JP6777129B2 - Color curable resin composition - Google Patents

Description

The present invention relates to a colored curable resin composition.

The color curable resin composition is used in the manufacture of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. Such color-curable resin compositions include xanthene dyes and C.I. I. A color curable resin composition containing only Pigment Blue 15: 6 (Patent Document 1), a xanthene dye as a colorant, C.I. I. A colored curable resin composition containing Pigment Blue 15: 6 and a phthalocyanine dye (Patent Document 2) is known.

Japanese Unexamined Patent Publication No. 2010-32999

Japanese Unexamined Patent Publication No. 2011-28236

However, the contrast of the color filter obtained by the above-mentioned color curable resin composition known conventionally has not always been sufficiently satisfactory.

［式（１ｂ）中、Ｒ^４１〜Ｒ^４８は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、置換または未置換のアルキル基、置換または未置換のアルコキシ基、置換または未置換のアリール基、置換または未置換のアリールオキシ基、置換または未置換のアラルキルオキシ基、あるいは置換または未置換のアミノ基を表し、Mは２個の水素原子、２個の１価の金属原子、２価の金属原子、３価の置換金属原子、または酸化金属原子を表す。］
［２］ テトラアザポルフィリン染料の含有量が、キサンテン染料１００質量部に対して、１質量部以上１００質量部以下である［１］記載の着色硬化性樹脂組成物。
［３］ キサンテン染料の含有量が、着色剤の総量に対して、０．１質量％以上５０質量％以下である［１］又は［２］記載の着色硬化性樹脂組成物。
［４］ キサンテン染料が下記式（１a）で表される化合物を含む［１］〜［３］のいずれかに記載の着色硬化性樹脂組成物。 The present inventor has arrived at the present invention as a result of studies in order to solve the above problems.
The present invention includes the following inventions.
[1] Contains a colorant, a resin, a polymerizable compound and a polymerization initiator.
A color curable resin composition containing a xanthene dye, a tetraazaporphyrin dye containing a compound represented by the following formula (1b), and a pigment as a colorant.

[In formula (1b), R ^{41 to} R ⁴⁸ are independently hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted. Represents an aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyloxy group, or a substituted or unsubstituted amino group, where M is two hydrogen atoms and two monovalent metal atoms. Represents a divalent metal atom, a trivalent substituted metal atom, or a metal oxide atom. ]
[2] The colored curable resin composition according to [1], wherein the content of the tetraazaporphyrin dye is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the xanthene dye.
[3] The color curable resin composition according to [1] or [2], wherein the content of the xanthene dye is 0.1% by mass or more and 50% by mass or less with respect to the total amount of the colorant.
[4] The colored curable resin composition according to any one of [1] to [3], wherein the xanthene dye contains a compound represented by the following formula (1a).

［式（１ａ）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。Ｒ¹及びＲ^２は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ^３及びＲ^４は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上のとき、複数のＲ⁵は同一でも異なってもよい。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表し、４つのＲ¹¹は同一でも異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^８−で置き換っていてもよく、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子と一緒に３〜１０員含窒素複素環を形成していてもよい。
Ｒ¹¹は、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］
［５］ ［１］〜［４］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。
［６］ ［５］記載のカラーフィルタを含む表示装置。

[In the formula (1a), R ^{1 to} R ⁴ each independently have a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a substituent which may have a substituent. It represents a monovalent aromatic hydrocarbon group which may having 6 to 10 carbon atoms and, _-CH 2 contained in the saturated hydrocarbon group - is, -O -, - CO- or ^{-NR 11} - in optionally replaced May be good. R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atom, and R ³ and R ⁴ may be bonded to each other to form a ring containing the nitrogen atom. You may form a ring containing.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ Represents NR ⁹ R ¹⁰ .
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer from 0 to 5. when m is 2 or more, plural R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ^{+ _{is, + N (R 11) 4}} , represents Na ⁺ or K ^+, 4 one R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and are contained in the saturated aliphatic hydrocarbon group-. CH ₂ - is, -O -, - CO -, - NH- or -NR ⁸ - may have I placed conversion in, R ⁹ and R ^10, 3-10 membered together with the nitrogen atom bonded with each other It may form a nitrogen-containing heterocycle.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]
[5] A color filter formed by the colored curable resin composition according to any one of [1] to [4].
[6] A display device including the color filter according to [5].

According to the present invention, it is possible to provide a color curable resin composition capable of forming a high-contrast color filter.

It is the schematic explaining the manufacturing method of the color filter of this invention. It is the schematic explaining the manufacturing method of the color filter of this invention. It is the schematic explaining the manufacturing method of the color filter of this invention.

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 colorant (A) includes a xanthene dye (Aa), a tetraazaporphyrin dye (Ab) and a pigment (Ad). Further, the colorant (A) may contain a dye different from the xanthene dye (Aa) and the tetraazaporphyrin dye (Ab) (hereinafter, may be referred to as "dye (Ac)").
The colored curable resin composition of the present invention preferably further contains a solvent (E) and / or a leveling agent (F).
The color curable resin composition of the present invention may contain a polymerization initiator (D1).
The color curable resin composition of the present invention can produce a high-contrast color filter by containing the xanthene dye (Aa), the tetraazaporphyrin dye (Ab) and the pigment (Ad) as the colorant (A).

<Colorant (A)>
The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (Aa) include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. The same applies to the others), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic Violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modant Red 27, C.I. I. Examples thereof include reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in Japanese Patent Application Laid-Open No. 2010-32999, and xanthene dyes described in Japanese Patent No. 4492760. preferable.

Among these, as the xanthene dye (Aa), a dye containing a compound represented by the formula (1a) (hereinafter, may be referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (Aa).

式（１ａ）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。Ｒ¹及びＲ^２は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ^３及びＲ^４は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上のとき、複数のＲ⁵は同一でも異なってもよい。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表し、４つのＲ¹¹は同一でも異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^８−で置き換っていてもよく、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子と一緒に３〜１０員含窒素複素環を形成していてもよい。
Ｒ¹¹は、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。

In the formula (1a), R ^{1 to} R ⁴ each independently have a hydrogen atom and a monovalent saturated hydrocarbon group or substituent having 1 to 20 carbon atoms which may have a substituent. represents also good monovalent aromatic hydrocarbon group having a carbon number of 6 to 10, _-CH 2 contained in the saturated hydrocarbon group - is, -O -, - CO- or ^{-NR 11} - be replaced by Good. R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atom, and R ³ and R ⁴ may be bonded to each other to form a ring containing the nitrogen atom. You may form a ring containing.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ Represents NR ⁹ R ¹⁰ .
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer from 0 to 5. when m is 2 or more, plural R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ^{+ _{is, + N (R 11) 4}} , represents Na ⁺ or K ^+, 4 one R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and are contained in the saturated aliphatic hydrocarbon group-. CH ₂ - is, -O -, - CO -, - NH- or -NR ⁸ - may have I placed conversion in, R ⁹ and R ^10, 3-10 membered together with the nitrogen atom bonded with each other It may form a nitrogen-containing heterocycle.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xsilyl group, a mesityl group, a propylphenyl group and a butylphenyl group.

The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - Examples thereof include CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . Among them, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and preferably _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ Is more preferable. In this case, as −SO ₃ ⁻ Z ⁺ , −SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable. When R ^{1 to} R ⁴ are these groups, a color filter containing less foreign matter and excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1a).

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁴ and R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. , Octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched chain alkyl groups; Examples thereof include an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group.
The hydrogen atom contained in the saturated hydrocarbon group in R ^{1 to} R ⁴ may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.
The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted with a hydroxy group or a halogen atom.

A ring containing a nitrogen atom formed by bonding R ¹ and R ² together with a nitrogen atom, and a ring containing a nitrogen atom formed by bonding R ³ and R ⁴ together with a nitrogen atom. Examples include the following.

Examples of −OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, an icosyloxy group and the like.

Examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, an icosyloxycarbonyl group and the like.

Examples of −SR ⁸ include methylsulfanil group, ethylsulfanil group, butylsulfanil group, hexylsulfanil group, decylsulfanil group, icosylsulfanil group and the like.
Examples of −SO ₂ R ⁸ include a methyl sulfonyl group, an ethyl sulfonyl group, a butyl sulfonyl group, a hexyl sulfonyl group, a decyl sulfonyl group, and an icosyl sulfonyl group.
Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, an icosyloxysulfonyl group and the like.

-SO ₂ NR ⁹ R ¹⁰ includes, for example, sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-Butyl sulfamoyl group, N-tert-Butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3) -Methylbutyl) sulfamoyl group, N-cyclopentyl sulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N- Heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- N-1-substituted sulfamoyl groups such as (1,5-dimethyl) hexyl sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl Examples thereof include N, N-2 substituted sulfamoyl groups such as groups.

The _{^{R 5, -CO 2 H, -CO}} 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H and _SO 2 NHR ⁹ are preferred, SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H and SO ₂ NHR ⁹ are more preferred.
m is preferably 1 to 4, more preferably 1 and 2.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include those having 1 to 6 carbon atoms among the alkyl groups listed above.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, a phenylbutyl group and the like.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
The ⁺ a N (R ¹¹⁾ _4, of the four R ^11, it is preferred that at least two of a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N (R ¹¹ ) ₄ is present in the compound (1a), if R ¹¹ is these groups, the color filter containing the compound (1a) and having less foreign matter can be obtained from the colored curable resin composition of the present invention. Can be formed.

As the compound (1a), a compound represented by the formula (2a) (hereinafter, may be referred to as “compound (2a)”) is preferable. Compound (2a) may be a tautomer thereof.

［式（２ａ）中、Ｒ²¹〜Ｒ²⁴は、それぞれ独立に、水素原子、−Ｒ²⁶又は置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表す。Ｒ²¹及びＲ²²は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ²³及びＲ²⁴は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよい。
Ｒ²⁵は、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ１⁺又は−ＳＯ₂ＮＨＲ²⁶を表す。
ｍ１は、０〜５の整数を表す。ｍ１が２以上のとき、複数のＲ²⁵は同一でも異なってもよい。
ａ１は、０又は１の整数を表す。
Ｘ１は、ハロゲン原子を表す。
Ｒ²⁶は、炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｚ１⁺は、⁺Ｎ（Ｒ²⁷）₄、Ｎａ⁺又はＫ⁺を表し、４つのＲ²⁷は同一でも異なってもよい。
Ｒ²⁷は、炭素数１〜２０の１価の飽和炭化水素基又はベンジル基を表す。］

[In the formula (2a), R ^{21 to} R ²⁴ each independently represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a hydrogen atom, −R ²⁶ or a substituent. .. R ²¹ and R ²² may be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atom, and R ²³ and R ²⁴ may be bonded to each other to form a ring containing the nitrogen atom. May form a ring containing.
R ²⁵ is, -SO ₃ ^- represents a Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents an integer from 0 to 5. When m1 is 2 or more, a plurality of R ^25s may be the same or different.
a1 represents an integer of 0 or 1.
X1 represents a halogen atom.
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and the four R ^27s may be the same or different.
R ²⁷ represents a monovalent saturated hydrocarbon group or benzyl group having 1 to 20 carbon atoms. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{21 to} R ²⁴ include the same groups as those mentioned as the aromatic hydrocarbon groups in R ^{1 to} R ⁴ . Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, it may be substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26.
As a combination of R ^{21 to} R ²⁴ , R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbons. hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, those substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ preferred. A more preferable combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and hydrogen contained in the aromatic hydrocarbon groups. Atomic atoms are substituted with -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ .
When R ^{21 to} R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Contains a ring containing a nitrogen atom formed by bonding R ²¹ and R ²² together with a nitrogen atom, and a nitrogen atom formed by bonding R ²³ and R ²⁴ together with a nitrogen atom. Examples of the ring include a ring similar to a ring containing a nitrogen atom formed by bonding R ¹ and R ² to each other together with a nitrogen atom. Of these, an aliphatic heterocycle is preferable. Examples of the aliphatic heterocycle include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those mentioned as the saturated hydrocarbon group in R ^{8 to} R ¹¹ .
When R ^{21 to} R ²⁴ are -R ^26, it is preferable that -R ²⁶ is a methyl group or an ethyl group, respectively. As the R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, 2-Ethylhexyl groups are more preferred. When R ²⁶ is these groups, a color filter containing less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
The ⁺ a N (R ²⁷⁾ _4, among the four R ^27, it is preferred that at least two of a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ²⁷ is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), when R ²⁷ is these groups, less foreign matter is generated from the colored curable resin composition of the present invention containing the compound (2a). A color filter can be formed.

m1 is preferably 1 to 4, more preferably 1 and 2.

Further, as the compound (1a), a compound represented by the formula (3a) (hereinafter, may be referred to as “compound (3a)”) is also preferable. Compound (3a) may be a tautomer thereof.

［式（３ａ）中、Ｒ³¹及びＲ³²は、それぞれ独立に、炭素数１〜１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、炭素数６〜１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ³³及びＲ³⁴は、それぞれ独立に、炭素数１〜４のアルキル基、炭素数１〜４のアルキルスルファニル基又は炭素数１〜４のアルキルスルホニル基を表す。
Ｒ³¹及びＲ³³は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ³²及びＲ³⁴は、互いに結合して窒素原子と一緒になって窒素原子を含む環を形成してもよい。
ｐ及びｑは、それぞれ独立に、０〜５の整数を表す。ｐが２以上のとき、複数のＲ³³は同一でも異なってもよく、ｑが２以上のとき、複数のＲ³⁴は同一でも異なってもよい。
Ｒ^１１は、上記と同じ意味を表す。］

[In the formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group has 6 to 10 carbon atoms. It may be substituted with 10 aromatic hydrocarbon groups or halogen atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and the saturated hydrocarbon may be substituted. it is, -O - - _-CH 2 contained in the hydrogen radical, - CO- or ^{-NR 11} - may be replaced by.
R ³³ and R ³⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl sulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ³¹ and R ³³ may bond to each other to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may bond to each other to form a ring containing a nitrogen atom. May form a ring containing.
p and q each independently represent an integer of 0-5. When p is 2 or more, the plurality of R ^33s may be the same or different, and when q is 2 or more, the plurality of R ^34s may be the same or different.
R ¹¹ has the same meaning as above. ]

Examples of monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms in R ³¹ and R ³² include groups having 1 to 10 carbon atoms among those in R ⁸ .
The aromatic hydrocarbon group having 6 to 10 carbon atoms that may have a substituent group, include the same groups as in R ^1.
Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and the like.
R ³¹ and R ³² are preferably monovalent saturated hydrocarbon groups having 1 to 3 carbon atoms, respectively.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl sulfanyl group, an ethyl sulfanyl group, a propyl sulfanyl group, a butyl sulfanyl group, an isopropyl sulfanyl group and the like.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl sulfonyl group, an ethyl sulfonyl group, a propyl sulfonyl group, a butyl sulfonyl group, and an isopropyl sulfonyl group.
R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

p and q are preferably integers of 0 to 2, preferably 0 and 1.

Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-43). In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.

Among the above compounds, the compounds represented by the formulas (1-1) to (1-23) or the formulas (1-37) to (1-43) correspond to the compound (2a) and are represented by the formula (1- 24) The compound represented by any of the formulas (1-36) corresponds to the compound (3a).
Among these, C.I. I. Sulfonamides of Acid Red 289, C.I. I. Quaternary Ammonium Salt of Acid Red 289, C.I. I. Sulfonamides of Acid Violet 102 or C.I. I. A quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such compounds include compounds represented by formulas (1-1) to (1-8), formulas (1-11), and formulas (1-12).
Further, a compound represented by any of the formulas (1-24) to (1-33) is also preferable because of its excellent solubility in an organic solvent.

As the xanthene dye (Aa), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugai Pharmaceutical Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Co., Ltd.) can be used. it can. Further, it is also possible to synthesize using a commercially available xanthene dye as a starting material with reference to JP-A-2010-32999.

The tetraazaporphyrin dye (Ab) is 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. The tetraazaporphyrin dye (Ab) is preferably dissolved in an organic solvent. In particular, when the colored curable resin composition of the present invention is prepared as a blue colored curable resin composition, the tetraazaporphyrin dye is at least one dye selected from the group consisting of blue, violet and red. Is preferable.

In the color curable resin composition of the present invention, among these, the compound represented by the formula (1b) (hereinafter, may be referred to as “compound (1b)”) is contained in the tetraazaporphyrin dye (Ab). Including. The content of the compound (1b) in the tetraazaporphyrin dye (Ab) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1b) as the tetraazaporphyrin dye (Ab).

［式（１ｂ）中、Ｒ^４１〜Ｒ^４８は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、置換または未置換のアルキル基、置換または未置換のアルコキシ基、置換または未置換のアリール基、置換または未置換のアリールオキシ基、置換または未置換のアラルキルオキシ基、あるいは置換または未置換のアミノ基を示し、Mは２個の水素原子、２個の１価の金属原子、２価の金属原子、３価の置換金属原子、または酸化金属原子を表す。

[In formula (1b), R ^{41 to} R ⁴⁸ are independently hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted. Indicates an aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyloxy group, or a substituted or unsubstituted amino group, where M is two hydrogen atoms and two monovalent metal atoms. Represents a divalent metal atom, a trivalent substituted metal atom, or a metal oxide atom.

In the present specification, the aryl group represents, for example, a carbocyclic aromatic group such as a phenyl group or a naphthyl group, for example, a heterocyclic aromatic group such as a frill group, a thienyl group or a pyridyl group, and preferably. It is a carbocyclic aromatic group.
In formula (1b), R ^{41 to} R ⁴⁸ are preferably independent hydrogen atoms, halogen atoms, cyano groups, nitro groups, substituted or unsubstituted alkyl groups having 1 to 24 carbon atoms, and carbon atoms 1 to 24, respectively. Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group having 4 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 5 to 30 carbon atoms. It is an oxy group or a substituted amino group having 1 to 30 carbon atoms.
More preferably, R ^{41 to} R ⁴⁸ each independently have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, and 1 to 16 carbon atoms. Substituent or unsubstituted alkoxy group, substituted or unsubstituted aryl group having 6 to 24 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, substituted or unsubstituted aralkyloxy having 7 to 24 carbon atoms It is a group or a substituted amino group having 1 to 16 carbon atoms.
More preferably, R ^{41 to} R ⁴⁸ each independently have a hydrogen atom, a fluorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. Substituted alkoxy groups, substituted or unsubstituted aryl groups having 6 to 16 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 16 carbon atoms, substituted or unsubstituted aralkyloxy groups having 7 to 16 carbon atoms, or It is a substituted amino group having 1 to 12 carbon atoms.
Specific examples of R ^{41 to} R ^{48 in} the formula (1b) are shown below.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom, and examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. , Se-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl Group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,2-dimethylheptyl group 6-Dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-Hexylheptyl group, n-tetradecyl group, n-pentadecyl group, 1-heptyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octylnonyl group, n-octadecyl group, 1-nonyldecyl group, 1- Decylundecyl group, n-eicosyl group, n-docosyl group, n-tetracosyl group, 1-adamantyl group, cyclopentyl group, cyclohexyl group, norbornyl group and other linear, branched or cyclic alkyl groups consisting only of carbon and hydrogen atoms. Can be mentioned.
In the substituted alkyl group, examples of the substituent include an alkyloxy group having 1 to 16 carbon atoms, an alkyloxyalkyloxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, a halogen atom, a halogenoalkyloxy group, an aryloxy group and the like. Can be mentioned.
Specific examples of the alkyl group having a substituent include, for example, a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, an n-hexyloxymethyl group, a (2-ethylbutyloxy) methyl group, and an n-octyloxymethyl group. Group, n-decyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxy Ethyl group, 2-n-hexyloxyethyl group, 2- (2'-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2'-ethylhexyl) Oxy) Ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl Group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyl) Oxy) propyl group, 3- (2'-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2'-ethylhexyloxy) propyl group, 3- (n-decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-Isopropoxybutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group , 5-methoxypentyl group, 5-ethoxypentyl group, 5-n-propoxypentyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group , 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12 An alkyl group having an alkyloxy group, such as a −ethoxydodecyl group, a 12-isopropoxidedecyl group, a tetrahydrofurfuryl group;
For example, (2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) methyl group, (2-n-hexyloxyethoxy) methyl group, (3-methoxypropyloxy) ) Methyl group, (3-ethoxypropyloxy) methyl group, (3-n-butyloxypropyloxy) methyl group, (3-n-pentyloxypropyloxy) methyl group, (4-methoxybutyloxy) methyl group, (6-methoxyhexyloxy) methyl group, (10-ethoxydecyloxy) methyl group, 2- (2'-methoxyethoxy) ethyl group, 2- (2'-ethoxyethoxy) ethyl group, 2- (2'- n-Butoxyethoxy) ethyl group, 3- (2'-ethoxyethoxy) propyl group, 3- (2'-methoxypropyloxy) propyl group, 3- (2'-isopropyloxypropyloxy) propyl group, 3-( An alkyl group having an alkyloxyalkyloxy group, such as a 3'-methoxypropyloxy) propyl group, a 3- (3'-ethoxypropyloxy) propyl group; for example, a benzyloxymethyl group, a 2-benzyloxyethyl group, 2 -Phenetyloxyethyl group, 2- (4'-methylbenzyloxy) ethyl group, 2- (2'-methylbenzyloxy) ethyl group, 2- (4'-fluorobenzyloxy) ethyl group, 2- (4' -Chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4'-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 2- (benzyloxymethoxy) ethyl group, 2- (4' -Alkyl group having an aralkyloxy group, such as (methylbenzyloxymethoxy) ethyl group;
For example, phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyl Oxymethyl group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4'-methylphenyloxy) ethyl group, 2- (4'-ethylphenyloxy) ethyl group, 2- (4'- Methyl phenyloxy) ethyl group, 2- (4'-chlorophenyloxy) ethyl group, 2- (4'-bromophenyloxy) ethyl group, 2- (1'-naphthyloxy) ethyl group, 2- (2'- Naftyloxy) ethyl group, 3-phenyloxypropyl group, 3- (2'-naphthyloxy) propyl group, 4-phenyloxybutyl group, 4- (2'-ethylphenyloxy) butyl group, 5- (4' -Tert-Butylphenyloxy) pentyl group, 6- (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3'-chlorophenyloxy) decyl group, 2- An alkyl group having an aryloxy group, such as a (2'-phenyloxyethoxy) ethyl group, a 3- (2'-phenyloxyethoxy) propyl group, a 4- (2'-phenyloxyethoxy) butyl group;
For example, n-butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n -Octylthioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthio Alkylthio such as butyl group, 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, 8-methylthiooctyl group, etc. Alkyl group having a group;
For example, fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n. -Propyl group, 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group, 1,1-dihydroperfluoro-n-butyl group, 1,1- Dihydroperfluoro-n-pentyl group, 1,1-dihydroperfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydroperfluoro-n-octyl group, 1,1-Dihydroperfluoro-n-decyl group, 1,1-dihydroperfluoro-n-dodecyl group, 1,1-dihydroperfluoro-n-tetradecyl group, 1,1-dihydroperfluo Raw n-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 2,2-bis (trifluoromethyl) propyl group, dichloromethyl An alkyl group having a halogen atom such as a group, a 2-chloroethyl group, a 3-chloropropyl group, a 4-chlorocyclohexyl group, a 7-chloroheptyl group, an 8-chlorooctyl group, a 2,2,2-trichloroethyl group;
For example, fluoromethyloxymethyl group, 3-fluoro-n-propyloxymethyl group, 6-fluoro-n-hexyloxymethyl group, trifluoromethyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1,1-dihydroperfluoro-n-propyloxymethyl group, 2-hydro-perfluoro-2-propyloxymethyl group, 1,1-dihydroperfluoro-n-butyloxymethyl group, 1,1- Dihydroperfluoro-n-pentyloxymethyl group, 1,1-dihydroperfluoro-n-hexyloxymethyl group, 1,1-dihydroperfluoro-n-octyloxymethyl group, 1,1-dihydro Roperfluoro-n-decyloxymethyl group, 1,1-dihydroperfluoro-n-tetradecyloxymethyl group, 2,2-bis (trifluoromethyl) propyloxymethyl group, 3-chloro-n-propyloxy Methyl group, 2- (8-fluoro-n-octyloxy) ethyl group, 2- (1,1-dihydro-perfluoroethyloxy) ethyl group, 2- (1,1,3-trihydro-perfluoro-n) -Propyloxy) ethyl group, 2- (1,1-dihydroperfluoro-n-pentyloxy) ethyl group, 2- (6-fluoro-n-hexyloxy) ethyl group, 2- (1,1-di) Hydroperfluoro-n-octyloxy) ethyl group, 3- (4-fluorocyclohexyloxy) propyl group, 3- (1,1-dihydro-perfluoroethyloxy) propyl group, 3- (1,1-dihydro) Roperfluoro-n-dodecyloxy) propyl group, 4- (perfluoro-n-hexyloxy) butyl group, 4- (1,1-dihydro-perfluoroethyloxy) butyl group, 6- (2-chloroethyloxy) ) Alkyl groups having halogenoalkyloxy groups, such as hexyl groups, 6- (1,1-dihydro-perfluoroethyloxy) hexyl groups;
For example, phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-ethylphenyloxymethyl group, 4-n-propylphenyloxymethyl group, 4 -N-Butylphenyloxymethyl group, 4-tert-butylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-octylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4 -Methylphenyloxymethyl group, 4-ethoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-n-pentyloxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 3-fluorophenyloxymethyl group, 2-Fluorophenyloxymethyl group, 3,4-difluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-chlorophenyloxymethyl group, 4-phenylphenyloxymethyl group, 1-naphthyloxymethyl group, 2-naphthyl Oxymethyl group, 2-furyloxymethyl group, 1-phenyloxyethyl group, 2-phenyloxyethyl group, 2- (4'-methylphenyloxy) ethyl group, 2- (4'-ethylphenyloxy) ethyl group , 2- (4'-n-hexylphenyloxy) ethyl group, 2- (4'-methoxyphenyloxy) ethyl group, 2- (4'-n-butoxyphenyloxy) ethyl group, 2- (4'- Fluorophenyloxy) ethyl group, 2- (4'-chlorophenyloxy) ethyl group, 2- (4'-bromophenyloxy) ethyl group, 2- (1'-naphthyloxy) ethyl group, 2- (2'- Naphthyloxy) ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3- (4'-methylphenyloxy) propyl group, 3- (2'-naphthyloxy) propyl group, 4-phenyloxybutyl Group, 4- (2'-ethylphenyloxy) butyl group, 4-phenyloxypentyl group, 5-phenyloxypentyl group, 5- (4'-tert-butylphenyloxy) pentyl group, 6-phenyloxyhexyl group , 6- (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3'-methylphenyloxy) decyl group, and other alkyl groups having an aryloxy group can give.
The substituted or unsubstituted alkoxy group is an alkoxy group which may have a substituent similar to the above-mentioned alkyl group, and an alkoxy group derived from the alkyl group shown as a specific example of the alkyl group is used. Can be mentioned.
Examples of the unsubstituted aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthrasenyl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 1-pyrenyl group, and 2-. Examples thereof include pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group and 8-fluoranthenyl group.
In the substituted aryl group, examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, an aryl group, a halogen atom and the like.
Specific examples of the aryl group having a substituent include, for example, 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4'-tert-butylcyclohexyl) phenyl group, 3 Aryl groups having alkyl groups such as −cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2,4-dimethylphenyl group;
For example, 4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2-isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group, etc. Aryl group having an alkoxy group and an aryloxy group;
For example, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4- (2'-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1- An aryl group having an aryl group such as a phenyl-2-naphthyl group or a 7-phenyl-1-pyrenyl group;
For example, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group. , 2-Methyl-3-chlorophenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group and other aryl groups having halogen atoms;
Furthermore, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl Examples include a group, 4-ethylthiophenyl group, 4-cyanophenyl group, 3-cyanophenyl group and the like.
The substituted or unsubstituted aryloxy group is an aryloxy group which may have the same substituent as the substituted aryl group mentioned above, and is shown as a specific example of the substituted aryl group mentioned above. Substituted or unsubstituted aryloxy groups derived from substituents can be mentioned.
Examples of the substituted or unsubstituted aralkyloxy group include a benzyloxy group, an α-methylbenzyloxy group, a phenethyloxy group, an α-methylphenetyloxy group, an α, α-dimethylbenzyloxy group, an α, α-dimethylphenethyl. Aralkyloxy groups having an unsubstituted or alkyl group, such as an oxy group, a 4-methylphenethyloxy group, a 4-methylbenzyloxy group, a 4-isopropylbenzyloxy group;
An aralkyloxy group having an allyl group such as a 4-benzylbenzyloxy group, a 4-phenylbenzyloxy group, a 4-phenylbenzyloxy group or an aralkyl group;
4-methoxybenzyloxy group, 4-n-tetradecyloxybenzyloxy group, 4-n-heptadecyloxybenzyloxy group, 3,4-dimethoxybenzyloxy group, 4-methoxymethylbenzyloxy group, 4-vinyloxy An aralkyloxy group having a substituted oxy group such as a methylbenzyloxy group, a 4-benzyloxybenzyloxy group, or a 4-phenethyloxybenzyloxy group;
Aralkyloxy group having a hydroxyl group such as 4-hydroxybenzyloxy group and 4-hydroxy-3-methoxybenzyloxy group;
Aralkyloxy group having halogen atom such as 4-fluorobenzyloxy group, 3-chlorobenzyloxy group, 3,4-dichlorobenzyloxy group;
Examples thereof include 2-furfuryloxy group, diphenylmethyloxy group, 1-naphthylmethyloxy group and 2-naphthylmethyloxy group.
In the substituted amino group, examples of the substituent include an alkyl group having 1 to 14 carbon atoms, an aralkyl group, an aryl group and the like.
Specific examples of the amino group having a substituent include N-methylamino group, N-ethylamino group, Nn-butylamino group, N-cyclohexylamino group, Nn-octylamino group and N-. Amino group having an alkyl group such as n-decylamino group;
For example, N-benzylamino group, N-phenylamino group, N- (3-methylphenyl) amino group, N- (4-methylphenyl) amino group, N- (4-n-butylphenyl) amino group, N -(4-methoxyphenyl) amino group, N- (3-fluorophenyl) amino group, N- (4-chlorophenyl) amino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group Amino group having an aralkyl group or an aryl group such as;
For example, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-butylamino group, N, N-di-n-hexylamino group, N, N-di-n-octyl. Amino group, N, N-di-n-decylamino group, N, N-di-n-dodecylamino group, N-methyl-N-ethylamino group, N-ethyl-Nn-butylamino group, N- Alkyl group such as methyl-N-phenylamino group, N-ethyl-N-phenylamino group, Nn-butyl-N-phenylamino group or aralkyl group disubstituted amino group;
For example, N, N-diphenylamino group, N, N-di (3-methylphenyl) amino group, N, N-di (4-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino. Group, N, N-di (4-tert-butylphenyl) amino group, N, N-di (4-n-hexylphenyl) amino group, N, N-di (4-methoxyphenyl) amino group, N, N-di (4-ethoxyphenyl) amino group, N, N-di (4-n-butoxyphenyl) amino group, N, N-di (4-n-hexyloxyphenyl) amino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, N-phenyl-N- (3-methylphenyl) amino group, N-phenyl-N- (4-methylphenyl) amino group , N-phenyl-N- (4-octylphenyl) amino group, N-phenyl-N- (4-methoxyphenyl) amino group, N-phenyl-N- (4-ethoxyphenyl) amino group, N-phenyl- N- (4-n-hexyloxyphenyl) amino group, N-phenyl-N- (4-fluorophenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- ( Examples thereof include an amino group disubstituted with an aryl group such as a 2-naphthyl) amino group, an N-phenyl-N- (3-phenylphenyl) amino group, and an N-phenyl-N- (4-phenylphenyl) amino group. Be done.
In formula (1b), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, or a metal oxide atom, more preferably two. It is a hydrogen atom, a divalent metal atom, or a metal oxide atom, and more preferably a divalent metal atom or a metal oxide atom.
Examples of the monovalent metal atom represented by M include Na, K, Li and the like.
Examples of the divalent metal atom represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, and Pb. , Sn and the like.
Examples of the trivalent substituted metal atom represented by M, for example, Al-Cl, Ga-Br , Ga-I, In-Cl, Al-C 6 H 5, In-C 6 H 5, Mn (OH) , Mn [OSI (CH ₃ ) ₃ ], Fe-Cl, and the like.
Examples of the metal oxide atom represented by M include VO, MnO, and TiO.
In formula (1b), M is more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO and TiO, still more preferably Cu, Ni, Pd and VO, and in particular. Preferred are Cu, Pd and VO.

Specific examples of the compound (1b) include compounds represented by the formulas (2-1) to (2-38).

The tetraazaporphyrin dye (Ab) preferably contains a compound represented by the formula (2-29). The composition containing the tetraazaporphyrin dye can form a high-contrast coating film or pattern and generate less foreign matter.

The dye (Ac) is not particularly limited as long as it is a dye different from the xanthene dye (Aa) and the tetraazaporphyrin dye (Ab), and is an oil-soluble dye, an acidic dye, a basic dye, a direct dye, a medium dye, and an acidic dye. Dyes such as amine salts of dyes and sulfonamide derivatives of acidic dyes include, for example, dyes in the Color Index (published by The Society of Dyers and Colorists), ie C.I. I. Examples thereof include compounds classified as having a hue other than pigments, and known dyes described in dyeing notes (color dyeing company). According to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, anthraquinone dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, aclysine dye, styryl dye, coumarin dye, quinoline. Examples include dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C. I. Solvent Red 45, 49, 125, 130;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 4, 5, 25, 35, 37, 45, 67, 70, 90;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dye,
C. I. Acid Yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 57, 66, 73, 80, 81, 82, 83, 88, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 356, 382, 383, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 17, 19, 29, 31, 33, 34, 36, 36: 1, 39, 41, 42, 43, 47, 48, 51, 63, 76, 103, 109, 118, 126;
C. I. Acid Blue 2,8,14,18,23,25,27,29,35,37,41,42,43,45,47,49,50,51,52,53,55,56,57,58, 59, 60, 62, 62: 1, 63, 64, 65, 68, 69, 70, 72, 74, 78, 79, 80, 81, 81: 1, 82, 87, 92, 96, 102, 111, 113, 117, 120, 122, 124, 126, 127, 127: 1, 129, 129: 1, 130, 131, 137, 138, 140, 142, 143, 145, 145: 1, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 176, 182, 183, 184, 187, 192, 198, 199, 203, 204, 205, 208, 210, 220, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Acid Green 1, 58, 63, 65, 80, 104, 105, 106, 109 and the like. I. Acid dye,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 2,6,8,15,22,25,57,71,76,78,80,81,84,85,86,90,93,94,95,97,98,99,100,101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214,222,225,226,228,229,236,237,238,242,243,244,245,246,247,248,249,250,251,252,256,257,259,260,268, 274, 275, 293;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. Direct dye,
C. I. Basic Blue 1, 3, 5, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modant Red 1,2,3,4,5,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modant Blue 1,2,3,7,9,12,13,15,16,19,20,21,22,26,30,31,39,40,41,43,44,49,53,61 , 74, 77, 83, 84;
C. I. Modant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Examples include modern dyes.

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).
Examples of the pigment include C.I. I. Pigment Yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Examples thereof include black pigments such as Pigment Blacks 1 and 7.

As the pigment, C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments are preferred. I. Pigment Blue 15: 3, 15: 6 and C.I. I. Pigment Violet 23 is more preferred, C.I. I. Pigment Blue 15: 6 is even more preferred. By including the above pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment is treated with rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, atomization by a sulfuric acid atomization method, or the like. Treatment, cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out the dispersion treatment by adding a pigment dispersant, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include cation-based, anion-based, nonionic-based, amphoteric, polyester-based, polyamine-based, and acrylic-based pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. As pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Kagaku Co., Ltd.), Solspers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), Ajinomoto Fine (Ajinomoto Fine) Examples include Techno Co., Ltd. and Disperbyk (manufactured by Big Chemie).
When a pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (Ad). When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the xanthene dye (Aa) is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.5% by mass or more and 50% by mass or less, based on the total amount of the colorant (A).
The content of the tetraazaporphyrin dye (Ab) is preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the xanthene dye (Aa).
The content of the pigment (Ad) is preferably 10% by mass or more and 99.9% by mass or less, and more preferably 30% by mass or more and 99% by mass or less, based on the total amount of the colorant (A).
When the colorant (A) contains the dye (Ac), the content of the dye (Ac) is preferably 0.1% by mass or more and 50% by mass or less, preferably 0.5% by mass or less, based on the total amount of the colorant (A). More preferably, it is by mass% or more and 30% by mass or less.

The colorant (A) is preferably composed of a xanthene dye (Aa), a tetraazaporphyrin dye (Ab) and a pigment (Ad). In this case, the content of each of these components is, respectively, with respect to the total amount of the colorant (A).
Xanthene dye (Aa); 0.1% by mass or more and 50% by mass or less Tetraazaporphyrin dye (Ab); 0.1% by mass or more and 50% by mass or less Pigment (Ad); 49.9% by mass or more and 99.8% by mass It is preferably
Xanthene dye (Aa); 0.5% by mass or more and 50% by mass or less Tetraazaporphyrin dye (Ab); 0.5% by mass or more and 50% by mass or less Pigment (Ad); 49.5% by mass or more and 99% by mass or less More preferably.

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 cyclic ether having 2 to 4 carbon atoms. Copolymer with monomer (b) having a structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)");
Resin [K2]; (a) and (b) and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter "(c)" Copolymer with);
Resin [K3]; copolymer of (a) and (c);
Resin [K4]; Resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5]; Resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6]; A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

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 and 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 copolymerizability 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 (b1) 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), 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 and * -CH ₂ CH _2- O− (* represents a bond with O).

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

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

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio thereof [the compound represented by the formula (I): the compound represented by the formula (II)] is On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 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, methacrylonitrile, 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 of (b) having 2 to 4 carbon atoms 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, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value due to 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 within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the coloring pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and 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 by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of solids. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include 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.
Examples of the polymerization initiator that generates an active radical include an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound.

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

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-] (2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,, 3-dimethyl-2,) 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole] -3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane- 1-on-2-imine and the like can be mentioned. Commercially available products such as Irgacure OXE01, OXE02 (all manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxym compounds are N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1. At least one selected from the group consisting of −on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy is preferable. -1- (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 a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4). -Morholinophenyl) -2-benzyl butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one And so on. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

Examples of the triazine compound 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-methoxy) Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-) 2-Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. 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'-tetraphenylbimidazole, 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 (tri) Alkoxyphenyl) 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 replaced by a carboalkoxy group. Examples thereof include imidazole compounds (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-phenanthlenquinone, Kinone compounds such as 2-ethylanthraquinone and phenylquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, titanosen compounds and the like. These are preferably used in combination with the polymerization initiator (D1) (particularly amines) described later.

Examples of the acid generator that generates an acid and functions as a polymerization initiator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p-. Toluene Sulfonate, 4-acetoxyphenyl methyl benzyl sulfonium hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyl iodonium p-toluene sulfonate, diphenyl iodonium hexafluoroantimonate, etc. Onium salts, nitrobenzyltosylates, benzointosylates and the like can be mentioned.

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.

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. The polymerization initiator (D1) 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, and 4 -Dimethylaminobenzoate 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis Examples thereof include (ethylmethylamino) benzophenone, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. 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-di. Butoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

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, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, and dichlorophenylsulfanyl acetic acid. Examples thereof include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When these polymerization initiators (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 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, dimethyl sulfoxide and the like.

Examples of the ester solvent 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, mesitylene and the like.

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

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 dryness, and propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropion. Ethyl acid acid, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are more preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Ethyl lactate and ethyl 3-ethoxypropionate are more preferred.

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), etc. ..

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.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

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. The content of the pigment dispersant is not included in this content. When the content of the leveling agent (F) is within 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.
It is preferable that the pigment (Ad) is mixed with a part or all of the solvent (E) in advance and dispersed by 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.
The dyes (Aa, Ab, Ac) 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 to filter the colored curable resin composition after mixing with a filter having a pore size of about 0.1 to 10 μm.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Of these, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the purpose, application and the like. For example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5. It is ~ 6 μm.

The substrate includes a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or on the substrate. Aluminum, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit, etc. may be formed on these substrates.

The formation of each color pixel by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows.
First, a color curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and / or vacuum drying to obtain a smooth color composition layer.
Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

The coloring composition layer is then exposed via a photomask to form the desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like.
An exposure device such as a mask aligner and a stepper should be used because it is possible to uniformly irradiate the entire exposed surface with parallel rays and accurately align the photomask with the substrate on which the coloring composition layer is formed. Is preferable.

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

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

According to the present invention, it is possible to provide a color curable resin composition capable of producing a color filter having particularly excellent contrast. 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.
Further, according to the present invention, it is also possible to provide a color curable resin composition capable of forming a high-definition color filter having a sharp pattern (for example, a good short shape).

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)).

[Synthesis Example 1]
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, and dried under reduced pressure at 60 ° C. to prepare the dyes (Aa-1) (forms (A1-1) to (A1-8)). Mixture) 11.3 parts were obtained.

[Synthesis Example 2]
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 the compound represented by the formula (1-24). The yield was 80%.

The structure of the compound represented by the formula (1-24) was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

式（１−３２）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]^＋６５９．９
Ｅｘａｃｔ Ｍａｓｓ： ６５８．９ [Synthesis Example 3]
A compound represented by the formula (1-32) was obtained in the same manner as in Synthesis Example 1 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of the compound represented by the formula (1-32) (mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 659.9
Exact Mass: 658.9

[Synthesis Example 4]
A compound represented by a dye (Ab-1) (formula (2-29), formula (2-39), formula (2-40), formula (2-41) in the synthetic method described in Japanese Patent No. 3961078. A mixture of) was obtained.

[Synthesis Example 5]
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Then 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] ^{. 6} ] A mixed solution prepared by dissolving 225 parts of a mixture of decane-9-ylacrylate (content ratio is 50:50 in molar ratio) and 81 parts of vinyl toluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate. Was dropped into the flask over 4 hours.
On the other hand, a solution prepared by dissolving 30 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropping of the initiator solution, the mixture was kept at 85 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer solution. This copolymer is designated as resin B2. The solid content of the resin B2 solution was 37.5%, and the viscosity measured with a B-type viscometer (23 ° C.) was 246 mPa · s. The weight average molecular weight of the resin B1 is 1.06 × 10 ^4, acid value on solid basis is 115mg-KOH / g, the molecular weight distribution was 2.01. Resin B1 has the following structural units.

[Synthesis Example 6]
182 g 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, the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton. ) And 136 g of propylene glycol monomethyl ether acetate were added with a solution containing 3.6 g of 2,2'-azobisisobutyronitrile, and the mixture was further stirred at 100 ° C.
Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxy group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g 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 mg-KOH / 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.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin 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.

[Example 1]
(Preparation of Color Curable Resin Composition)
(A) Colorant: C.I. I. Pigment Blue 15: 6 (Pigment) 33.8 parts Acrylic pigment dispersant 12.8 parts Propylene glycol monomethyl ether acetate 225 parts are mixed and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant: Xantene dye (Aa-1) 4.0 parts (A) Colorant: Tetraazaporphyrin dye (Ab-1) 2.0 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 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) ) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (D1) Polymerization initiator: 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; Japan Yakuhin Co., Ltd .; thioxanthone compound) 5 parts (F) Leveling agent: polyether-modified silicone oil (Torre Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.2 parts (E) Solvent: 4-hydroxy-4 -Methyl-2-pentanone 477 parts (E) Solvent: 204 parts of propylene glycol monomethyl ether acetate was mixed to obtain a colored curable resin composition.

<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 230 ° 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 CIE XYZ color system are used 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 1.

<Contrast evaluation>
A colored coating film was prepared by performing the same operation as the production of the colored pattern except that a photomask was not used at the time of exposure. Contrast meter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5A; manufactured by Topcon Co., Ltd., light source; F-10, polarizing film; manufactured by Tsubosaka Electric Co., Ltd.) was used for the obtained colored coating film. The contrast was measured with a blank value of 30,000. If the contrast in the coating film is high, it can be said that the contrast in the coloring pattern is also high. The results are shown in Table 1.

[Example 2]
(Preparation of Color Curable Resin Composition)
(A) Colorant: C.I. I. Pigment Blue 15: 6 (Pigment) 17.2 parts Acrylic pigment dispersant 6.5 parts Propylene glycol monomethyl ether acetate 114 parts are mixed, and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant: Xantene dye (1-24) 3.4 parts (A) Colorant: Tetraazaporphyrin dye (Ab-1) 2.3 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 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) ) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 10 parts (D1) Polymerization initiator: 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; Japan Yakuhin Co., Ltd .; thioxanthone compound) 5 parts (F) Leveling agent: polyether-modified silicone oil (Torre Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 parts (E) Solvent: 4-hydroxy-4 -Methyl-2-pentanone 510 parts (E) Solvent: propylene glycol monomethyl ether acetate 201 parts were mixed to obtain a colored curable resin composition.
The colored curable resin composition was subjected to the same operation as in Example 1 and further evaluated in the same manner. The results are shown in Table 1.

[Example 3]
The same operation as in Example 2 was carried out except that the xanthene dye (1-24) was replaced with the xanthene dye (1-32) to obtain a colored curable resin composition. The color curable resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
(A) Colorant: C.I. I. Pigment Blue 15: 6 (Pigment) 20 parts Acrylic pigment dispersant 5 parts Propylene glycol monomethyl ether acetate 137 parts are mixed and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant: Xantene dye (Aa-1) 3.5 parts (B) Resin: Resin B2 solution 157 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: OXE 01 (manufactured by BASF) 15 parts (E) Solvent: 4-hydroxy-4-methyl-2-pentanone 289 parts were mixed to obtain a colored curable resin composition. The color curable resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
(A) Colorant: C.I. I. Pigment Blue 15: 6 (Pigment) 25 parts Acrylic pigment dispersant 8.4 parts Propylene glycol monomethyl ether acetate 181 parts are mixed and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant: Xanthene dye (Aa-1) 4.8 parts (A) Colorant: C.I. I. Salt of Direct Blue 264 and dodecylbenzene sulfonic acid (manufactured by Orient Chemical Industry Co., Ltd.) 2.3 parts (B) Resin: Resin B2 solution 152 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Nippon Kayaku) 50 parts (D) Polymerization initiator: OXE 01 (manufactured by BASF) 15 parts (E) Solvent: 308 parts of ethyl lactate was mixed to obtain a colored curable resin composition. The color curable resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 3]
(A) Colorant: C.I. I. Pigment Blue 15: 6 (Pigment) 25 parts Acrylic pigment dispersant 8.4 parts Propylene glycol monomethyl ether acetate 181 parts are mixed and the pigment is sufficiently dispersed using a bead mill, and then
(A) Colorant: Xantene dye (Aa-1) 4.8 parts (A) Colorant: Tetraazaporphyrin dye (B90401 manufactured by Hiroyuki Kyojin Co., Ltd.) 2.3 parts (B) Resin: Resin B2 solution 152 Part (C) Polymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: OXE 01 (manufactured by BASF) 15 parts (E) Solvent: Ethyl lactate 308 parts The mixture was mixed to obtain a colored curable resin composition. The color curable resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

According to the examples, it was confirmed that the coating film obtained from the colored curable resin composition of the present invention showed high contrast. From this, it can be seen that the colored coating film and the coloring pattern obtained from the colored curable resin composition of the present invention are useful as a high-contrast color filter, and the liquid crystal display device including the color filter is excellent in display characteristics. ..

According to the color curable resin composition of the present invention, a high-contrast color filter can be formed.

21 Glass substrate 22 TFT (switching element)
22a Gate electrode 22b Gate insulating film 22c Polycrystalline silicon film 22d Protective film 23 Color filter layer 23A Color curable resin composition layer (color filter)
23a Red filter 23b Green filter 23c Blue filter 24 Pixel electrode 27 Signal line 29 Photosensitive resin film (protective film)
201, 202 connection hole

Claims (8)

Contains colorants, resins, polymerizable compounds and polymerization initiators
The colorant contains a xanthene dye, a tetraazaporphyrin dye and a pigment containing a compound represented by the following formula (1b), and the resin is styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide. , And a structural unit derived from one selected from the group consisting of bicyclo [2.2.1] hept-2-ene, a colored curable resin composition.

[In equation (1b),
In R ⁴¹ and R ⁴² , at least one is a substituted aryl group and the other is an unsubstituted alkyl group .
In R ⁴³ and R ⁴⁴ , at least one is a substituted aryl group and the other is an unsubstituted alkyl group .
In R ⁴⁵ and R ⁴⁶ , at least one is a substituted aryl group and the other is an unsubstituted alkyl group .
In R ⁴⁷ and R ⁴⁸ , at least one is a substituted aryl group and the other is an unsubstituted alkyl group .
M represents a divalent metal atom, a trivalent substituted metal atom, or a metal oxide atom. ] The colored curable resin composition according to claim 1, wherein the content of the tetraazaporphyrin dye is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the xanthene dye. The color-curable resin composition according to claim 1 or 2, wherein the content of the xanthene dye is 0.1% by mass or more and 50% by mass or less with respect to the total amount of the colorant. The colored curable resin composition according to any one of claims 1 to 3, wherein the xanthene dye contains a compound represented by the following formula (1a).

[In the formula (1a), R ^{1 to} R ⁴ each independently have a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a substituent which may have a substituent. It represents a monovalent aromatic hydrocarbon group which may having 6 to 10 carbon atoms and, _-CH 2 contained in the saturated hydrocarbon group - is, -O -, - CO- or ^{-NR 11} - in optionally replaced May be good. R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atom, and R ³ and R ⁴ may be bonded to each other to form a ring containing the nitrogen atom. May form a ring containing.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO Represents ₂ NR ⁹ R ¹⁰ .
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer from 0 to 5. when m is 2 or more, plural R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ^{+ _{is, + N (R 11) 4}} , represents Na ⁺ or K ^+, 4 one R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and is contained in the saturated hydrocarbon group -CH _2. - is -O -, - CO -, - NH- or -NR ⁸ - may have I placed conversion in, R ⁹ and R ^10, 3-10 membered nitrogen-containing together with the nitrogen atom bonded with each other It may form a heterocycle.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ] The colored curable resin composition according to any one of claims 1 to 4, wherein the tetraazaporphyrin dye is an aryl group in which the substituted aryl group in the formula (1b) is substituted with a halogen atom . The resin is a monomer having at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (a), a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond (a monomer). Resin [K1] which is a copolymer with b), or (a) and (b), and a monomer (c) which is copolymerizable with (a) (however, (a) and (b) are The colored curable resin composition according to any one of claims 1 to 5, which comprises at least a resin [K2] which is a copolymer with (different). A color filter formed by the colored curable resin composition according to any one of claims 1 to 6. A display device including the color filter according to claim 7.


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