental analysis (VARIO-EL; (Elemental)).

式（１−２４）で表される化合物の同定；
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝ [Ｍ＋Ｈ]^＋６０３．４
Ｅｘａｃｔ Ｍａｓｓ： ６０２．２ [Synthesis Example 1]
20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed under light-shielding conditions, and the obtained solution is stirred at 110 ° C. for 6 hours. did. The obtained reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour, and crystals were precipitated. The precipitated crystals were obtained as a residue of suction filtration and then dried to obtain 24 parts of a compound represented by the formula (1-24) (hereinafter referred to as "xanthene dye 1"). The yield was 80%.

Identification of the compound represented by the formula (1-24);
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

[Synthesis Example 2]
In a flask equipped with a cooling tube and a stirrer, 15 a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (trade name: Chugai Aminol Fast Pink R; manufactured by Chugai Kasei). A portion, 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added, and 10.9 parts of thionyl chloride was added dropwise while maintaining 20 ° C. or lower under stirring. After completion of the dropping, the temperature was raised to 50 ° C., maintained at the same temperature for 5 hours for reaction, and then cooled to 20 ° C. The reaction solution after cooling was added dropwise with a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine while maintaining the temperature below 20 ° C. with stirring. Then, the reaction was carried out by stirring at the same temperature for 5 hours. Then, the obtained reaction mixture was solvent-distilled on a rotary evaporator, a small amount of methanol was added, and the mixture was vigorously stirred. This mixture was added to a mixture of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals are separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and the compounds represented by the xanthene dyes 2 (formulas (Aa-1-1) to (Aa-1-8)). 11.3 parts of the mixture was obtained.

[Synthesis Example 3]
The following reaction was carried out in a nitrogen atmosphere. 36.3 parts of potassium thiocyanate and 160.0 parts of acetone were put into a flask equipped with a cooling tube and a stirrer, and then the mixture was stirred at room temperature for 30 minutes. Then, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropping, the mixture was further stirred at room temperature for 2 hours. Then, after ice-cooling the reaction mixture, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of the dropping, the mixture was further stirred at room temperature for 30 minutes. Then, after ice-cooling the reaction mixture, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of the dropping, the mixture was further stirred at room temperature for 30 minutes.
Then, 35.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropping, the mixture was stirred under heating under reflux for 7 hours. Then, the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped and the mixture was allowed to stand for 30 minutes to separate into an organic layer and an aqueous layer. After discarding the aqueous layer by a liquid separation operation, the organic layer was washed with 200 parts of standard hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bow show was added to the organic layer, and the mixture was stirred for 30 minutes and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 52.0 parts of the compound represented by the formula (BI-1). Yield 50%

The following reaction was carried out in a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirrer, 9.3 parts of the compound represented by the formula (BI-1), 4, 4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) 10. After adding 0 part and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added, and the mixture was stirred at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then diluted with 170.0 parts isopropanol. Then, the diluted reaction solution was poured into 300.0 parts of saturated brine, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped and the mixture was allowed to stand for 30 minutes to separate into an organic layer and an aqueous layer. After discarding the aqueous layer by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bow show was added to the organic layer, and the mixture was stirred for 30 minutes and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with an evaporator to obtain a bluish purple solid. Further, the blue-purple solid was dried under reduced pressure at 60 ° C. to obtain 19.8 parts of a compound represented by the formula (AI-a1). Yield 100%

Identification of the compound represented by the formula (AI-a1) (mass spectrometry) Ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺
Exact Mass: 636.3

The following reaction was carried out in a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirrer, 10.0 parts of the compound represented by the formula (AI-a1) and 4.5 parts of bis (trifluoromethanesulfonyl) imidelithium (manufactured by Tokyo Kasei Co., Ltd.) , And 100.0 parts of N, N-dimethylformamide were added, and then the mixture was stirred at 50 to 60 ° C. for 3 hours. Then, the reaction mixture was cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a turquoise solid. Further, the blue-green solid was dried under reduced pressure at 60 ° C. to obtain 11.3 parts of the compound represented by the formula (AI-a9). Yield 82%

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０質量部を乳酸エチル２２５質量部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗは、９．１×１０^３、分子量分布は２．１、固形分２６質量％、固形分酸価１２０ｍｇ−ＫＯＨ／ｇの樹脂Ｂ１溶液を得た。樹脂Ｂ１は下記に示す構造単位を有する。

[Synthesis Example 4]
Nitrogen was flowed at 0.02 L / min into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added and heated to 70 ° C. with stirring.
Then, Table 46 parts by weight of acrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl acrylate (Formula (compounds and the formula represented by I-1) (II-1 ) The compound is mixed at a molar ratio of 50:50.) 240 parts by mass is dissolved in 185 parts by mass of ethyl lactate to prepare a solution, and the solution is prepared by using a dropping funnel over 4 hours. The mixture was dropped into a flask kept warm at 70 ° C.

On the other hand, a solution prepared by dissolving 30 parts by mass of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was added dropwise into the flask over 4 hours using another dropping funnel. did. After the addition of the solution of the polymerization initiator is completed, 4 hours, kept at 70 ° C., and then cooled to room temperature, a weight average molecular weight Mw, 9.1 × 10 ^3, the molecular weight distribution is 2.1, solids A resin B1 solution having a solid content of 120 mg-KOH / g and a solid content of 26% by mass was obtained. Resin B1 has the structural units shown below.

[Synthesis Example 5]
182 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 nitrogen introduction tube, and the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. , Benzyl methacrylate 70.5 parts, methacrylic acid 43.0 parts, tricyclodecane skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22.0 parts and propylene glycol monomethyl ether acetate 136 parts in a mixture of 2 A solution containing 3.6 parts of 2,2'-azobisisobutyronitrile was added dropwise, and stirring was continued at 100 ° C.
Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxy group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9. 9 parts and 0.145 parts of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. to obtain a resin B2 solution having a solid content of 29% and a solid content acid value of 79 mgKOH / g. The polystyrene-equivalent weight average molecular weight measured by GPC was 30,000.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin obtained in the synthetic example were measured by using the GPC method under the following conditions.
Equipment: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shima-pack GPC-80M
Column temperature; 40 ° C
Solvent; THF (tetrahydrofuran)
Flow velocity; 1.0 mL / min
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was used as the molecular weight distribution.

[Synthesis Example 6]
To 28.52 parts of bis N-ethyl-N-hydroxyethylaminobenzophenone and 17.80 parts of triethylamine, 50 mL of dichloromethane was added and dissolved by stirring. Then, 13.56 parts of methacrylic anhydride was added, and the temperature was raised to 40 ° C. for maintenance. After completion of the reaction, the mixture was cooled to room temperature, water was added, the layers were separated, 20 mL of saturated sodium chloride solution was added, and the mixture was stirred for 30 minutes. After layer separation, the organic layer was distilled off, and the remaining solid was dried under reduced pressure to obtain 21.4 parts of the compound represented by the formula (aa2).

21.4 parts of the compound represented by the formula (aa2) was added to 500 mL of chloroform and stirred. Then, 49.08 parts of phosphorus oxychloride was added and stirred for 15 minutes. After adding 14.56 parts of N-phenyl-1-naphthylamine, the mixture was refluxed. After completion of the reaction, the mixture was cooled to room temperature, water was added, and the mixture was stirred. After stirring, the mixture was allowed to stand, the layers were separated, the organic layer was distilled off, and the remaining solid was dried under reduced pressure and purified to obtain 20.3 parts of the compound represented by the formula (aa3).

[Synthesis Example 7]
After dissolving 10.00 parts of the compound represented by the formula (aa3) in 100 mL of methanol, 2.50 parts of sodium trifluolmethanesulfonate was added to replace the salt. After filtration, the obtained compound was washed with water, and the remaining solid was dried under reduced pressure to obtain 5.5 parts of the compound represented by the formula (aa4).

[Synthesis Example 8]
After dissolving 10.00 parts of the compound represented by the formula (aa3) in 100 mL of methanol, 2.09 parts of lithium bistrifluolmethanesulfonimide was added to replace the salt. After filtration, the obtained compound was washed with water and dried under reduced pressure to obtain 7.5 parts of the compound represented by the formula (aa5).

[Synthesis Example 9]
After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. It was dissolved in 2.54 parts of the compound represented by the formula (aa4), 0.16 parts of 2,2'-azobisisobutyronitrile, and 20 parts of methyl ethyl ketone, and added to the reactor at 70 ° C. for 3 hours. .. After the addition is completed, the temperature is maintained at 70 ° C. for 8 hours, the methyl ethyl ketone is partially concentrated, the reaction solution is added to hexane, crystals are precipitated, filtered, the remaining solid is washed with hexane, and then dried under reduced pressure. To obtain 1.80 parts of the polymer compound (aa4).

[Synthesis Example 10]
After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. 2.54 parts of the compound represented by the formula (aa4), 0.25 part of 2,2'-azobisisobutyronitrile, 0.51 part of benzyl methacrylate, 0.51 part of methacrylic acid, N-phenylmaleimide 0.42 part was dissolved in 50 parts of methyl ethyl ketone and charged into the reactor at 70 ° C. for 3 hours. After the addition is completed, the temperature is maintained at 70 ° C. for 8 hours, the methyl ethyl ketone is partially concentrated, the reaction solution is added to hexane, crystals are precipitated, filtered, the remaining solid is washed with hexane, and then dried under reduced pressure. To obtain 2.35 parts of the polymer compound (aa4').

[Synthesis Example 11]
After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. It was dissolved in 2.54 parts of the compound represented by the formula (aa5), 0.16 parts of 2,2'-azobisisobutyronitrile, and 20 parts of methyl ethyl ketone, and added to the reactor at 70 ° C. for 3 hours. .. After the addition is completed, the temperature is maintained at 70 ° C. for 8 hours, the methyl ethyl ketone is partially concentrated, the reaction solution is added to hexane, crystals are precipitated, filtered, the remaining solid is washed with hexane, and then dried under reduced pressure. To obtain 1.63 parts of the polymer compound (aa5).

[Synthesis Example 12]
In a nitrogen atmosphere, 30 parts of methyl ethyl ketone is added, and then the temperature is raised to 70 ° C. 2.54 parts of the compound represented by the formula (aa5), 0.25 part of 2,2'-azobisisobutyronitrile, 0.51 part of benzyl methacrylate, 0.51 part of methacrylic acid, N-phenylmaleimide 0.42 part is dissolved in 50 parts of methyl ethyl ketone and charged into the reactor at 70 ° C. for 3 hours. After the addition is completed, the temperature is maintained at 70 ° C. for 15 hours, the methyl ethyl ketone is partially concentrated, the reaction solution is added to hexane, crystals are precipitated, filtered, and the remaining solid is dried under reduced pressure to form a polymer compound ( aa5') Obtain 3.80 copies.

[Synthesis Example 13]
After dissolving 5.00 parts of the compound represented by the formula (aa3) in 50 mL of methanol, 1.46 parts of p-toluenesulfonic acid sodium salt is added to replace the salt. After filtration, the obtained compound is washed with water and dried under reduced pressure to obtain 2.84 parts of the compound represented by the formula (aa6).

[Synthesis Example 14]
C. I. After dissolving 5.00 parts of Basic Blue 26 by adding 50 mL of methanol, 2.10 parts of sodium p-toluenesulfonic acid salt is added to replace the salt. After filtration, the obtained compound is washed with water and dried under reduced pressure to obtain 2.71 parts of the compound represented by the formula (aa7).

[Synthesis Example 15-18]
In a flask equipped with a cooling tube and a stirrer, a monomer represented by the formula (aa5) (hereinafter, may be referred to as dye Dy), benzyl methacrylate, methacrylate, methyl methacrylate and N-benzyl maleimide are placed in Table 1 below. 2,2'-Azobis (2,4-dimethylvaleronitrile) (initiator) was added in an amount of 6 parts by weight based on 100 parts by weight of the total amount of the monomer. Next, 300 parts by weight of propylene glycol monomethyl ether acetate was added to 100 parts by weight of the total amount of the initiator and the monomer, and then stirring was gradually started in a nitrogen atmosphere. The reaction solution was heated to 90 ° C. and stirred for 10 hours to obtain a copolymer solution.

[Synthesis Example 19-22]
In a flask equipped with a cooling tube and a stirrer, the monomer represented by the formula (aa8), benzyl methacrylate, methacrylic acid, methyl methacrylate and N-benzyl maleimide are charged in the weights shown in Table 2 below, and the process is started. As an agent, 2,2'-azobis (2,4-dimethylvaleronitrile) is added in an amount of 6 parts by weight based on 100 parts by weight of the total amount of the monomer. Then, 100 parts by weight of the initiator and the monomer are added. On the other hand, after adding 300 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, stirring is gradually started in a nitrogen atmosphere. The reaction solution is heated to 90 ° C. and stirred for 10 hours. Obtain a copolymer solution.

[Synthesis Example 23-26]
The copolymer solution was prepared in the same manner as in Synthesis Example 19-22, except that the monomer represented by the formula (aa9) was used instead of the monomer represented by the formula (aa8). obtain.

[Synthesis Example 27-30]
The copolymer solution was prepared in the same manner as in Synthesis Example 19-22, except that the monomer represented by the formula (aa10) was used instead of the monomer represented by the formula (aa8). obtain.

[Synthesis Example 31-42]
3.5% by weight of each copolymer solution prepared in Synthesis Example 19-30, 12% by weight of blue pigment (BASF, B 15: 6), 6% by weight of dispersant (BYK, Diperbyk 6919) and propylene glycol. 78.5% by weight of monomethyl ether acetate is mixed and dispersed using a paint shaker for 24 hours to produce each of the copolymer dispersion solutions 1 to 12.

[Synthesis Example 43]
25 parts of pararosaniline hydrochloride and 500 parts of ethanol are added to the reactor, and the mixture is stirred at 200 ° C. for 8 hours. Then, the temperature of the solution is lowered to 25 ° C., and 174 parts of 2-methyl-2-propenoic-carboxyoxy ethyl ester is slowly added dropwise to the solution in 5 hours. Then, the temperature of the solution is raised to 70 ° C., and then the mixture is stirred for 24 hours. After the reaction is completed, it is slowly recrystallized from ethanol to obtain 54.5 parts of the compound represented by the formula (aa11).

[Synthesis Example 44]
25 parts of pararosanilin hydrochloride and 500 parts of ethanol are added to the reactor, and the mixture is stirred at 200 ° C. for 8 hours.
The temperature is then lowered to 25 ° C. and 209 parts of 2-methyl-2-propenoic-sulfamino ethyl ester is slowly added dropwise to the solution over 5 hours. Then, the temperature of the solution is raised to 70 ° C., and then the mixture is stirred for 24 hours.
After the reaction is completed, it is slowly recrystallized from ethanol to obtain 58.2 parts of the compound represented by the formula (aa12).

[Synthesis Example 45]
In Synthesis Example 6, the compound represented by the formula (BI-1) is used instead of N-phenyl-1-naphthylamine, and the compound is synthesized in the same manner as in Synthesis Example 6 and represented by the formula (aa13). The compound was obtained.

[Synthesis Example 46-49]
Copolymer solutions in the same manner as in Synthesis Examples 19-22, except that the monomer represented by the formula (aa13) was used instead of the monomer represented by the formula (aa8). Got

[Synthesis Example 50-53]
3.5% by weight of each copolymer solution prepared in Synthesis Example 46-49, C.I. I. Pigment Blue Pigment 15: 6 (BASF) 12% by weight, dispersant (BYK, Diperbyk 6919) 6% by weight and propylene glycol monomethyl ether acetate 78.5% by weight were mixed and dispersed using a paint shaker for 24 hours. , Each copolymer dispersion liquid 50 to 53 is produced.

[Example 1]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 130 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): Xanthene dye 1 2.2 parts (A) Colorant: C.I. I. Acid Red 52 1.5 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Torre Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 2]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 130 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): Xanthene dye 2 1.3 parts (A) Colorant: C.I. I. Acid Red 52 1.5 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Torre Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 3]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 130 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A4): Basic Blue 7 1.3 parts (A) Colorant: C.I. I. Acid Red 52 0.3 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Torre Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 4]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 130 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A5): Compound represented by the formula (2-29) 1.3 parts (A) Colorant: C.I. I. Acid Red 52 0.8 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Torre Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 5]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 130 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A6): Compound represented by the formula (3-11) 1.3 parts (A) Colorant: C.I. I. Acid Red 52 1.1 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 6]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 130 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A7): Compound represented by the formula (AI-a9) 1.8 parts (A) Colorant: C.I. I. Acid Red 52 0.3 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Torre Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Comparative Example 1]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 130 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): Xantene dye 2 2.2 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; BASF 10 parts (F) Leveling agent: Polyether-modified silicone oil (Tore Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Propylene glycol Eight parts of monomethyl ether acetate was mixed to obtain a colored curable resin composition.

[Comparative Example 2]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 130 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): Xanthene dye 2 2.3 parts (A) Colorant: C.I. I. Acid Red 52 3.0 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

<Making a colored pattern>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to obtain a colored layer.
After allowing to cool, the distance between the substrate on which the colored layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere at 150 mJ / cm ² . Light was irradiated at an exposure amount (based on 365 nm). As the photomask, a photomask having a 100 μm line and space pattern formed was used. The colored layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and then in an oven at 200 ° C. Post-baking was performed for 30 minutes to obtain a coloring pattern.

<Film thickness measurement>
The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Saturation evaluation>
The obtained coloring pattern is spectrophotometrically measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates in the XYZ color system of CIE using the characteristic function of the C light source. (X, y) and the tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 6.

[Heat resistance evaluation]
The coating film of the obtained color-curable resin composition is heated at 230 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film is measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). It was measured. As a result of performing the above heat resistance evaluation on the obtained coating film, the color difference (ΔEab *) is shown in Table 6. The smaller ΔEab *, the smaller the color change before and after heating, indicating that the heat resistance is excellent.

[Example 7]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the compound represented by the formula (aa4) obtained in Synthesis Example 7 is used instead of the xanthene dye 1.

[Example 9]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the compound represented by the formula (aa5) obtained in Synthesis Example 8 is used instead of the xanthene dye 1.

[Example 10]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the polymer compound (aa4) obtained in Synthesis Example 9 is used instead of the xanthene dye 1.

[Example 11]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the polymer compound (aa4') obtained in Synthesis Example 10 is used instead of the xanthene dye 1.

[Example 11]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the polymer compound (aa5) obtained in Synthesis Example 11 is used instead of the xanthene dye 1.

[Example 12]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the polymer compound (aa5') obtained in Synthesis Example 12 is used instead of the xanthene dye 1.

[Example 13]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the formula (aa6) obtained in Synthesis Example 13 is used instead of the xanthene dye 1.

[Example 14]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the polymer compound (aa7) obtained in Synthesis Example 14 is used instead of the xanthene dye 1.

[Example 15]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 2 parts Acrylic pigment dispersant 0.5 part Propylene glycol monomethyl ether acetate 30 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): Copolymer solution obtained in Synthesis Example 15 Part 3.2 (A) Colorant: C.I. I. Acid Red 52 0.1 part (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 16]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 2 parts Acrylic pigment dispersant 0.5 part Propylene glycol monomethyl ether acetate 30 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): Copolymer solution obtained in Synthesis Example 16 3.3 parts (A) Colorant: C.I. I. Acid Red 52 0.1 part (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 17]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 2 parts Acrylic pigment dispersant 0.5 part Propylene glycol monomethyl ether acetate 30 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): 3.0 parts of the copolymer solution obtained in Synthesis Example 17 (A) Colorant: C.I. I. Acid Red 52 0.08 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 18]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 2 parts Acrylic pigment dispersant 0.5 part Propylene glycol monomethyl ether acetate 30 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): Copolymer solution obtained in Synthesis Example 18 3.1 parts (A) Colorant: C.I. I. Acid Red 52 0.1 part (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

Each of the colored curable resin compositions obtained in Examples 15 to 18 was subjected to film thickness measurement, chromaticity evaluation and heat resistance evaluation in the same manner as in Examples 1 to 6 and Comparative Examples 1 and 2. The results are shown in Table 7. The larger the value of Y, the higher the brightness, and the smaller the ΔEab *, the smaller the color change before and after heating, and the better the heat resistance.

[Example 19]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 31 is used instead of the xanthene dye 1.

[Example 20]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 32 is used instead of the xanthene dye 1.

[Example 21]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 33 is used instead of the xanthene dye 1.

[Example 22]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 34 is used instead of the xanthene dye 1.

[Example 23]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 35 is used instead of the xanthene dye 1.

[Example 24]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 36 is used instead of the xanthene dye 1.

[Example 25]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 37 is used instead of the xanthene dye 1.

[Example 26]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 38 is used instead of the xanthene dye 1.

[Example 27]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 39 is used instead of the xanthene dye 1.

[Example 28]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 40 is used instead of the xanthene dye 1.

[Example 29]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 41 is used instead of the xanthene dye 1.

[Example 30]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 42 is used instead of the xanthene dye 1.

[Example 31]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the compound represented by the formula (aa11) obtained in Synthesis Example 43 is used instead of the xanthene dye 1.

[Example 32]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the compound represented by the formula (aa12) obtained in Synthesis Example 44 is used instead of the xanthene dye 1.

[Example 33]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the compound represented by the formula (aa13) obtained in Synthesis Example 45 is used instead of the xanthene dye 1.

[Example 34]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 0.8 parts Acrylic pigment dispersant 0.2 parts Propylene glycol monomethyl ether acetate 30 parts are mixed and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): 3.0 parts of the copolymer solution obtained in Synthesis Example 46 (A) Colorant: C.I. I. Acid Red 52 0.03 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 35]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 0.8 parts Acrylic pigment dispersant 0.2 parts Propylene glycol monomethyl ether acetate 30 parts are mixed and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): 3.0 parts of the copolymer solution obtained in Synthesis Example 47 (A) Colorant: C.I. I. Acid Red 52 0.04 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 36]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 0.8 parts Acrylic pigment dispersant 0.2 parts Propylene glycol monomethyl ether acetate 30 parts are mixed and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): 2.9 parts of the copolymer solution obtained in Synthesis Example 48 (A) Colorant: C.I. I. Acid Red 52 0.04 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

[Example 37]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 0.8 parts Acrylic pigment dispersant 0.2 parts Propylene glycol monomethyl ether acetate 30 parts are mixed and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant (A3): Copolymer solution obtained in Synthesis Example 49 3.1 parts (A) Colorant: C.I. I. Acid Red 52 0.05 parts (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling Agent: Polyether-modified silicone oil (Torre Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Prochyl glycol Monomethyl ether acetate 8 parts mixed A color curable resin composition was obtained.

Each of the colored curable resin compositions obtained in Examples 34 to 37 was subjected to film thickness measurement, chromaticity evaluation and heat resistance evaluation in the same manner as in Examples 1 to 6 and Comparative Examples 1 and 2. The results are shown in Table 7. The larger the value of Y, the higher the brightness, and the smaller the ΔEab *, the smaller the color change before and after heating, and the better the heat resistance.

[Example 38]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 50 is used instead of the xanthene dye 1.

[Example 39]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 51 is used instead of the xanthene dye 1.

[Example 40]
(Preparation of Color Curable Resin Composition)
A colored curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 52 is used instead of the xanthene dye 1.

[Example 41]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 53 is used instead of the xanthene dye 1.

[Example 42]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that Solvent Blue 38 (Orient Corp., Varifast blue 1605) is used instead of the xanthene dye 1.

[Example 43]
(Preparation of Color Curable Resin Composition)
A color curable resin composition is obtained in the same manner as in Example 1 except that Solvent Blue 129 (Orient Corp., Varifast blue 100) is used instead of the xanthene dye 1.

[Example 44]
(Preparation of Color Curable Resin Composition)
Instead of the xanthene dye 1, a compound represented by the formula (4-9) should be used, and C.I. I. A colored curable resin composition is obtained in the same manner as in Example 1 except that the pigment violet 23 is contained.

[Example 45]
(Preparation of Color Curable Resin Composition)
Instead of the xanthene dye 1, use a compound represented by the formula (1-44), and further C.I. I. A colored curable resin composition is obtained in the same manner as in Example 1 except that the pigment violet 23 is contained.

[Example 46]
(Preparation of Color Curable Resin Composition)
(A) Colorant (A1): C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 130 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant: C.I. I. Acid Red 52 Amount shown in Table 9 (B) Resin: Resin B1 (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part (E) Solvent: Ethyl lactate 556 parts (E) Solvent: Protinic glycol Monomethyl ether acetate 8 parts mixed A colored curable resin composition was obtained.

For each of the colored curable resin compositions obtained in Examples 46 to 50 and Comparative Examples 3 to 4, film thickness measurement, chromaticity evaluation and heat resistance evaluation were carried out in the same manner as in Examples 1 to 6 and Comparative Examples 1 and 2. Was done. The results are shown in Table 9. The larger the value of Y, the higher the brightness, and the smaller the ΔEab *, the smaller the color change before and after heating, and the better the heat resistance.

The colored coating film and the coloring pattern formed from the colored curable resin composition of the present invention have good heat resistance and good brightness. It can be seen that the color filter formed from the color curable resin composition of the present invention is useful, and the liquid crystal display device including the color filter is excellent in display characteristics.

Claims (6)

A color curable resin composition containing a colorant, a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E).
The colorants are triarylmethane dye, blue pigment (A1) and C.I. I. A colorant containing Acid Red 52, wherein the triarylmethane dye is a polymer, C.I. I. The content of acid red 52 is 0.1 to 10 parts by mass with respect to 100 parts by mass of the blue pigment (A1), and the blue pigment (A1) is C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, and C.I. I. Pigment Blue 15: 6, at least one selected from the group
A curable resin composition in which the solvent (E) contains at least ethyl lactate. The blue pigment (A1) is C.I. I. The curable resin composition according to claim 1, which comprises Pigment Blue 15: 6. The blue pigment (A1) is C.I. I. The curable resin composition according to claim 2, which comprises only Pigment Blue 15: 6. The resin (B) has at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. Resin [K1] which is a copolymer with monomer (b) , or monomer (c) which is copolymerizable with ( a) and (b) and (a) (however, (a) and ( The curable resin composition according to any one of claims 1 to 3, which is a resin [K2] which is a copolymer with b) . A color filter formed by the colored curable resin composition according to any one of claims 1 to 4. A display device including the color filter according to claim 5.