JP2015172189A - colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition capable of forming a color filter excellent in lightness.SOLUTION: The colored curable resin composition contains a colorant, a resin, a polymerizable compound, and a polymerization initiator. The colorant contains at least one selected from the group consisting of a yellow dye and a yellow pigment, a blue dye, and a green pigment. In the colored curable resin composition, the content of the blue dye is preferably 0.1-20 mass% inclusive based on the total content of the colorant.

Description

  The present invention relates to a colored curable resin composition.

  Colored curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. In order to reduce the power consumption of a display device, a color filter with high transmittance and high brightness is required. As a colored curable resin composition for producing such a color filter, a colored curable resin composition containing a halogenated phthalocyanine pigment and a coumarin dye as colorants is known (Patent Document 1).

JP2013-231165A

  The above-mentioned colored curable resin composition known hitherto is not sufficiently satisfactory in the color pattern obtained, that is, the brightness of the color filter.

The present invention includes the following inventions.
[1] contains a colorant, a resin, a polymerizable compound and a polymerization initiator,
A colored curable resin composition, wherein the colorant comprises at least one selected from the group consisting of a yellow dye and a yellow pigment, a blue dye, and a green pigment.
[2] The colored curable resin composition according to [1], wherein the content of the blue dye is 0.1% by mass or more and 20% by mass or less with respect to the total content of the colorant.
[3] The colored curable resin composition according to [1] or [2], wherein the polymerization initiator is a polymerization initiator containing an O-acyloxime compound.
[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].

  According to the colored curable resin composition of the present invention, a color filter having excellent brightness can be formed.

The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) includes a yellow dye and a yellow pigment. And at least one selected from the group consisting of: a blue dye, and a green pigment.
The colored curable resin composition of the present invention preferably further contains a solvent (E) and / or a leveling agent (F).
The colored curable resin composition of the present invention may contain a polymerization initiation assistant (D1) and / or a thiol compound (T).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
The colorant (A) is at least one selected from the group consisting of a blue dye (A1), a green pigment (A2), a yellow dye and a yellow pigment (hereinafter sometimes referred to as “yellow colorant (A3)”). Including.

In the present invention, the blue dye (A1) means a pigment that has a maximum absorption wavelength in the range of 580 nm to 650 nm, preferably 600 nm to 645 nm and is soluble in the solvent.
Examples of the blue dye (A1) include phthalocyanine dyes, compounds represented by the formula (Ab1), diarylmethane dyes, anthraquinone dyes, methine dyes, and azomethine dyes. Among these, a phthalocyanine dye, a compound represented by the formula (Ab1), a polymethine dye, and an azomethine dye are preferable, and a compound represented by the formula (Ab1), a methine dye, and an azomethine dye are more preferable.

  The phthalocyanine dye (Aa) is a dye containing a compound having a phthalocyanine skeleton in the molecule. Examples of the phthalocyanine dye (Aa) include C.I. described in the Color Index (published by The Society of Dyers and Colorists). I. Solvent Blue 67, 70; C.I. I. Direct Blue 86, 87, 189, 199; C.I. I. Acid Blue 249; I. Modern Blue 77; dyes described in JP-A-5-333207, JP-A-6-51115, JP-A-6-194828, and the like.

  Examples of the compound represented by the formula (Ab1) (hereinafter sometimes referred to as “compound (Ab1)”) include C.I. described in Color Index (published by The Society of Dyers and Colorists). I. Solvent Blue 2, 4, 5, 43, 124; I. Basic Blue 1, 5, 7, 26; C.I. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 48, 75, 83, 86, 88, 90, 91, 99, 100, 103, 104, The dyes described in 108, 109, 110, 119, 123, 147, 213, 269 and Japanese Patent No. 4492760 are also included.

式（Ａｂ１）中、Ｒ^１Ａ〜Ｒ^８Ａは、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）を表す。Ｒ^４ＡとＲ^５Ａとは互いに結合して、−ＮＨ−、−Ｓ−、または−ＳＯ_２−を形成していてもよい。
Ｒ^９Ａ〜Ｒ^１２Ａは、それぞれ独立に、アミノ基若しくはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されてもよい）、置換されていてもよいアラルキル基、または置換されていてもよいアリール基、又は水素原子を表し、好ましくは、水素原子、アミノ基若しくはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されてもよい）、または置換されていてもよいアリール基を表す。Ｒ^９ＡとＲ^１０Ａとが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^１１AとＲ^１２Aとが結合してそれらが結合する窒素原子とともに環を形成してもよい。
Ａは、置換されていてもよい芳香族炭化水素基、または置換されていてもよい芳香族複素環基を表す。
Ｇ^ｇ−は、対アニオンを表す。
ｇは、０又は任意の自然数を表す。ｇが０の場合、対アニオンを有しないことを表す。

In formula (Ab1), R ^{1A to} R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 20 carbon atoms (an oxygen atom between carbon atoms constituting the alkyl group). May be inserted). R ^4A and R ^5A may be bonded to each other to form —NH—, —S—, or —SO ₂ —.
R ^{9A to} R ^12A are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom (an oxygen atom may be inserted between carbon atoms constituting the alkyl group). ), An aralkyl group which may be substituted, or an aryl group which may be substituted, or a hydrogen atom, preferably 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom An alkyl group (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an optionally substituted aryl group. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic hydrocarbon group which may be substituted or an aromatic heterocyclic group which may be substituted.
G ^g- represents a counter anion.
g represents 0 or an arbitrary natural number. When g is 0, it represents that there is no counter anion.

The compound represented by the formula (Ab1) includes tautomers thereof.
R ^{1A to} R ^8A are each independently preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In R ^{1A to} R ^8A , the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group.
In R ^{9A to} R ^12A , the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group. Examples of the aryl group which may be substituted include a phenyl group which may be substituted with a halogen atom, a nitro group or a hydroxy group. In R ^{9A to} R ^12A , examples of the aralkyl group include a benzyl group and a phenylethyl group. Examples of the aralkyl group which may be substituted include an aralkyl group which may have —SO ₃ ^— or —SO ₃ J (J represents a cation) as a substituent.
R ^{9A to} R ^12A are each independently preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an optionally substituted benzyl group.
In A, examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 10 carbon atoms such as a phenyl group, a naphthyl group, a toluyl group, and a xylyl group. Examples of the aromatic heterocyclic group include aromatic heterocyclic groups containing a 5-membered heterocyclic ring containing oxygen, nitrogen and sulfur, such as a pyrrolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, and an indolyl group.

In A, the aromatic hydrocarbon group and the aromatic heterocyclic group may have a halogen atom, an optionally substituted amino group, a hydroxy group, a sulfo group, —SO ₃ ^— , — SO ₃ J (J represents a cation) and the like.
Examples of the substituent in the amino group include an alkyl group having 1 to 4 carbon atoms; an aryl group that may have an alkoxy group having 1 to 4 carbon atoms as a substituent; and —SO ₃ ^— and —SO ₃ J as a substituent. And a benzyl group that may be present.
Examples of J include inorganic cations and organic cations. Examples of inorganic cations include alkali metal cations and ammonium cations. Examples of the organic cation include an imidazolium cation such as an organic ammonium cation and a cation represented by the following formula.

式中、Ｒ^Ｂ１は、１価の有機基を表す。該有機基としては、メチル基、エチル基、プロピル基、ブチル基等の炭素数１〜２０の脂肪族炭化水素基；フェニル基、ナフチル基、トルイル基等の炭素数６〜２０の芳香族炭化水素基が挙げられ、該脂肪族炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子等で置換されていてもよい。
Ｒ^Ｂ２及びＲ^Ｂ３は、ハロゲン原子又はハロゲン化炭化水素基を表し、Ｒ^Ｂ２及びＲ^Ｂ３は、互いに結合して−ＳＯ_２−Ｎ⁻−ＳＯ_２−を含む環を形成してもよい。前記ハロゲン化炭化水素基は、好ましくはフッ化炭化水素基、より好ましくは炭素数１〜４のフッ化アルキル基、更に好ましくはペルフルオロアルキル基である。
Ｒ^Ｂ４及びＲ^Ｂ５は、２価の有機基を表す。該有機基は、好ましくは２価の芳香族基である。該芳香族基としては、フェニレン基、ナフタレンジイル基等の２価の炭素数６〜１０の芳香族炭化水素基が挙げられ、該芳香族炭化水素基に含まれる水素原子は、ヒドロキシ基等で置換されていてもよい。
Ｍは、アルミニウム原子又はホウ素原子を表す。 Examples of G ^g- include anions represented by formula (y1), formula (y2), or formula (y3).

In the formula, R ^B1 represents a monovalent organic group. Examples of the organic group include aliphatic hydrocarbon groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, and butyl group; aromatic carbonization having 6 to 20 carbon atoms such as phenyl group, naphthyl group, and toluyl group. Examples thereof include a hydrogen group, and a hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a halogen atom or the like.
R ^B2 and R ^B3 represent a halogen atom or a halogenated hydrocarbon group, and R ^B2 and R ^B3 may be bonded to each other to form a ring containing —SO ₂ —N ^—— SO ₂ —. The halogenated hydrocarbon group is preferably a fluorinated hydrocarbon group, more preferably a fluorinated alkyl group having 1 to 4 carbon atoms, and still more preferably a perfluoroalkyl group.
R ^B4 and R ^B5 represent a divalent organic group. The organic group is preferably a divalent aromatic group. Examples of the aromatic group include divalent aromatic hydrocarbon groups having 6 to 10 carbon atoms such as a phenylene group and a naphthalenediyl group. The hydrogen atom contained in the aromatic hydrocarbon group is a hydroxy group or the like. May be substituted.
M represents an aluminum atom or a boron atom.

  Examples of the anion represented by the formula (y1) include a methanesulfonate anion, a toluenesulfonate anion, a dodecylbenzenesulfonate anion, a trifluoromethanesulfonate anion, and a perfluorobutanesulfonate anion.

As an anion represented by a formula (y2), the anion of a following formula etc. are mentioned, for example.

As an anion represented by a formula (y3), the anion of a following formula etc. are mentioned, for example.

Furthermore, ^examples of G ^g- include halide ions, silicon tungstate anions, resins having sulfonate anions, and trisperfluoroalkylsulfonylmethideate anions.
G ^g− is preferably a halide ion or an anion represented by the formula (y2) or the formula (y3), and more preferably a halide ion and an anion represented by the formula (y2).

As a compound (Ab1), the compound of a following formula is mentioned, for example. In the following formula, J is as defined above.

式（Ａｂ２）中、ｍは任意の自然数を表す。
Ｘは、酸素原子、−ＮＲ^５６−または硫黄原子を示す。
［Ｙ］^ｍ−は、ｍ価のアニオンを表す。
Ｒ^５６は、水素原子又は炭素数１〜１０のアルキル基を表す。
Ｒ^４１〜Ｒ^４６は、それぞれ独立して、アミノ基若しくはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）、置換されていてもよいアラルキル基、置換されていてもよいアリール基、又は水素原子を表し、好ましくは、アミノ基若しくはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）、置換されていてもよいアリール基、又は水素原子を表す。Ｒ^４１とＲ^４２とが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^４３とＲ^４４とが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^４５とＲ^４６とが結合してそれらが結合する窒素原子とともに環を形成してもよい。
Ｒ^４７〜Ｒ^５４は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、炭素数１〜８のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）を表す。Ｒ^４８とＲ^５２とが互いに結合して、−ＮＨ−、−Ｓ−または−ＳＯ_２−を形成していてもよい。
Ｒ^５５は、水素原子、炭素数１〜２０のアルキル基、または置換されていてもよいアリール基を表す。
なお、１分子中に複数の

が含まれる場合、それらは同じ構造であっても異なる構造であってもよい。 The compound (Ab1) is preferably a compound represented by the formula (Ab2) (hereinafter sometimes referred to as “compound (Ab2)”). The compound represented by the formula (Ab2) includes tautomers thereof.

In the formula (Ab2), m represents an arbitrary natural number.
X represents an oxygen atom, —NR ⁵⁶ — or a sulfur atom.
[Y] ^m- represents an m-valent anion.
R ⁵⁶ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ^{41 to} R ⁴⁶ are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom (an oxygen atom is inserted between carbon atoms constituting the alkyl group). Or an aralkyl group which may be substituted, an aryl group which may be substituted, or a hydrogen atom, preferably an alkyl having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom A group (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), an optionally substituted aryl group, or a hydrogen atom; R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms (an oxygen atom is inserted between carbon atoms constituting the alkyl group). May be). R ⁴⁸ and R ⁵² may be bonded to each other to form —NH—, —S—, or —SO ₂ —.
^R55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted.
In addition, a plurality of molecules per molecule

May be the same or different structures.

R ^{41 to} R ⁴⁶ are each independently a benzyl group which may be substituted, an alkyl group having 1 to 20 carbon atoms or an aryl group which may be substituted, or a ring formed together with the above nitrogen atom It is preferable that it is a C1-C20 alkyl group or the aryl group which may be substituted, or it is more preferable that it is a ring formed with the above-mentioned nitrogen atom.
In R ^{41A to} R ^46A , the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group.
In R ^{41A to} R ^46A , the aryl group is preferably an aryl group having 6 to 10 carbon atoms such as a phenyl group or a toluyl group.
In R ^{41A to} R ^46A , the benzyl group which may be substituted includes a benzyl group which may have —SO ₃ ^— or —SO ₃ J (J represents a cation) as a substituent.
R ^{47 to} R ⁵⁴ are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ⁵⁵ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an optionally substituted phenyl group. Examples of the substituent in the phenyl group include a halogen atom, a methyl group, an alkylsulfonyl group having 1 to 4 carbon atoms, and a trifluoromethyl group.

Examples of the cation moiety of the formula (Ab2) include cations 1 to 15 represented by the formula (Ab2-0) shown in Table 1 below. In the table, * represents a bond.

  Among them, the cation moiety of the formula (Ab2) is preferably cation 1 to cation 6, cation 8, cation 11 or cation 12, and cation 1, cation 2, cation 8 or cation 12 is particularly preferable.

[Y] ^m- includes known anions. From the viewpoint of heat resistance, preferred anions are selected from the group consisting of boron-containing anions, aluminum-containing anions, fluorine-containing anions, and tungsten, molybdenum, silicon and phosphorus. An anion containing at least one selected element and oxygen as essential elements.

As a compound (Ab2), the compound represented by a following formula is mentioned, for example.

［式（Ｂ−Ｉ）及び式（Ｃ−Ｉ）中、各符号は、それぞれ前記と同じ意味を表す。］ Compound (Ab2) can be produced by reacting a compound represented by formula (BI) with a compound represented by formula (CI). Such a reaction may be performed in the presence of an organic solvent or may be performed without a solvent.

[In formulas (BI) and (CI), each symbol represents the same meaning as described above. ]

［式（Ｂ−ＩＩ）、式（Ｃ−ＩＩ）及び式（Ｃ−ＩＩ’）中、各符号は、それぞれ上記と同じ意味を表す。］ Compound (Ab2) is obtained by reacting a compound represented by formula (B-II) with a compound represented by formula (C-II) and a compound represented by formula (C-II ′). Can also be manufactured. Such a reaction may be performed in the presence of an organic solvent or may be performed without a solvent.

[In Formula (B-II), Formula (C-II) and Formula (C-II ′), each symbol represents the same meaning as described above. ]

  Examples of the method for producing the compounds (BI) and (B-II) include various known methods, for example, the methods described in West German Patent Application No. P3928243.0.

  As a manufacturing method of compound (CI) and (C-II), a well-known various method, for example, the method described in patent document 1, is mentioned.

The desired compound (Ab2) can be produced by further anion exchange of the compound (Ab2) produced in the above method. Anion exchange can be produced by mixing the compound (Ab2) produced in the above method and the desired [Y] ^m- alkali metal salt in a solvent. Examples of the alkali metal include lithium, sodium and potassium.
[Y] Examples of alkali metal salts of ^m- include Japanese Patent No. 4097704, Japanese Patent No. 4341251 and Journal of The Electronic Society, Vol. 148, Phase 1, 2001. And those described in International Publication No. 2008/077562 and Japanese Patent Application Laid-Open No. 2010-280586.

The tin dye is a dye containing a compound having a structure in which two groups are connected by an odd number of methine chains, and at least one of the two groups is a heterocyclic ring or an aromatic ring (the methine dye is referred to as “polymethine”). Sometimes referred to as "dye").
Specific examples of the compound include compounds having a structure represented by Xa-CH (= CH-CH) _x = Xb (Xa and Xb each represents an arbitrary group, x is an integer of 0 or more). .
The azomethine dye refers to a dye in which one or two or more methine groups in the methine chain are substituted with nitrogen atoms.
Methine dyes and azomethine dyes (hereinafter sometimes collectively referred to as “methine dyes (Ac)”) are preferably compounds having a structure in which the two groups are connected by one methine group or one imino group. The compound represented by (Ac1) is more preferable.

［式（Ａｃ１）中、Ｘ^６１は、窒素原子またはＣＨを表す。
Ｒ^６１は、水素原子または炭素数１〜４のアルキル基を表す。
Ｒ^６２は、水素原子、シアノ基、カルバモイル基、カルボキシ基または炭素数１〜４のアルコキシカルボニル基を表す。
Ｒ^６３は、酸素原子、Ｃ（ＣＮ）₂、Ｃ（ＣＮ）ＣＯ₂Ｌ^１またはＣ（ＣＯ₂Ｌ^１）₂を表す。Ｌ^１は、炭素数１〜８のアルキル基を表し、該アルキル基を構成するメチレン単位の１つまたは２つが酸素原子で置き換わっていてもよい。
Ｒ^６４〜Ｒ^６６は、それぞれ独立に、アミノ基またはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよいアミノ基、置換されていてもよいアリール基、水素原子、またはヒドロキシ基を表し、該アルキル基を構成する炭素原子間には酸素原子が挿入されていてもよい。］

[In the formula (Ac1), X ⁶¹ represents a nitrogen atom or CH.
R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
^R62 represents a hydrogen atom, a cyano group, a carbamoyl group, a carboxy group, or an alkoxycarbonyl group having 1 to 4 carbon atoms.
R ⁶³ represents an oxygen atom, C (CN) ₂ , C (CN) CO ₂ L ¹ or C (CO ₂ L ¹ ) ₂ . L ¹ represents an alkyl group having 1 to 8 carbon atoms, and one or two methylene units constituting the alkyl group may be replaced with an oxygen atom.
R ^{64 to} R ⁶⁶ are each independently an amino group or an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, an amino group that may be substituted, an aryl group that may be substituted, Represents a hydrogen atom or a hydroxy group, and an oxygen atom may be inserted between carbon atoms constituting the alkyl group. ]

X ⁶¹ is preferably a nitrogen atom.
R ⁶¹ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
R ⁶² is preferably a cyano group.
R ⁶³ is preferably an oxygen atom.
R ⁶⁴ is preferably a methyl group, an ethyl group, or —CH (L ² ) (L ³ ). In —CH (L ² ) (L ³ ), L ² and L ³ each independently represent an alkyl group, and the total carbon number of L ² and L ³ is 2 to 19, more preferably 2 to 9. L ² and L ³ are preferably linear alkyl groups.
R ⁶⁵ is preferably an amino group substituted with two alkyl groups having 1 to 10 carbon atoms (more preferably an alkyl group having 3 to 6 carbon atoms), more preferably an N, N-diisopropylamino group. N, N-di-n-butylamino group, N, N-di-n-pentylamino group, and N, N-di-n-hexylamino group.
R ⁶⁶ is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a naphthyl group, a phenyl group or one or more halogen atoms (preferably a fluorine atom or a chlorine atom). More preferably a hydrogen atom, a branched alkyl group having 3 to 5 carbon atoms (preferably isopropyl group, isopentyl group, tert-butyl group), phenyl group or chlorophenyl group.

Examples of the compound represented by the formula (Ac1) include the following compounds. The compound represented by the formula (Ac1) can be produced, for example, by the method described in JP-A-3-166268.

In the present invention, the green pigment (A2) means a dye having a maximum absorption wavelength in the range of 650 nm to 700 nm and insoluble or hardly soluble in a solvent such as water or an organic solvent. For example, pigments classified as pigments in the color index (published by The Society of Dyers and Colorists) can be mentioned.
Examples of the green pigment include C.I. I. Pigment Green 7, 36, 58, JP-A-2004-70342, JP-A-2008-19383, JP-A-2007-320986 and the like, and halogenated phthalocyanine pigments such as green pigments. Preferably, C.I. I. Pigment Green 7, 36, 58.

The yellow colorant (A3) is at least one selected from the group consisting of yellow dyes and yellow pigments. In the present invention, the yellow colorant (A3) means a dye having a maximum absorption wavelength in the range of 400 nm to 470 nm, preferably in the range of 430 nm to 470 nm.
Examples of yellow dyes include azo dyes, metal complex dyes, methine dyes, coumarin dyes, and styrene dyes. Of these, coumarin dyes are preferable.

  The coumarin dye is a dye containing a compound having a coumarin skeleton in the molecule. Examples of the coumarin dye include C.I. described in Color Index (published by The Society of Dyers and Colorists). I. Acid Yellow 227, 250, C.I. I. Disperse Yellow 82, 184, C.I. I. Solvent Orange 112, C.I. I. Examples include Solvent Yellow 160, 172 and Coumarin dyes described in Japanese Patent No. 1299948. Those that are soluble in organic solvents are preferred.

［式（Ａｄ１）中、Ｑ^１Ｂ及びＱ^２Ｂは、それぞれ独立して、水素原子又は−ＣＯ_２Ｍ^１Ｂを表すが、ただし、Ｑ^１Ｂ及びＱ^２Ｂのいずれかは−ＣＯ_２Ｍ^１Ｂを表す。
Ｒ^１Ｂ〜Ｒ^４Ｂは、それぞれ独立に、水素原子又は炭素数１〜２０の１価の炭化水素基を表すか、Ｒ^１Ｂ及びＲ^３Ｂが一緒になって隣接するベンゼン環上の炭素原子および隣接する窒素原子とともに環を形成し、Ｒ^２Ｂ及びＲ^４Ｂが一緒になって隣接するベンゼン環上の炭素原子および隣接する窒素原子とともに環を形成し、または、Ｒ^１Ｂ及びＲ^２Ｂが結合して隣接する窒素原子とともに環を形成する。該１価の炭化水素基を構成するメチレン基は、酸素原子、硫黄原子、−Ｎ（Ｒ^５Ｂ）−、スルホニル基又はカルボニル基に置き換わっていてもよく、該１価の炭化水素基に含まれる水素原子は、ハロゲン原子、シアノ基、ニトロ基、カルバモイル基、スルファモイル基、−ＳＯ_３Ｍ^１Ｂ、−ＣＯ_２Ｍ^１Ｂ、ヒドロキシ基又はアミノ基に置き換わっていてもよい。
Ｒ^５Ｂは、水素原子又は炭素数１〜２０の１価の炭化水素基を表す。Ｒ^５Ｂが複数存在する場合、それらは互いに同一又は相異なる。
Ｍ^１Ｂは、水素原子又はアルカリ金属原子を表す。］ Among these, as the coumarin dye, for example, a compound represented by the formula (Ad1) or the formula (Ad2) (hereinafter sometimes referred to as “compound (Ad1)” or “compound (Ad2)”) is preferable.

[In formula (Ad1), Q ^1B and Q ^2B each independently represent a hydrogen atom or —CO ₂ M ^1B , provided that either Q ^1B or Q ^2B represents —CO ₂ M ^1B .
R ^{1B to} R ^4B each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ^1B and R ^3B together are a carbon atom on the adjacent benzene ring and an adjacent one. To form a ring with the nitrogen atom to be bonded, and R ^2B and R ^4B together form a ring with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom, or R ^1B and R ^2B are bonded to form an adjacent ring To form a ring with the nitrogen atom. The methylene group constituting the monovalent hydrocarbon group may be replaced with an oxygen atom, a sulfur atom, —N (R ^5B ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M ^1B , —CO ₂ M ^1B , a hydroxy group or an amino group.
R ^5B represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^5B are present, they are the same or different from each other.
M ^1B represents a hydrogen atom or an alkali metal atom. ]

R ^1B and R ^2B are each independently preferably a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an ethyl group, a butyl group, a hexyl group, a 2-ethylhexyl group or an octyl group. More preferably an ethyl group, a butyl group, a hexyl group and a 2-ethylhexyl group.
R ^3B and R ^4B are preferably a hydrogen atom.

-R ^1B -R ^3B -and -R ^2B -R ^4B- when R ^1B and R ^3B or R ^2B and R ^4B together form a ring containing the nitrogen and carbon atoms to which they are attached Are each independently —CH ₂ —CH ₂ —, —CF ₂ —CF ₂ —, —CH ₂ —C (CH ₃ ) ₂ — or the like, preferably —CH ₂ —CH ₂ — or —CH. _2- C (CH ₃ ) ₂ —, more preferably —CH ₂ —C (CH ₃ ) ₂ —.
In the case where R ^1B and R ^2B are bonded to form a ring with an adjacent nitrogen atom, —R ^1B —R ^2B — is — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ -,-(CH ₂ ) ₅ -,-(CH ₂ ) ₆ -,-(CH ₂ ) ₇ -,-(CF ₂ ) ₂ -,-(CF ₂ ) ₃ -,-(CF ₂ ) ₄ -,-(CF ₂ ) ₅ -,-(CF ₂ ) ₆ -,-(CF ₂ ) _7- and the like, preferably-(CH ₂ ) ₄ -,-(CH ₂ ) ₅ -,-( CH ₂ ) ₆ —, — (CF ₂ ) ₄ —, — (CF ₂ ) ₅ — or — (CF ₂ ) ₆ —, more preferably — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —. Or — (CH ₂ ) ₆ —, more preferably — (CH ₂ ) ₄ — or — (CH ₂ ) ₅ —.

M ^1B is preferably a hydrogen atom, a sodium atom or a potassium atom, more preferably a hydrogen atom.

As a compound (Ad1), the compound of a following formula and the compound of Unexamined-Japanese-Patent No. 2013-231165 are mentioned, for example.

In formula (Ad2), L ^C represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group, and the hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom.
X ^C represents an oxygen atom or a sulfur atom.
R ^1C and R ^2C each independently represent a phenyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between carbon atoms constituting the alkyl group. May be.
R ^7C to R ^{@ 13 C} are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, formyl group, an amino group, Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, —N (R ^14C ) —, a sulfonyl group or a carbonyl group is inserted between the carbon atoms constituting the hydrocarbon group. at best, hydrogen atoms contained in the hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, formyl group or an amino group May be substituted.
R ^14C represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^14C are present, they may be the same or different.
M ^C represents a hydrogen atom or an alkali metal atom.

The R ^1C and ^{R 2C} substituent which may be a phenyl group optionally having a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, Examples include a formyl group, an amino group, and a monovalent hydrocarbon group having 1 to 20 carbon atoms.

L ^C is preferably a ^C 1-5 divalent hydrocarbon group or sulfonyl group which may be substituted with a fluorine atom, more preferably a propane-2,2-diyl group or hexafluoropropane. -2,2-diyl group or sulfonyl group.
X ^C is preferably an oxygen atom.

Examples of the compound (Ad2) include a compound represented by the following formula.

  Examples of the yellow pigment include C.I. described in Color Index (published by The Society of Dyers and Colorists). I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, 214 and the like. Among them, C.I. I. Pigment Yellow 129, 138, 139, 150 are preferred.

  The yellow colorant (A3) is preferably a yellow dye. If the yellow colorant (A3) is a yellow dye, the content of the yellow colorant (A3) tends to be reduced, so that the resin (B) and the polymerizable compound (C) in the colored curable resin composition The content can be increased, and the durability of the obtained color filter, such as heat resistance and chemical resistance, can be improved.

  The colorant (A) may further contain other dyes and / or pigments to the extent that the performance of the colored curable resin composition of the present application is not impaired. Other dyes include, for example, compounds classified as having a hue other than pigment in the Color Index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (Color Dyeing) Among these, dyes other than the blue dye (A1) and the yellow colorant (A3) are mentioned. In addition, according to the chemical structure, azo dyes, phthalocyanine dyes, anthraquinone dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, squarylium dyes, acridine dyes, styryl dyes, quinoline dyes, nitro dyes, and the like can be given.

Other pigments are not particularly limited as long as they are other than the yellow pigments of the green pigment (A2) and the yellow colorant (A3), and known pigments can be used. For example, a color index (The Society of Dyers and Colourists publication).
Examples of the pigment include C.I. I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. And Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, and 38.

In the colorant (A), the content of the blue dye (A1), the green pigment (A2) and the yellow colorant (A3) is preferably in the following ranges.
Blue dye (A1): 0.1% by mass or more and 20% by mass or less (more preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less)
Green pigment (A2): 30% to 85% by mass (more preferably 45% to 75% by mass, and still more preferably 50% to 70% by mass)
Yellow colorant (A3): 5% to 60% by mass (more preferably 10% to 50% by mass, and still more preferably 15% to 45% by mass)

The content of the blue dye (A1) is preferably 0.2 parts by mass or more and 100 parts by mass or less, more preferably 0.4 parts by mass or more and 50 parts by mass, with respect to 100 parts by mass of the green pigment (A2). It is not more than mass parts, more preferably not less than 0.6 parts by mass and not more than 20 parts by mass.
The content of the yellow colorant (A3) is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more and 150 parts by mass or less, with respect to 100 parts by mass of the green pigment (A2). Preferably they are 30 to 120 mass parts.
In particular, it is preferable that the content of the blue dye (A1) is within the above range because the brightness of the obtained color filter tends to be further increased.

  In the colorant (A), the combination of the blue dye (A1), the green pigment (A2) and the yellow colorant (A3) is preferably a phthalocyanine dye (Aa) /C.I. I. Pigment Green 7 / coumarin dye, phthalocyanine dye (Aa) /C.I. I. Pigment Green 58 / coumarin dye, phthalocyanine dye (Aa) /C.I. I. Pigment Green 7 / Azo dye, phthalocyanine dye (Aa) /C.I. I. Pigment Green 58 / azo dye, compound represented by formula (Ab1) /C.I. I. Pigment Green 7 / coumarin dye, compound represented by formula (Ab1) /C.I. I. Pigment Green 36 / coumarin dye, compound represented by formula (Ab1) /C.I. I. Pigment Green 58 / coumarin dye, compound represented by formula (Ab1) /C.I. I. Pigment Green 7 / Azo dye, compound represented by formula (Ab1) /C.I. I. Pigment Green 7 / C.I. I. Pigment Yellow 129, a compound represented by formula (Ab1) /C.I. I. Pigment Green 7 / C.I. I. Pigment Yellow 138, a compound represented by the formula (Ab1) /C.I. I. Pigment Green 58 / C.I. I. Pigment Yellow 129, a compound represented by formula (Ab1) /C.I. I. Pigment Green 58 / C.I. I. Pigment Yellow 138, a compound represented by the formula (Ab1) /C.I. I. Pigment Green 58 / azo dye, methine dye (Ac) /C.I. I. Pigment Green 7 / coumarin dye, methine dye (Ac) /C.I. I. Pigment Green 36 / coumarin dye, methine dye (Ac) /C.I. I. Pigment Green 58 / coumarin dye, methine dye (Ac) /C.I. I. Pigment Green 7 / Azo dye, Methine dye (Ac) /C.I. I. Pigment Green 58 / azo dye, methine dye (Ac) /C.I. I. Pigment Green 7 / C.I. I. Pigment Yellow 129, methine dye (Ac) /C.I. I. Pigment Green 7 / C.I. I. Pigment Yellow 138, methine dye (Ac) /C.I. I. Pigment Green 58 / C.I. I. Pigment Yellow 129, polymethine dye (Ac) /C.I. I. Pigment Green 58 / C.I. I. Pigment Yellow 138, and more preferably, a compound represented by formula (Ab1) /C.I. I. Pigment Green 7 / coumarin dye, compound represented by formula (Ab1) /C.I. I. Pigment Green 58 / coumarin dye, methine dye (Ac) /C.I. I. Pigment Green 7 / coumarin dye, methine dye (Ac) /C.I. I. Pigment Green 58 / coumarin dye.

The pigment such as green pigment (A2) is optionally treated with rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid, etc. An atomization process by an atomization method or the like, a cleaning process with an organic solvent or water for removing impurities, a removal process by an ion exchange method of an ionic impurity, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

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

  The content of the colorant (A) is preferably 5 to 65% by mass, more preferably 8 to 60% by mass, and further preferably 10 to 55% by mass with respect to the total amount of the solid content. When the content of the colorant (A) is in the above range, the color density when used as a color filter is sufficient, and a resin or a polymerizable compound can be contained in the composition in a necessary amount. A pattern with sufficient strength can be formed. Here, the “total amount of solid content” in this specification refers to an amount obtained by removing 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 thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]; at least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and a cyclic ether having 2 to 4 carbon atoms A copolymer of a monomer (b) having a structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2]; (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases)
Resin [K3]; Copolymer of (a) and (c);
Resin [K4]; a resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5]; a resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6]: A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

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

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

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

  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)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

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

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

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

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

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

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

  The compound represented by 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.

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

  (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. preferable.

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

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

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

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored 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 of the structural units constituting the resin [K2]
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, There is a tendency to be excellent in heat resistance and mechanical strength.

  Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

In the resin [K3], the proportion of structural units derived from each of the structural units constituting the resin [K3]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50-90 mol%
It is more preferable that
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

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

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making it within this range, the storage stability of the colored curable resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern are improved. Tend. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 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 and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is respectively based on the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol%
Structural unit derived from (c); 5-95 mol%
It is preferable that
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c); 10 to 90 mol%
It is more preferable that

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5].
Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Glycidyl (meth) acrylate was added to resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic Resins such as resins obtained by adding glycidyl (meth) acrylate to an acid copolymer [K4]; resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid , Tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin [K5] such as a resin obtained by reacting a copolymer with (meth) acrylic acid; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Furthermore, resin [K6] such as a resin obtained by reacting tetrahydrophthalic anhydride may be used.
Especially, as resin (B), resin [K1], resin [K2], and resin [K3] are preferable, and resin [K1] and resin [K2] are more preferable.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is 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 developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

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

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

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

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

  The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator 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（登録商標）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-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

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

  Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF) As a compound having a partial structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, alpha, alpha-diethoxyacetophenone, and benzyl dimethyl ketal.

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

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial 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, 2,2′-bis (2,3-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913).

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

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium. Onium salts such as hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate Examples include rates.

  The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, and a biimidazole compound. More preferred is a polymerization initiator containing a sulfur compound.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

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

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

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

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) .

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

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

  The content of the leveling agent (F) is preferably 0.001% by mass to 0.2% by mass, and preferably 0.002% by mass to 0.1%, based on the total amount of the colored curable resin composition. It is not more than mass%, more preferably not less than 0.01 mass% and not more than 0.05 mass%. This content does not include the content of the pigment dispersant. 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 colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored 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 the leveling agent (F), the polymerization initiation assistant (D1), the thiol compound (T) and other components.
The pigment such as the green pigment (A2) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The dye such as the blue dye (A1) may be dissolved in part or all of the solvent (E) to prepare a solution in advance. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

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

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

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

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

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

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

  According to the colored curable resin composition of the present invention, a color filter having particularly excellent brightness can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors. Especially, it is useful as a color filter for liquid crystal display devices, and is particularly useful as a color filter for liquid crystal display devices using LEDs as a backlight.

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

[Synthesis Example 1]
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 36.3 parts of potassium thiocyanate and 160 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with ice, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 35.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain an organic layer from which moisture was removed. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 52 parts of a compound represented by the formula (BI-1). Yield 50%

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.3 parts of the compound represented by the formula (BI-1), 10 parts of 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, 20.0 parts of toluene was added, and then 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170 parts of isopropanol. Next, the diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain an organic layer from which moisture was removed. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 19.8 parts of a compound represented by the formula (A-II-1). Yield 100%

Identification of compound represented by formula (A-II-1) (mass spectrometry) ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺
Exact Mass: 636.3

式（Ａｂ２−１）で表される化合物０．３５ｇをクロロホルムに溶解して体積を２５０ｃｍ^３とし、そのうちの２ｃｍ^３をイオン交換水で希釈して体積を１００ｃｍ^３として（濃度：０．０２８ｇ／Ｌ）、分光光度計（石英セル、光路長；１ｃｍ）を用いて吸収スペクトルを測定した。この化合物は、極大吸収波長λｍａｘ＝６２８ｎｍで吸光度２．９（任意単位）を示した。 The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10 parts of the compound represented by the formula (A-II-1), 4.5 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), and After adding 100 parts of N, N-dimethylformamide, the mixture was stirred at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.3 parts of a compound represented by the formula (Ab2-1). Yield 82%

0.35 g of the compound represented by the formula (Ab2-1) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at the maximum absorption wavelength λmax = 628 nm.

[Synthesis Example 2]
The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 11 parts of potassium thiocyanate and 39.4 parts of acetone were added, followed by stirring at room temperature for 30 minutes. Subsequently, 13 parts of benzoic acid chloride was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, the reaction solution was ice-cooled, and 23 parts of di (2-ethylhexyl) amine was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, the reaction solution was ice-cooled, and 30 parts of 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 9.2 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction solution to cool to room temperature, the reaction solution was poured into 13 parts of tap water, and then 26 parts of ethyl acetate was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 13 parts of 1N hydrochloric acid, then with 13 parts of tap water, and finally with 13 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain an organic layer from which moisture was removed. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. Further, the pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 14 parts of a compound represented by the formula (BI-2). Yield 48%

The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 1000 parts of normal pentanol, 133 parts of 3-aminocrotonitrile and 250 parts of N-cyanoacetyl-N ′-(2-ethylhexanoyl) hydrazine, and then heated to reflux. Stirring under 2 hours. Next, after adding 166.4 parts of zinc chloride, the mixture was further stirred for 4 hours while heating under reflux. Subsequently, 225 parts of concentrated hydrochloric acid was added dropwise. After completion of dropping, normal pentanol was distilled off together with water vapor. The remaining suspension was filtered with suction, and the residue was washed with water to obtain a pale yellow solid. Further, the pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 215 parts of a compound represented by the formula (C-II-1). Yield 71%

The following reaction was performed in a nitrogen atmosphere. 120 parts of the compound represented by the formula (C-II-1), 1200 parts of glacial acetic acid and 1200 parts of concentrated hydrochloric acid were added to a flask equipped with a condenser and a stirring device, and then stirred at room temperature for 30 minutes. Next, after cooling the reaction solution with ice, 28.5 parts of a 23% aqueous sodium nitrite solution was added and stirred for 3 hours to obtain a reddish brown suspension. After the obtained reddish brown suspension is filtered by suction. The residue was washed with water to obtain a reddish brown solid. Furthermore, the reddish brown solid was dried at 60 ° C. under reduced pressure to obtain 120 parts of a compound represented by the formula (C-I-1). Yield 90%

The following reaction was performed in a nitrogen atmosphere. To a flask equipped with a condenser and a stirrer, 2 parts of concentrated hydrochloric acid, 7 parts of acetic acid and 1.5 parts of the compound represented by the formula (C-I-1) were added and stirred at room temperature for 30 minutes. Next, 1.6 parts of the compound represented by the formula (BI-2) and 0.5 parts of water were added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes. Next, 0.05 part of amidosulfonic acid was added to the reaction solution, followed by stirring at room temperature for 20 minutes. Subsequently, after adding 7 parts of 30% sodium hydroxide aqueous solution to the reaction solution, it stirred at 60 degreeC for 4 hours. Next, after the reaction solution was allowed to cool to room temperature, the reaction solution was poured into 15 parts of tap water, and then 15 parts of ethyl acetate was added and stirred for 30 minutes.
Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After discarding the aqueous layer by liquid separation, the obtained organic layer was evaporated using an evaporator to obtain a blue-green solid. Further, the blue-green solid was purified by silica gel column chromatography to obtain 1.2 parts of a compound represented by the formula (Ac1-7). Yield 36%

0.35 g of the compound represented by the formula (Ac1-7) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.6 (arbitrary unit) at λmax = 621 nm.

Identification of compound represented by formula (Ac1-7) (mass spectrometry) ionization mode = ESI +: m / z = 684.4 [M + H] ⁺
Exact Mass: 683.4

[Synthesis Example 3]
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 5 parts of 2-bromo-3′-nitroacetophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 parts of a 50% isopropanol aqueous solution, and then stirred at room temperature for 30 minutes. . Next, 3 parts of potassium thiocyanate was added over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 3 hours. Next, 50 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was filtered off, the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 4.2 parts of a compound represented by the formula (B-II-21). Yield 92%

The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 5 parts of the compound represented by the formula (B-II-13) and 50 parts of ethanol, and then stirred at room temperature for 30 minutes. Next, 2.9 parts of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.4 parts of glacial acetic acid were added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred for 2 hours with heating under reflux. After allowing the reaction solution to cool to room temperature, 70 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was filtered off, the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 4.2 parts of a compound represented by the formula (B-I-21). Yield 64%

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.4 parts of the compound represented by the formula (BI-13), 10 parts of 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, 20.0 parts of toluene was added, and then 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170 parts of isopropanol. Next, the diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes.
Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain an organic layer from which moisture was removed. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 10.2 parts of a compound represented by the formula (A-II-21). Yield 52%

Identification of compound represented by formula (A-II-21) (mass spectrometry) ionization mode = ESI +: m / z = 596.3 [M-Cl] ⁺
Exact Mass: 631.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10 parts of the compound represented by the formula (A-II-13), 5.9 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), and After charging 30 parts of N, N-dimethylformamide, the mixture was stirred at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.5 parts of a compound represented by the formula (Ab2-21). Yield 83%

0.35 g of the compound represented by the formula (Ab2-21) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 3.0 (arbitrary unit) at λmax = 634 nm.

[Synthesis Example 4]
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 33 parts of potassium thiocyanate and 160 parts of acetone, and then stirred at room temperature for 30 minutes. Subsequently, 50 parts of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with ice, 41.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 32.1 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline.
An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain an organic layer from which moisture was removed. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 40.5 parts of a compound represented by the formula (BI-9). Yield 41%

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.7 parts of the compound represented by the formula (BI-9), 10 parts of 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, after adding 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170 parts of isopropanol. Next, the diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain an organic layer from which moisture was removed. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 15.1 parts of a compound represented by the formula (A-II-9). Yield 75%

Identification of compound represented by formula (A-II-9) (mass spectrometry) ionization mode = ESI +: m / z = 615.4 [M-Cl] ⁺
Exact Mass: 650.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10 parts of the compound represented by the formula (A-II-9), 5.7 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), and After charging 30 parts of N, N-dimethylformamide, the mixture was stirred at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 13.2 parts of a compound represented by the formula (Ab2-9). Yield 96%

0.35 g of the compound represented by the formula (Ab2-9) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.7 (arbitrary unit) at λmax = 627 nm.

[Synthesis Example 5]
4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 parts, 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.8 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) )) 2.73 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 157 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 7.43 parts are mixed and stirred at 120 ° C. for 3 hours. did. 7.46 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.79 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 49.8 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) And 12.7 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 120 ° C. for 14 hours. Ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 3.76 parts, Benzoic acid (Tokyo Chemical Industry Co., Ltd.) 1.41 parts, 1-Pentanol (Tokyo Chemical Industry Co., Ltd.) 52.5 parts And 6.35 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C. for 8 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. To this residue was added 140 parts of tetrahydrofuran, and the mixture was stirred at 70 ° C. for 1 hour, and insoluble matter was obtained as a residue of suction filter. To this residue was added 120 parts of tetrahydrofuran, and the mixture was stirred at 70 ° C. for 1 hour, and insoluble matter was obtained as a residue of a suction filter. To this residue, 340 parts of N, N-dimethylformamide was added, dissolved by heating to 90 ° C., and then allowed to stand at 0 ° C. to 5 ° C. The precipitated crystals were obtained as a suction filtration residue. This residue was dried under reduced pressure at 60 ° C. to obtain 5.69 parts of a compound represented by the formula (Ad1-1). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (Ad1-1)>
¹ H-NMR (500 MHz, DMSO-d6): 1.14 (6H, t), 3.47 (4H, q), 6.57 (1H, d), 6.78 (1H, dd), 7. 68 (1H, d), 7.79 (1H, d), 7.96 (1H, dd), 8.15 (1H, d), 8.80 (1H, s), 13.11 (1H, s ).

[Synthesis Example 6]
275 parts of resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 101 parts of n-hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 150 to 155 ° C. for 20 hours while removing the water produced. After allowing to cool, the reaction mixture was dissolved in 433 parts of toluene, and this toluene solution was washed three times with 1000 parts of warm water at 40 ° C. 50 parts of anhydrous magnesium sulfate was added to this toluene solution and stirred, followed by filtration. The solvent of the filtrate was distilled off to obtain a crude product. This crude product was dissolved in 234 parts of toluene and stirred at 0 ° C. or lower, and the crystallized product was collected by filtration. This crystallized product was dried under reduced pressure at 50 ° C. to obtain 95.7 parts of a compound represented by the formula (pt1).

<Identification of Compound Represented by Formula (pt1)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 194.2
Exact Mass: 193.2

95.3 parts of the compound represented by the formula (pt1) and 48.0 parts of water were mixed and stirred at 80 ° C. Subsequently, while adding 107 parts of 1-bromo-2-ethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.), the mixture was stirred at 80 ° C. for 3 hours, and then 22.4 parts of a 48% aqueous sodium hydroxide solution was added.
The mixture was stirred at 110 ° C. for 18 hours. After allowing to cool, the pH of the reaction mixture was adjusted to 5 using 10% aqueous sodium hydroxide solution, 130 parts of toluene was added and stirred, and the toluene layer was extracted. The toluene extract was washed twice with 500 parts of warm water, added with 25 parts of anhydrous magnesium sulfate, stirred and filtered. The solvent of the filtrate was distilled off to obtain 154 parts of a residue containing the compound represented by the formula (pt2) as a main component.

<Identification of Compound Represented by Formula (pt2)>
(Mass Spectrometry) ionization mode = ESI +: m / z = [M + H] + 306.3
Exact Mass: 305.3

154 parts of the residue containing the compound represented by (pt2) as a main component and 597 parts of N, N-dimethylformamide were mixed and stirred at -6 ° C to 3 ° C. To this, 258 parts of phosphoryl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added while maintaining the liquid temperature at −6 ° C. to 3 ° C. The mixture was stirred at room temperature for 1 hour and then stirred at 60 ° C. for 4 hours. After allowing to cool, the reaction mixture was added to 1500 parts of ice and neutralized with a 48% aqueous sodium hydroxide solution. To this, 867 parts of toluene was added, and the toluene layer was extracted. This toluene extract was washed twice with 1200 parts of a 15% aqueous sodium chloride solution. 60 parts of anhydrous magnesium sulfate was added to this toluene extract and stirred, followed by filtration. The filtrate was evaporated to give a residue. This residue was purified by column chromatography to obtain 94.4 parts of a compound represented by the formula (pt3).

<Identification of compound represented by formula (pt3)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 334.3
Exact Mass: 333.3

10.6 parts of bis (3-amino-4-hydroxyphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 25.3 parts of a compound represented by the formula (pt3), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 3.2 parts, 184 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.59 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 25.4 parts of the compound represented by the formula (pt3), 3.21 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 90 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.59 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 120 ° C. for 12 hours. The reaction solution was cooled to room temperature, added to 1800 parts of methanol, and the precipitated crystals were obtained as a residue of suction filtration. The residue was purified by column chromatography to obtain 20.6 parts of a compound represented by the formula (Ad2-10). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (Ad2-10)>
¹ H-NMR (500 MHz, DMSO-d ₆ ): 0.85 (6H, t), 0.87 (6H, t), 0.87 (6H, t), 1.20 to 1.40 (28H) , 1.56 (4H, tt), 1.75 (2H, ttt), 3.34 (4H, d), 3.43 (4H, t), 6.55 (2H, d), 6.79 ( 2H, dd), 7.64 (2H, d), 7.91 (2H, d), 8.01 (2H, dd), 8.36 (2H, d), 8.73 (2H, s)

[Synthesis Example 7]
A suitable amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Then 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution prepared by dissolving 225 parts of a mixture of decan-9-yl acrylate (content ratio is 50:50 in molar ratio) and 81 parts of vinyl toluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate. Was dropped into the flask over 4 hours.
On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion | finish of dripping of an initiator solution, after hold | maintaining at 85 degreeC for 4 hours, it cooled to room temperature and obtained the copolymer (resin Ba) solution. The solid content of the resin Ba solution was 37%, and the viscosity measured with a B-type viscometer (23 ° C.) was 246 mPa · s. The weight average molecular weight of Resin Ba was 1.06 × 10 ⁴ , the acid value in terms of solid content was 115 mg-KOH / g, and the molecular weight distribution was 2.01.
Resin Ba has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Examples 1-8 and Comparative Examples 1-2
<Preparation of pigment dispersion>
Preparation Example 1
Colorant (A): C.I. I. Pigment Green 7 (pigment; λmax = 660 nm) 27 parts,
12 parts acrylic pigment dispersant,
Resin (B): Methacrylic acid / benzyl methacrylate copolymer (copolymerization ratio (mass ratio); 30/70, Mw; 1.2 × 10 ⁴ ) (solid content conversion) 9.5 parts, and solvent (E) : 180 parts of propylene glycol monomethyl ether acetate was mixed, and the pigment dispersion 1 was prepared by sufficiently dispersing the pigment using a bead mill.

Preparation Example 2
C. I. Pigment Green 7 (pigment) was changed to C.I. I. A pigment dispersion 2 was prepared in the same manner as in Preparation Example 1, except that Pigment Green 58 (pigment; λmax = 675 nm) was used.

<Preparation of colored curable resin composition>
Each component of Table 2 was mixed to obtain a green colored curable resin composition. In Table 2, the number of parts of resin indicates a value in terms of solid content.

Blue dye (A1); Aa; compound represented by formula (Ab2-1) (λmax = 628 nm) Blue dye (A1); Ab; compound represented by formula (Ac1-7) (λmax = 621 nm) Blue dye (A1); Ac; compound represented by formula (Ab2-13) (λmax = 634 nm)
Blue dye (A1); Ad; compound represented by formula (Ab2-9) (λmax = 627 nm) Blue dye (A1); Ae; I. Acid Blue 1 (λmax = 639nm)
Yellow colorant (A3); Af; compound represented by formula (Ad1-1) (λmax = 453 nm)
Yellow colorant (A3); Ag; compound represented by formula (Ad2-10) (λmax = 455 nm)
Resin (B); Ba; Resin Ba
Polymerizable compound (C); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D); Da; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime Compound)
Solvent (E); Ea; Propylene glycol monomethyl ether acetate Solvent (E); Eb; Ethyl lactate Solvent (E); Ec; 4-Hydroxy-4-methyl-2-pentanone Leveling agent (F); Polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Preparation of colored pattern>
A colored curable resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After standing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and the amount of light (365 nm) was measured in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). (Reference). A photomask having a 100 μm line and space pattern was used. The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, Post-baking was performed for 30 minutes at ° C.
A colored pattern was obtained from the colored curable resin compositions of Examples 1 to 8 and Comparative Example 1.
In the colored curable resin composition of Comparative Example 2, the unexposed portion of the colored composition layer by development was not sufficiently removed, and a colored pattern was not obtained. In the pattern formation column in Table 3, “O” indicates that the colored pattern was obtained, and “X” indicates that the colored pattern was not obtained.

<Film thickness measurement>
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

<Chromaticity evaluation>
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 3.

  According to the colored curable resin composition of the present invention, a color filter having excellent brightness can be produced.

Claims (5)

Containing a colorant, a resin, a polymerizable compound and a polymerization initiator,
A colored curable resin composition, wherein the colorant comprises at least one selected from the group consisting of a yellow dye and a yellow pigment, a blue dye, and a green pigment.   The colored curable resin composition according to claim 1, wherein the content of the blue dye is 0.1% by mass or more and 20% by mass or less with respect to the total content of the colorant.   The colored curable resin composition according to claim 1 or 2, wherein the polymerization initiator is a polymerization initiator containing an O-acyloxime compound.   A color filter formed from the colored curable resin composition according to claim 1.   A display device comprising the color filter according to claim 4.