JP6098158B2 - Compound - Google Patents

Description

  The present invention relates to a compound useful as a dye.

Dyes are used for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jets, and the like. As such a dye, coumarin 6 (a compound represented by the following formula) is known (Patent Document 1).

JP 2006-154740 A (Example 8)

  Said compound was not fully satisfactory as a dye used for the color filter of display apparatuses, such as a liquid crystal display device, by the point of thermal stability.

［式（Ｉ）中、
Ｌは、炭素数１〜２０の２価の炭化水素基を表す。該２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^１０）−、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２価の炭化水素基に含まれる水素原子は、シアノ基、ニトロ基、カルバモイル基、スルファモイル基、スルホ基、カルボキシ基、ヒドロキシ基、塩素原子、臭素原子、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｘは、酸素原子、硫黄原子又は−Ｎ（Ｒ^１０）−を表す。
Ａは、炭素数６〜２０の芳香族基を表す。該芳香族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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基、アミノ基又は炭素数１〜２０の１価の炭化水素基に置き換わっていてもよい。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^１０）−、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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｒ^１〜Ｒ^４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、或いは、Ｒ^１とＲ^３とが結合して、隣接するベンゼン環上の炭素原子及び隣接する窒素原子とともに環を形成し、またはＲ^２とＲ^４とが結合して、隣接するベンゼン環上の炭素原子及び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^１０）−、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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｒ^５〜Ｒ^９は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、カルバモイル基、スルファモイル基、スルホ基、カルボキシ基、ヒドロキシ基、アミノ基又は炭素数１〜２０の１価の炭化水素基を表すか、Ｒ^５とＲ^６とが結合して、隣接する炭素原子とともに環を形成するか、或いは、Ｒ^７とＲ^８とが結合して、隣接する炭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^１０）−、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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｒ^１０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^１０が複数存在する場合、それらは互いに同一又は相異なる。］
［２］式（Ｉ’）で表される化合物。

［式（Ｉ’）中、
Ｌは、炭素数１〜２０の２価の炭化水素基を表す。該２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^１０）−、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２価の炭化水素基に含まれる水素原子は、シアノ基、ニトロ基、カルバモイル基、スルファモイル基、スルホ基、カルボキシ基、ヒドロキシ基、塩素原子、臭素原子、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｘは、酸素原子、硫黄原子又は−Ｎ（Ｒ^１０）−を表す。
Ｒ^１〜Ｒ^４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、或いは、Ｒ^１とＲ^３とが結合して、隣接するベンゼン環上の炭素原子及び隣接する窒素原子とともに環を形成し、またはＲ^２とＲ^４とが結合して、隣接するベンゼン環上の炭素原子及び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^１０）−、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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｒ^５〜Ｒ^９は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、カルバモイル基、スルファモイル基、スルホ基、カルボキシ基、ヒドロキシ基、アミノ基又は炭素数１〜２０の１価の炭化水素基を表すか、Ｒ^５とＲ^６とが結合して、隣接する炭素原子とともに環を形成するか、或いは、Ｒ^７とＲ^８とが結合して、隣接する炭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^１０）−、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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｒ^１０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^１０が複数存在する場合、それらは互いに同一又は相異なる。］
［３］Ｘが、酸素原子又は硫黄原子である［１］又は［２］に記載の化合物。
［４］Ｘが、酸素原子である［１］〜［３］のいずれかに記載の化合物。
［５］Ｌが、置換基を有していてもよいメチレン基又はスルホニル基である［１］〜［４］のいずれかに記載の化合物。
［６］Ｌが、ジメチルメチレン基又はスルホニル基である［１］〜［５］のいずれかに記載の化合物。
［７］Ｒ^５〜Ｒ^９が、いずれも水素原子である［１］〜［６］のいずれかに記載の化合物。
［８］［１］〜［７］のいずれかに記載の化合物を含む染料。
［９］［１］〜［７］のいずれかに記載の化合物、樹脂、重合性化合物、重合開始剤及び溶剤を含む着色感光性樹脂組成物。
［１０］式（Ｉ）又は式（Ｉ’）で表される化合物を含む着色剤、樹脂、重合性化合物、重合開始剤及び溶剤を含む着色感光性樹脂組成物。
［１１］着色剤が、さらに顔料を含む［１０］に記載の着色感光性樹脂組成物。
［１２］顔料が、ハロゲン化銅フタロシアニン顔料及びハロゲン化亜鉛フタロシアニン顔料からなる群から選ばれる少なくとも一種である［１１］に記載の着色感光性樹脂組成物。
［１３］顔料が、塩素化銅フタロシアニン顔料、臭素化銅フタロシアニン顔料及び臭素化亜鉛フタロシアニン顔料からなる群から選ばれる少なくとも一種である［１１］又は［１２］に記載の着色感光性樹脂組成物。
［１４］顔料が、緑色顔料である［１１］〜［１３］のいずれかに記載の着色感光性樹脂組成物。
［１５］顔料が、Ｃ．Ｉ．ピグメントグリーン７、Ｃ．Ｉ．ピグメントグリーン３６及びＣ．Ｉ．ピグメントグリーン５８からなる群から選ばれる少なくとも一種である［１１］〜［１４］のいずれかに記載の着色硬化性樹脂組成物。
［１６］顔料が、Ｃ．Ｉ．ピグメントグリーン７である［１１］〜［１５］のいずれかに記載の着色硬化性樹脂組成物。
［１７］［９］〜［１６］のいずれかに記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［１８］［１７］に記載のカラーフィルタを含む液晶表示装置。 The present invention includes the following inventions.
[1] A compound represented by the formula (I).

[In the formula (I),
L represents a C1-C20 bivalent hydrocarbon group. The methylene group constituting the divalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the divalent hydrocarbon group. The hydrogen atom may be replaced with a cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, chlorine atom, bromine atom, imidazol-1-yl group or amino group.
X represents an oxygen atom, a sulfur atom, or —N (R ¹⁰ ) —.
A represents an aromatic group having 6 to 20 carbon atoms. The hydrogen atom contained in the aromatic group is a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group, amino group, or C1-20. May be replaced by a monovalent hydrocarbon group. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ³ are bonded to each other to form a carbon atom on an adjacent benzene ring. A ring is formed with an atom and an adjacent nitrogen atom, or R ² and R ⁴ are combined to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ^{5 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxy group, a hydroxy group, an amino group, or a monovalent group having 1 to 20 carbon atoms. Represents a hydrocarbon group, R ⁵ and R ⁶ combine to form a ring with adjacent carbon atoms, or R ⁷ and R ⁸ combine to form a ring with adjacent carbon atoms To do. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ¹⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ¹⁰ are present, they are the same or different from each other. ]
[2] A compound represented by the formula (I ′).

[In the formula (I ′),
L represents a C1-C20 bivalent hydrocarbon group. The methylene group constituting the divalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the divalent hydrocarbon group. The hydrogen atom may be replaced with a cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, chlorine atom, bromine atom, imidazol-1-yl group or amino group.
X represents an oxygen atom, a sulfur atom, or —N (R ¹⁰ ) —.
R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ³ are bonded to each other to form a carbon atom on an adjacent benzene ring. A ring is formed with an atom and an adjacent nitrogen atom, or R ² and R ⁴ are combined to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ^{5 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxy group, a hydroxy group, an amino group, or a monovalent group having 1 to 20 carbon atoms. Represents a hydrocarbon group, R ⁵ and R ⁶ combine to form a ring with adjacent carbon atoms, or R ⁷ and R ⁸ combine to form a ring with adjacent carbon atoms To do. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ¹⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ¹⁰ are present, they are the same or different from each other. ]
[3] The compound according to [1] or [2], wherein X is an oxygen atom or a sulfur atom.
[4] The compound according to any one of [1] to [3], wherein X is an oxygen atom.
[5] The compound according to any one of [1] to [4], wherein L is a methylene group or sulfonyl group which may have a substituent.
[6] The compound according to any one of [1] to [5], wherein L is a dimethylmethylene group or a sulfonyl group.
[7] The compound according to any one of [1] to [6], wherein R ^{5 to} R ⁹ are all hydrogen atoms.
[8] A dye comprising the compound according to any one of [1] to [7].
[9] A colored photosensitive resin composition comprising the compound, resin, polymerizable compound, polymerization initiator and solvent according to any one of [1] to [7].
[10] A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent containing a compound represented by formula (I) or formula (I ′).
[11] The colored photosensitive resin composition according to [10], wherein the colorant further contains a pigment.
[12] The colored photosensitive resin composition according to [11], wherein the pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment.
[13] The colored photosensitive resin composition according to [11] or [12], wherein the pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment, and a brominated zinc phthalocyanine pigment.
[14] The colored photosensitive resin composition according to any one of [11] to [13], wherein the pigment is a green pigment.
[15] The pigment is C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. The colored curable resin composition according to any one of [11] to [14], which is at least one selected from the group consisting of CI Pigment Green 58.
[16] The pigment is C.I. I. The colored curable resin composition according to any one of [11] to [15], which is CI Pigment Green 7.
[17] A color filter formed from the colored curable resin composition according to any one of [9] to [16].
[18] A liquid crystal display device comprising the color filter according to [17].

  Since the compound of the present invention has high thermal stability, it is excellent as a dye used for a color filter of a display device such as a liquid crystal display device.

［式（Ｉ）及び式（Ｉ’）中、
Ｌは、炭素数１〜２０の２価の炭化水素基を表す。該２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^１０）−、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２価の炭化水素基に含まれる水素原子は、シアノ基、ニトロ基、カルバモイル基、スルファモイル基、スルホ基、カルボキシ基、ヒドロキシ基、塩素原子、臭素原子、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｘは、酸素原子、硫黄原子又は−Ｎ（Ｒ^１０）−を表す。
Ａは、炭素数６〜２０の芳香族基を表す。該芳香族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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基、アミノ基又は炭素数１〜２０の１価の炭化水素基に置き換わっていてもよい。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^１０）−、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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｒ^１〜Ｒ^４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、或いは、Ｒ^１とＲ^３とが結合して、隣接するベンゼン環上の炭素原子及び隣接する窒素原子とともに環を形成し、またはＲ^２とＲ^４とが結合して、隣接するベンゼン環上の炭素原子及び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^１０）−、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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｒ^５〜Ｒ^９は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、カルバモイル基、スルファモイル基、スルホ基、カルボキシ基、ヒドロキシ基、アミノ基又は炭素数１〜２０の１価の炭化水素基を表すか、Ｒ^５とＲ^６とが結合して、隣接する炭素原子とともに環を形成するか、或いは、Ｒ^７とＲ^８とが結合して、隣接する炭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^１０）−、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、スルホ基、カルボキシ基、ヒドロキシ基、イミダゾール−１−イル基又はアミノ基に置き換わっていてもよい。
Ｒ^１０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^１０が複数存在する場合、それらは互いに同一又は相異なる。］ The compound of the present invention is a compound represented by formula (I) or formula (I ′) (hereinafter sometimes referred to as compound (I) or compound (I ′), respectively). The compounds of the present invention include tautomers and salts thereof.

[In Formula (I) and Formula (I ′),
L represents a C1-C20 bivalent hydrocarbon group. The methylene group constituting the divalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the divalent hydrocarbon group. The hydrogen atom may be replaced with a cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, chlorine atom, bromine atom, imidazol-1-yl group or amino group.
X represents an oxygen atom, a sulfur atom, or —N (R ¹⁰ ) —.
A represents an aromatic group having 6 to 20 carbon atoms. The hydrogen atom contained in the aromatic group is a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group, amino group, or C1-20. May be replaced by a monovalent hydrocarbon group. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ³ are bonded to each other to form a carbon atom on an adjacent benzene ring. A ring is formed with an atom and an adjacent nitrogen atom, or R ² and R ⁴ are combined to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ^{5 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxy group, a hydroxy group, an amino group, or a monovalent group having 1 to 20 carbon atoms. Represents a hydrocarbon group, R ⁵ and R ⁶ combine to form a ring with adjacent carbon atoms, or R ⁷ and R ⁸ combine to form a ring with adjacent carbon atoms To do. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ¹⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ¹⁰ are present, they are the same or different from each other. ]

Sulfo group, a group represented by -SO ₃ M, carboxy groups, a group represented by -CO ₂ M. M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom, a sodium atom or a potassium atom, more preferably a hydrogen atom.

  Examples of the group represented by L include groups represented by formulas (L1) to (L29), and hydrogen atoms contained in these groups are a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, and a sulfo group. , A carboxy group, a hydroxy group, a chlorine atom, a bromine atom, an imidazol-1-yl group, or a group substituted with an amino group. In formula (L1) to formula (L29), ● represents a bond.

L is preferably a methylene group or a sulfonyl group which may have a substituent.
Specific examples of such preferable L include groups represented by formula (L1) and formula (L3) to formula (L14), respectively. Of these, groups represented by formula (L1), formula (L3), formula (L10), formula (L13) and formula (L14) are preferred, and among them, formula (L1), formula (L3) and formula (L13) And a group represented by the formula (L14) is more preferable. When L is these groups, it is easy to obtain raw materials.

X represents an oxygen atom, a sulfur atom or —N (R ¹⁰ ) —, preferably an oxygen atom and a sulfur atom, and more preferably an oxygen atom. When X is an oxygen atom, the brightness of the green color filter formed from the colored curable resin composition containing the compound of the present invention in which X is an oxygen atom tends to be high.

Examples of the aromatic group having 6 to 20 carbon atoms represented by A include groups represented by formulas (A1) to (A12), and a hydrogen atom contained in these groups is a halogen atom, a cyano group, Examples thereof include a group in which a nitro group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxy group, a hydroxy group, an imidazol-1-yl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms is substituted. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group. Of these, a group represented by the formula (A12) is preferable. The compound of the present invention in which A is a group represented by the formula (A12) tends to have a high thermal decomposition temperature. Further, the sublimation property tends to be low. In the following formulas (A1) to (A12), R ^{1 to} R ⁹ and X are the same as described above, and ● represents a bond to L.

Examples of the halogen atom in R ^{1 to} R ⁹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, a butyl group, Isobutyl, sec-butyl, tert-butyl, (2-ethyl) butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, 3-pentyl, neopentyl, tert-pentyl Group, 1-methylpentyl group, 2-methylpentyl group, 2-pentenyl group, (3-ethyl) pentyl group, hexyl group, isohexyl group, 5-methylhexyl group, (2-ethyl) hexyl group, heptyl group, Aliphatic hydrocarbon groups such as (3-ethyl) heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, okdadecyl group
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethyl Cyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group 2,2,6,6-tetramethyl-cyclohexyl, 3,3,5,5 alicyclic hydrocarbon group, such as tetramethyl cyclohexyl group;
Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, benzyl group, phenethyl group, biphenylyl group, 1- An aromatic hydrocarbon group such as a naphthyl group and a 2-naphthyl group;
And a combination thereof.

A group in which the methylene group constituting these monovalent hydrocarbon groups is replaced with an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the monovalent hydrocarbon group is , A halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxy group, a hydroxy group or an amino group,
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, (2-ethyl) hexyloxy group;
Aryloxy groups such as phenoxy groups;
An aralkyloxy group such as a benzyloxy group;
Alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group;
An acyloxy group such as an acetoxy group or a benzoyloxy group;

N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec-butylcarbamoyl group, N-tert-butylcarbamoyl Group, N-pentylcarbamoyl group, N- (1-ethylpropyl) carbamoyl group, N- (1,1-dimethylpropyl) carbamoyl group, N- (1,2-dimethylpropyl) carbamoyl group, N- (2, 2-dimethylpropyl) carbamoyl group, N- (1-methylbutyl) carbamoyl group, N- (2-methylbutyl) carbamoyl group, N- (3-methylbutyl) carbamoyl group, N-cyclopentylcarbamoyl group, N-hexylcarbamoyl group, N- (1,3-dimethylbutyl) carbonate Vamoyl group, N- (3,3-dimethylbutyl) carbamoyl group, N-heptylcarbamoyl group, N- (1-methylhexyl) carbamoyl group, N- (1,4-dimethylpentyl) carbamoyl group, N-octylcarbamoyl , N-substituted carbamoyl groups such as N- (2-ethylhexyl) carbamoyl group, N- (1,5-dimethyl) hexylcarbamoyl group, N- (1,1,2,2-tetramethylbutyl) carbamoyl group ;
N, N-dimethylcarbamoyl group, N, N-ethylmethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-propylmethylcarbamoyl group, N, N-isopropylmethylcarbamoyl group, N, N-tert-butyl Such as methylcarbamoyl group, N, N-butylethylcarbamoyl group, N, N-bis (1-methylpropyl) carbamoyl group, N, N-heptylmethylcarbamoyl group, N, N-bis (2-ethylhexyl) carbamoyl group, etc. An N, N-2 substituted carbamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group and the like N-1 substituted sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl An N, N-2 substituted sulfamoyl group such as a group, N, N-bis (2-ethylhexyl) sulfamoyl group;

N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino Group, N-pentylamino group, N- (1-ethylpropyl) amino group, N- (1,1-dimethylpropyl) amino group, N- (1,2-dimethylpropyl) amino group, N- (2, 2-dimethylpropyl) amino group, N- (1-methylbutyl) amino group, N- (2-methylbutyl) amino group, N- (3-methylbutyl) amino group, N-cyclopentylamino group, N-hexylamino group, N- (1,3-dimethylbutyl) amino group, N- (3,3-dimethylbutyl) amino group, N-heptylamino group, N- (1-methylhexyl) amino group, N (1,4-dimethylpentyl) amino group, N-octylamino group, N- (2-ethylhexyl) amino group, N- (1,5-dimethyl) hexylamino group, N- (1,1,2,2) -N-alkylamino groups such as tetramethylbutyl) amino group;
N, N-dimethylamino group, N, N-ethylmethylamino group, N, N-diethylamino group, N, N-propylmethylamino group, N, N-isopropylmethylamino group, N, N-tert-butylmethyl N such as amino group, N, N-butylethylamino group, N, N-bis (1-methylpropyl) amino group, N, N-heptylmethylamino group, N, N-bis (2-ethylhexyl) amino group, etc. , N-dialkylamino group;

N-methylaminomethyl group, N-ethylaminomethyl group, N-propylaminomethyl group, N-isopropylaminomethyl group, N-butylaminomethyl group, N-isobutylaminomethyl group, N-sec-butylaminomethyl group N-tert-butylaminomethyl group, N-pentylaminomethyl group, N- (1-ethylpropyl) aminomethyl group, N- (1,1-dimethylpropyl) aminomethyl group, N- (1,2- Dimethylpropyl) aminomethyl group, N- (2,2-dimethylpropyl) aminomethyl group, N- (1-methylbutyl) aminomethyl group, N- (2-methylbutyl) aminomethyl group, N- (3-methylbutyl) Aminomethyl group, N-cyclopentylaminomethyl group, N-hexylaminomethyl group, N- (1,3-dimethylbutyl) a Nomethyl group, N- (3,3-dimethylbutyl) aminomethyl group, N-heptylaminomethyl group, N- (1-methylhexyl) aminomethyl group, N- (1,4-dimethylpentyl) aminomethyl group, N-octylaminomethyl group, N- (2-ethylhexyl) aminomethyl group, N- (1,5-dimethyl) hexylaminomethyl group, N- (1,1,2,2-tetramethylbutyl) aminomethyl group An N-alkylaminomethyl group such as
N, N-dimethylaminomethyl group, N, N-ethylmethylaminomethyl group, N, N-diethylaminomethyl group, N, N-propylmethylaminomethyl group, N, N-isopropylmethylaminomethyl group, N, N -Tert-butylmethylaminomethyl group, N, N-butylethylaminomethyl group, N, N-bis (1-methylpropyl) aminomethyl group, N, N-heptylmethylaminomethyl group, N, N-bis ( N, N-dialkylaminomethyl groups such as 2-ethylhexyl) aminomethyl group;

Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroisopropenyl group, perfluoro (1-propenyl) group, perfluoro (2-propenyl) group, perfluorobutyl group, perfluoroisobutyl group, perfluoro (sec- Butyl) group, perfluoro (tert-butyl) group, perfluoro (2-butenyl) group, perfluoro (1,3-butadienyl) group, perfluoropentyl group, perfluoro (isopentyl) group, perfluoro (3-pentyl) group, perfluoroneo Pentyl group, perfluoro (tert-pentyl) group, perfluoro (1-methylpentyl) group, perfluoro (2-methylpentyl) group, perfluoro (2-pentenyl) group, perfluorohexyl Group, perfluoroisohexyl group, perfluoro (5-methylhexyl) group, perfluoro (2-ethylhexyl) group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, perfluoroundecyl group, perfluorododecyl group, perfluoro An aliphatic hydrocarbon group having a fluorine atom such as an octadecyl group;

Perfluorocyclopropyl group, perfluorocyclobutyl group, perfluorocyclopentyl group, perfluorocyclohexyl group, perfluorocyclohexenyl group, perfluorocycloheptyl group, perfluoro (1-methylcyclohexyl) group, perfluoro (2-methylcyclohexyl) group, perfluoro (3- Methylcyclohexyl) group, perfluoro (4-methylcyclohexyl) group, perfluoro (1,2-dimethylcyclohexyl) group, perfluoro (1,3-dimethylcyclohexyl) group, perfluoro (1,4-dimethylcyclohexyl) group, perfluoro (2 , 3-dimethylcyclohexyl) group, perfluoro (2,4-dimethylcyclohexyl) group, perfluoro (2,5-dimethylcyclohexyl) group, perfluoro (2,6-dimethylcyclohexyl) group, perfluoro (3,4-dimethylcyclohexyl) group, perfluoro (3,5-dimethylcyclohexyl) group, perfluoro (2,2-dimethylcyclohexyl) group, perfluoro (3,3-dimethyl) Cyclohexyl) group, perfluoro (4,4-dimethylcyclohexyl) group, perfluoro (2,4,6-trimethylcyclohexyl) group, perfluoro (2,2,6,6-tetramethylcyclohexyl) group, perfluoro (3,3,3) An alicyclic hydrocarbon group having a fluorine atom such as a 5,5-tetramethylcyclohexyl) group;

Perfluorophenyl group, perfluoro (o-tolyl) group, perfluoro (m-tolyl) group, perfluoro (p-tolyl) group, perfluoroxylyl group, perfluoromesityl group, perfluoro (o-cumenyl) group, perfluoro (m- Cumenyl) group, perfluoro (p-cumenyl) group, perfluorobenzyl group, perfluorophenethyl group, perfluorobiphenylyl group, perfluoro (1-naphthyl) group, perfluoro (2-naphthyl) group, 1-trifluoromethylphenyl group, 2 -An aromatic hydrocarbon group having a fluorine atom such as a trifluoromethylphenyl group, a 3-trifluoromethylphenyl group, or a 4-trifluoromethylphenyl group;

Perfluoromethoxy group, perfluoroethoxy group, perfluoropropoxy group, perfluoro (isopropoxy) group, perfluorobutoxy group, perfluoro (isobutoxy) group, perfluoro (sec-butoxy) group, perfluoro (tert-butoxy) group, perfluoropentyloxy group, Perfluorophenoxy group, perfluorobenzyloxy group, 2,2,2-trifluoroethoxy group, (perfluoroethyl) methoxy group, (perfluoropropyl) methoxy group, (perfluoro (isopropyl)) methoxy group, (perfluoro (isopropenyl)) Methoxy group, (perfluoro (1-propenyl)) methoxy group, (perfluoro (2-propenyl)) methoxy group, (perfluorobutyl) methoxy group, (perfluoro (iso (Til)) methoxy group, (perfluoro (sec-butyl)) methoxy group, (perfluoro (tert-butyl)) methoxy group, (perfluoro (2-butenyl)) methoxy group, (perfluoro (1,3-butadienyl)) methoxy Group, (perfluoropentyl) methoxy group, (perfluoro (isopentyl)) methoxy group, (perfluoro (3-pentyl)) methoxy group, (perfluoro (neopentyl)) methoxy group, (perfluoro (tert-pentyl)) methoxy group, Perfluoro (1-methylpentyl)) methoxy group, (perfluoro (2-methylpentyl)) methoxy group, (perfluoro (2-pentenyl)) methoxy group, (perfluorohexyl) methoxy group, (perfluoro (isohexyl)) methoxy group, (Perful (Ro (5-methylhexyl)) methoxy group, (perfluoro ((2-ethyl) hexyl)) methoxy group, (perfluoroheptyl) methoxy group, (perfluorooctyl) methoxy group, (perfluorononyl) methoxy group, (perfluorodecyl) A substituted oxy group having a fluorine atom such as a methoxy group, a (perfluoroundecyl) methoxy group, a (perfluorododecyl) methoxy group, or a (perfluorooctadecyl) methoxy group;

2,3-bis (trifluoromethyl) phenylmethyl group, 2,4-bis (trifluoromethyl) phenylmethyl group, 2,5-bis (trifluoromethyl) phenylmethyl group, 2,6-bis (trifluoro) And methyl) phenylmethyl group, 3,4-bis (trifluoromethyl) phenylmethyl group, 3,5-bis (trifluoromethyl) phenylmethyl group, and the like.

R ¹ and R ² are preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The hydrogen atom contained in the aliphatic hydrocarbon group may be replaced with an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group may be replaced with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The hydrogen atom contained in the aromatic hydrocarbon group may be replaced with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.

R ¹ is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Among them, an ethyl group, a butyl group, a hexyl group, a (2-ethyl) hexyl group and an octyl group are more preferable, an ethyl group, a butyl group, a hexyl group and a (2-ethyl) hexyl group are more preferable, and (2-ethyl) A hexyl group is particularly preferred. The compound of the present invention in which R ¹ is these groups is excellent in solubility in a solvent.

R ² is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Among them, an ethyl group, a butyl group, a hexyl group, a (2-ethyl) hexyl group and an octyl group are more preferable, an ethyl group, a butyl group, a hexyl group and a (2-ethyl) hexyl group are more preferable, and a hexyl group and (2 -Ethyl) hexyl groups are particularly preferred. The compound of the present invention in which R ² is these groups is excellent in solubility in a solvent.

R ^{3 to} R ⁹ are each preferably a hydrogen atom.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹⁰ include methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, (2-ethyl) butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, 3-pentyl group, neopentyl group, tert-pentyl group, 1 -Methylpentyl group, 2-methylpentyl group, 2-pentenyl group, (3-ethyl) pentyl group, hexyl group, isohexyl group, 5-methylhexyl group, (2-ethyl) hexyl group, heptyl group, (3- Ethyl) aliphatic hydrocarbon groups such as heptyl, octyl, nonyl, decyl, undecyl, dodecyl, okdadecyl;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethyl Cyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group 2,2,6,6-tetramethyl-cyclohexyl, 3,3,5,5 alicyclic hydrocarbon group, such as tetramethyl cyclohexyl group;
Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, benzyl group, phenethyl group, biphenylyl group, 1- An aromatic hydrocarbon group such as a naphthyl group and a 2-naphthyl group;
And a combination thereof.

を「Ｆ」とし、

を「Ｇ」として、化合物（Ｉ）をＦ−Ｇで表す場合、Ｆとしては、式（Ｆ１）〜式（Ｆ２０）で表される基が挙げられる。式中、●は結合手を表す。

Among compounds (I),

To "F"

Is represented by “G” and the compound (I) is represented by FG, examples of F include groups represented by formulas (F1) to (F20). In the formula, ● represents a bond.

Examples of G include groups represented by formula (G1) to formula (G109).

  Specific examples of compound (I) are shown in Tables 1 to 5 as combinations of F and G described above. In Tables 1 to 5, the F column and the G column indicate the numbers of the formulas of the groups exemplified above, respectively.

を「Ｈ」として、化合物（Ｉ’）をＦ−Ｈ−Ｆで表す場合、Ｆとしては、上記式（Ｆ１）〜式（Ｆ２０）で表される基が挙げられ、Ｈとしては、式（Ｈ１）〜式（Ｈ９３）で表される基が挙げられる。式中、●は結合手を表す。 Subsequently, among the compounds (I ′),

Is represented by “H” and the compound (I ′) is represented by F—H—F, examples of F include groups represented by the above formulas (F1) to (F20). And groups represented by H1) to Formula (H93). In the formula, ● represents a bond.

  Specific examples of compound (I ′) are shown in Tables 6 to 22 as combinations of F and H described above. In Tables 6 to 22, the F column and the H column respectively indicate the numbers of the formulas of the groups exemplified above.

  From the viewpoint of obtaining raw materials, the compound (I) is preferably a compound shown in Table 23 to Table 27, and more preferably a compound shown in Table 28 to Table 29.

［式（ｐａ１）及び式（ｐａ２）中、Ｒ^１〜Ｒ^５、Ｒ^７〜Ｒ^９、Ａ、Ｘ及びＬは、それぞれ上記と同じ意味を表す。］ As a manufacturing method of compound (I), it can manufacture according to the method described in Dyes and Pigments (2008), 77, 556-558, for example. Specifically, the compound represented by the formula (pa1), the compound represented by the formula (pa2), and ethyl cyanoacetate can be produced by cyclization reaction in the presence of benzoic acid and a solvent. The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 100 ° C to 150 ° C. The reaction time is preferably 1 hour to 24 hours, more preferably 8 hours to 18 hours, and further preferably 8 hours to 16 hours. Examples of the solvent include methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol and N-methylpyrrolidone, with 1-pentanol being preferred.

[In Formula (pa1) and Formula (pa2), R ^{1 to} R ⁵ , R ^{7 to} R ⁹ , A, X, and L each have the same meaning as described above. ]

  In the production of compound (I), the amount of the compound represented by formula (pa1) is usually 1 mol to 10 mol, preferably 1 mol, relative to 1 mol of compound represented by formula (pa2). ˜2 mol, more preferably 1 mol.

  In the production of compound (I), the amount of ethyl cyanoacetate used is usually 1 mol to 10 mol, preferably 1 mol to 2 mol, relative to 1 mol of the compound represented by formula (pa2). More preferably, it is 1 mol.

  In the production of compound (I), the amount of benzoic acid to be used is generally 0.3 mol to 3 mol, preferably 0.3 mol to 0.00 mol, per 1 mol of the compound represented by formula (pa2). 6 mol, more preferably 0.3 mol to 0.4 mol.

［式（ｐａ３）中、Ｒ^７〜Ｒ^９、Ｘ及びＬは、それぞれ上記と同じ意味を表す。］ Compound (I ′) can be produced by cyclizing the compound represented by the above formula (pa1), the compound represented by the formula (pa3) and ethyl cyanoacetate in the presence of benzoic acid and a solvent. it can. The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 100 ° C to 150 ° C. The reaction time is preferably 1 hour to 24 hours, more preferably 8 hours to 18 hours, and further preferably 8 hours to 16 hours. Examples of the solvent include methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol and N-methylpyrrolidone, and 1-pentanol is preferable.

[In the formula (pa3), R ^{7 to} R ⁹ , X and L each have the same meaning as described above. ]

  In the production of the compound (I ′), the amount of the compound represented by the formula (pa1) is usually 2 mol or more and 20 mol or less, preferably 1 mol or less, preferably 1 mol of the compound represented by the formula (pa3). It is 2 mol-4 mol, More preferably, it is 2 mol.

  In the production of compound (I ′), the amount of ethyl cyanoacetate used is usually 2 to 20 mol, preferably 2 to 4 mol, relative to 1 mol of the compound represented by formula (pa3). More preferably 2 moles.

  In the production of compound (I ′), the amount of benzoic acid to be used is generally 0.6 mol to 6 mol, preferably 0.6 mol to 1 mol, relative to 1 mol of the compound represented by formula (pa3). .2 moles, more preferably 0.6 moles to 0.7 moles.

  The method for obtaining the target compound (I) or compound (I ′) of the present invention from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, it is preferable to appropriately adjust the temperature of the reaction mixture to precipitate crystals and to remove the crystals by filtration. The extracted crystal is washed with water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene or a mixed solution thereof. Then, it is preferable to dry. If necessary, dissolve in acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, chloroform or a mixed solution thereof. It may be further purified by a known method such as a drying method or recrystallization after washing with an aqueous sodium hydroxide solution.

  The dye of the present invention contains compound (I) or compound (I ′) as an active ingredient. The dye of the present invention may be a dye comprising only compound (I) or compound (I ′), or may contain a dye described later. The dye of the present invention contains compound (I) or compound (I ′) in a proportion of preferably 70% by mass to 100% by mass, more preferably 80% by mass to 100% by mass.

  The dye of the present invention is useful as a dye contained in a colored photosensitive resin composition used for a color filter of a display device such as a liquid crystal display device.

The colored curable resin composition of the present invention includes a colorant (AA), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorant (AA) includes compound (I) or compound (I ′).
The colored curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E) and a leveling agent (FF).

The colored curable resin composition of the present invention may further contain a polymerization initiation assistant (D1).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (AA)>
The colorant (AA) may further contain a dye and / or pigment different from the compound (I) or the compound (I ′) in addition to the compound (I) or the compound (I ′).

As dyes other than Compound (I) or Compound (I ′), Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, Reactive (Reactive), Direct (Dis), Disperse (Disperse) or a compound classified into bat (Vat). More specifically, dyes having the following color index (CI) numbers can be mentioned, but the dye is not limited thereto.
C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54,76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Green 1,5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1.

  The colorant (AA) preferably contains the compound (I) or the compound (I ′), and further contains the pigment (P).

  As the pigment (P), a known pigment can be used. Specifically, pigments classified as Pigment in the Color Index (published by The Society of Dyers and Colorists) can be used. Can be mentioned.

As a pigment,
C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 180, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38;
C. I. Green pigments such as CI Pigment Green 7, 10, 15, 25, 36, 47, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

The pigment (P) is preferably a phthalocyanine pigment, more preferably at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment, and more preferably C.I. I. It is at least one selected from the group consisting of CI Pigment Green 7, 36 and 58. These pigments are suitably used for green pigments, and by including the above-mentioned pigments, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.
[0122]
If necessary, the pigment can be atomized by 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 atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The pigments preferably have a uniform particle size.
The pigment can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.
[0123]
Examples of pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), and Ajispur (Ajinomoto Fine). (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion having a more uniform dispersion state tends to be obtained.

When the colorant (AA) contains, in addition to the compound (I) or the compound (I ′), a dye and / or pigment different from the compound (I) or the compound (I ′), the compound (I) or the compound (I The content of ') is preferably 1% by mass or more and 100% by mass or less, more preferably 3% by mass or more and 100% by mass or less, and further preferably 3% by mass with respect to the total amount of the colorant (AA). % To 70% by mass, particularly preferably 3% to 60% by mass.
When the pigment (P) is contained, the content of the pigment (P) is usually 1% by mass to 99% by mass, preferably 1% by mass to 97% by mass with respect to the total amount of the colorant (AA). More preferably, it is 30 mass% or more and 97 mass% or less, More preferably, it is 40 mass% or more and 97 mass% or less.
The content of the colorant (AA) is preferably 1% by mass or more and 70% by mass or less, more preferably 1% by mass or more and 60% by mass or less, and further preferably 5% by mass with respect to the total amount of the solid content. % To 60% by mass, particularly preferably 5% to 50% by mass. When the content of the colorant (AA) is within the above range, it becomes easier to obtain a desired spectrum and color density.

  In addition, in this specification, "the total amount of solid content" means the total amount of the component remove | excluding the solvent (E) from the colored curable resin composition of this invention. 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 not limited, but is preferably an alkali-soluble resin, and more preferably an addition polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. . Examples of such resins 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)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with a monomer (b) having 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.

As a specific example of (a),
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, 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.

Examples of (b) include polymerizable compounds having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. And a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferred.
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.

(B)
Monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter “ (B2) "in some cases), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as" (b3) "), and the like.

(B1)
Monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-1)”), an alicyclic group And a monomer (b1-2) having a structure in which a saturated hydrocarbon is epoxidized (hereinafter may be 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.

  (B1-2) includes vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, formula ( The compound represented by 1) and the compound represented by Formula (2) are mentioned.

［式（１）及び式（２）中、Ｒ^ａ及びＲ^ｂは、水素原子、又は炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｘ^ａ及びＸ^ｂは、単結合、−Ｒ^ｃ−、＊−Ｒ^ｃ−Ｏ−、＊−Ｒ^ｃ−Ｓ−又は＊−Ｒ^ｃ−ＮＨ−を表す。
Ｒ^ｃは、炭素数１〜６のアルカンジイル基を表す。
＊は、Ｏとの結合手を表す。］

[In Formula (1) and Formula (2), 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 a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, 1- Examples thereof include a hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

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

  As a compound represented by Formula (1), the compound represented by either of Formula (1-1)-Formula (1-15) is mentioned. Among them, Formula (1-1), Formula (1-3), Formula (1-5), Formula (1-7), Formula (1-9), Formula (1-11) to Formula (1-15) The compound represented by Formula (1-1), Formula (1-7), Formula (1-9), or the compound represented by Formula (1-15) is more preferable.

  As a compound represented by Formula (2), the compound represented by either of Formula (2-1)-Formula (2-15) is mentioned. Among them, the formula (2-1), the formula (2-3), the formula (2-5), the formula (2-7), the formula (2-9), or the formula (2-11) to the formula (2-15). The compound represented by Formula (2-1), Formula (2-7), Formula (2-9) or Formula (2-15) is more preferable.

  Even if the compound represented by Formula (1) and the compound represented by Formula (2) are each used independently, the compound represented by Formula (1) and the compound represented by Formula (2) are used in combination. May be. When these are used in combination, the content ratio of the compound represented by the formula (1) and the compound represented by the formula (2) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

  (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.

(C)
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8- Yl (meth) acrylate (in the art, it is referred to as “dicyclopentanyl (meth) acrylate” as a common name. It may also be referred to as “tricyclodecyl (meth) acrylate”), tricyclo [5 .2.1.0 ^2,6 ] Decen-8-yl (meth) acrylate (in this technical field, it is called "dicyclopentenyl (meth) acrylate" as a common name), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) (Meth) acrylic acid esters such as acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

  Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

  Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N from the viewpoint of copolymerization reactivity and heat resistance. -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

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 mol% to 60 mol%
Structural unit derived from (b); 40 mol% to 98 mol%
It is preferable that
Structural unit derived from (a); 10 mol% to 50 mol%
Structural unit derived from (b); 50 mol% to 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 more improved. It tends to be excellent.

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

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are 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 in the resin [K2]
Structural unit derived from (a); 2 mol% to 45 mol%
Structural unit derived from (b); 2 mol% to 95 mol%
Structural unit derived from (c); 1 mol% to 65 mol%
It is preferable that
Structural unit derived from (a); 5 mol% to 40 mol%
Structural unit derived from (b); 5 mol% to 80 mol%
Structural unit derived from (c); 5 mol% 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, Heat resistance and mechanical strength tend to be more excellent.

  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 mol% to 60 mol%
Structural unit derived from (c); 40 mol% to 98 mol%
It is preferable that
Structural unit derived from (a); 10 mol% to 50 mol%
Structural unit derived from (c); 50 mol% to 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 at, for example, 60 ° C. to 130 ° C. for 1 hour to 10 hours to produce resin [K4]. be able to.
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 in 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 to be. 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 mol% to 95 mol%
Structural unit derived from (c); 5 mol% to 95 mol%
It is preferable that
Structural unit derived from (b); 10 mol% to 90 mol%
Structural unit derived from (c); 10 mol% 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.
The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol per 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 mol-1 mol are preferable with respect to 1 mol of usage-amounts 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 (meth) acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3- menu Resin such as ru-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) Acrylic acid copolymer, resin such as benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer A resin in which glycidyl (meth) acrylate is added to a resin, a resin in which glycidyl (meth) acrylate is added to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / Benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate Resin [K4] such as a resin to which a relate is added; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / Resin such as a resin obtained by reacting a copolymer of styrene / glycidyl (meth) acrylate with (meth) acrylic acid [K5]; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) Examples thereof include a resin [K6] such as a resin obtained by reacting acrylic acid with a resin further reacted with tetrahydrophthalic anhydride.

  The resin (B) is preferably a kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], and more preferably from a group consisting of a resin [K2] and a resin [K3]. It is the kind chosen. When these resins are used, the colored curable resin composition is excellent in developability. Resin [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.

The weight average molecular weight in terms of polystyrene of the resin (B) is usually from 3,000 to 100,000, preferably from 5,000 to 50,000, more preferably from 5,000 to 35,000, Preferably it is 5,000-30,000, Most preferably, it is 6,000-30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B) is usually 20 mg-KOH / g to 170 mg-KOH / g, preferably 30 mg-KOH / g to 170 mg-KOH / g, more preferably 40 mg-KOH / g to 170 mg. -KOH / g, more preferably 50 mg-KOH / g to 170 mg-KOH / g. Among them, 50 mg-KOH / g to 150 mg-KOH / g are preferable, 60 mg-KOH / g to 150 mg-KOH / g are more preferable, 60 mg-KOH / g to 135 mg-KOH / g are further preferable, and 70 mg-KOH / g. -135 mg-KOH / g is particularly preferred. 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.

  The content of the resin (B) is preferably 7% by mass to 65% by mass, more preferably 10% by mass to 60% by mass, and still more preferably 13% by mass to 60% by mass with respect to the total amount of the solid content. It is mass%, Most preferably, it is 17 mass%-55 mass%. When the content of the resin (B) is in the above range, a colored pattern can be easily formed, and the resolution and remaining film ratio of the colored pattern tend to be improved.

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

  Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. And the above-mentioned (a), (a) and (c).

  Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

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 150 or more and 2,900 or less, more preferably 150 or more and 1,500 or less, further preferably 150 or more and 800, and particularly preferably 190 or more and 700. It is as follows.

The content of the polymerizable compound (C) is preferably 5% by mass to 65% by mass, more preferably 7% by mass to 65% by mass with respect to the total amount of the solid content, and 10% by mass to It is more preferably 60% by mass, particularly preferably 13% by mass to 60% by mass, and particularly preferably 17% by mass to 55% by mass.
Further, the content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 35: 65-80: 20.
When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

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

The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

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

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

  Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholino Phenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, and the like. Can be mentioned. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxy Ethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone, Examples include benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

［式（ｄ５）中、Ｒ^５１〜Ｒ^５６は、置換基を有していてもよい炭素数６〜１０のアリール基を表す。］ The biimidazole compound is, for example, a compound represented by the formula (d5).

[In formula (d5), R ^{51 to} R ⁵⁶ represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

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

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole (see, for example, JPH06-75372-A, JPH06-75373-A), 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 (trialkoxyphenyl) biimidazole (for example, , JPS48-38403-B, JPS62-174204-A etc.) 4,4'5,5'- position of the imidazole compound in which the phenyl group is substituted by carbalkoxy group (e.g., JPH07-10913-A, etc. See), and the like. Among these, compounds represented by the following formula and mixtures thereof are preferable.

  As triazine compounds, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) 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.

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

  The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably. Is a polymerization initiator containing an O-acyloxime compound.

  The content of the polymerization initiator (D) is preferably 0.1 parts by mass to 40 parts by mass, more preferably 0 with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 30 parts by mass, and particularly preferably 1 part by mass to 20 parts by mass.

<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 amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

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

  When using 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). More preferably, it is 1 mass part-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.

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

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

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

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

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

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

  These solvents may be used alone or in combination of two or more.

  Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and N-methylpyrrolidone are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene Glycol methyl ether acetate, ethyl lactate, 3-methoxy Chill acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and N- methylpyrrolidone is more preferred.

  The content of the solvent (E) is preferably 70% by mass to 95% by mass, more preferably 75% by mass to 92% by mass, and still more preferably 75% with respect to the total amount of the colored curable resin composition. It is mass%-90 mass%. In other words, the solid content of the colored curable resin composition is preferably 5% by mass to 30% by mass, more preferably 8% by mass to 25% by mass, and even more preferably 10% by mass to 25% by mass. preferable. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

<Leveling agent (FF)>
Examples of the leveling agent (FF) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

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

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

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 mentioned.
[0199]
The content of the leveling agent (FF) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.000% by mass or more based on the total amount of the colored curable resin composition. 1 mass% or less, More preferably, it is 0.005 mass% or more and 0.07 mass% or less. When the leveling agent (FF) content 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 (AA), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. It can be prepared by mixing a leveling agent (FF), a polymerization initiation assistant (D1) and other components.
The pigment in the case of containing the pigment (P) 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.
It is preferable to prepare a solution by dissolving Compound (I) in part or all of the solvent solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 μm to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 μm 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 appropriately adjusted according to the purpose and application, for example, 0.1 μm to 30 μm, preferably 0.1 μm to 20 μm, more preferably 0.5 μm. ~ 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.
The temperature when performing heat drying is preferably 30 ° C to 120 ° C, more preferably 50 ° C to 110 ° C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing drying under reduced pressure, it is preferable to carry out under a pressure of 50 Pa to 150 Pa in a temperature range of 20 ° C to 25 ° C.
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.
As the light source used for exposure, a light source that generates light having a wavelength of 250 nm to 450 nm is preferable. 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 0.02 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 ° C to 250 ° C, more preferably 160 ° C to 235 ° C. The post-bake time is preferably 1 minute to 120 minutes, and more preferably 10 minutes to 60 minutes.

  According to the colored curable resin composition of the present invention, a color filter having particularly high 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.

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

  In the following synthesis examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) or mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

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

Synthesis example 1
10.6 parts of bis (3-amino-4-hydroxyphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 14.6 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid ( 3.17 parts of Tokyo Chemical Industry Co., Ltd.), 183 parts of 1-pentanol (Tokyo Chemical Industry Co., Ltd.) and 8.61 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) were mixed. Stir at 0 ° C. for 3 hours. To this reaction solution, 14.6 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.17 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) )) 8.61 parts were added and stirred at 120 ° C. for 12 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. After adding 236 parts of acetonitrile and 234 parts of isopropyl alcohol to this residue and stirring, an insoluble matter was obtained as a residue of a suction filter. After adding 236 parts of acetonitrile and 234 parts of isopropyl alcohol to this residue and stirring, an insoluble matter was obtained as a residue of a suction filter. To this residue, 2220 parts of chloroform was added, stirred and filtered. To this filtrate, 530 parts of a 5% aqueous sodium hydroxide solution was added and stirred, and the chloroform solution layer was taken out. To this chloroform solution, 610 parts of an 18% aqueous sodium chloride solution was added and stirred, and the chloroform solution layer was taken out. To this chloroform solution, 10 parts of magnesium sulfate was added and stirred, followed by filtration. After the solvent of the filtrate was distilled off with a rotary evaporator, the filtrate was dried under reduced pressure at 60 ° C. to obtain 19.5 parts of a compound represented by the formula (I-148). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-148)>
¹ H-NMR (500 MHz, DMSO-d ₆ ): 1.14 (12H, t), 3.50 (8H, q), 6.61 (2H, d), 6.82 (2H, dd), 7 .71 (2H, d), 7.95 (2H, d), 8.04 (2H, dd), 8.43 (2H, d), 8.83 (2H, s)

Synthesis example 2
10.1 parts of bis (3-amino-4-hydroxyphenyl) dimethylmethane (manufactured by Changzhou Yoko Pharmaceutical Raw Materials Co., Ltd.), 15.2 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), Benzo 3.26 parts of acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 191 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.89 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed. , And stirred at 120 ° C. for 3 hours. In this reaction solution, 4- (diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) 8.39 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) 1.80 parts, 1-pentanol (Tokyo Chemical Industry ( Ltd.) 8.40 parts and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 4.91 parts were added and stirred at 120 ° C. for 12 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. After adding 332 parts of acetonitrile to this residue and stirring, an insoluble material was obtained as a residue of a suction filter. After adding 315 parts of acetonitrile to this residue and stirring, an insoluble material was obtained as a residue of a suction filter. This residue was dried under reduced pressure at 60 ° C. to obtain 23.6 parts of a compound represented by the formula (I-169). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-169)>
¹ H-NMR (500 MHz, DMSO-d ₆ ): 1.14 (12H, t), 1.80 (6H, s), 3.49 (8H, q), 6.60 (2H, d), 6 .81 (2H, dd), 7.19 (2H, dd), 7.59 (2H, d), 7.67 (2H, d), 7.68 (2H, d), 8.75 (2H, s)

Synthesis example 3
Bis (3-amino-4-hydroxyphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.57 parts, 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.89 parts, benzoic acid 1.67 parts (manufactured by Tokyo Chemical Industry Co., Ltd.), 96.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.52 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) And stirred at 120 ° C. for 3 hours. To this reaction solution, 9.97 parts of 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.71 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 20 parts) and 4.52 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) were added and stirred at 120 ° C. for 12 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. After adding 600 parts of isopropyl alcohol to this residue and stirring, an insoluble matter was obtained as a residue of a suction filter. This residue was dried under reduced pressure at 60 ° C. to obtain 14.2 parts of a compound represented by the formula (I-149). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-149)>
¹ H-NMR (500 MHz, CDCl ₃ ): 0.98 (12H, t), 1.39 (8H, qt), 1.62 (8H, tt), 3.37 (8H, t), 6.50 (2H, d), 6.63 (2H, dd), 7.41 (2H, d), 7.67 (2H, d), 7.96 (2H, dd), 8.39 (2H, d) , 8.62 (2H, s)

Synthesis example 4
1.29 parts of bis (3-amino-4-hydroxyphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 4- (bis (2-ethylhexyl) amino) salicylaldehyde (a method described in JP-T-2007-508275) 3.31 parts), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.385 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.3 parts and ethyl cyanoacetate (Tokyo) 1.06 part (made by Kasei Kogyo Co., Ltd.) was mixed and stirred at 120 ° C. for 3 hours. To this reaction solution, 3.29 parts of 4- (bis (2-ethylhexyl) amino) salicylaldehyde (synthesized according to the method described in JP-T-2007-508275), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.406 parts, 11.9 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.04 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 120 ° C. for 12 hours. The reaction solution was cooled to room temperature, added to 450 parts of methanol, and a precipitate was obtained by removing the supernatant. To the precipitate, 5.00 parts of acetone was added and stirred at 55 ° C. to prepare a solution. To this solution, 50.1 parts of methanol was added and stirred at 55 ° C. After cooling the mixture to room temperature, a precipitate was obtained by removing the supernatant. To the precipitate, 5.00 parts of acetone was added and stirred at 55 ° C. to prepare a solution. To this solution, 50.0 parts of methanol was added and stirred at 55 ° C. After cooling the mixture to room temperature, a precipitate was obtained by removing the supernatant. A solution was prepared by adding 23.0 parts of N, N-dimethylformaldehyde to the precipitate. This solution was added to 281 parts of 18% brine and stirred, and the precipitated crystals were obtained as a residue of suction filtration. To this residue, 200 parts of water was added and stirred to obtain an insoluble material as a residue of suction filtration. This residue was dried under reduced pressure at 60 ° C. to obtain 3.00 parts of a compound represented by the formula (I-156). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-156)>
¹ H-NMR (500 MHz, DMSO-d ₆ ): 0.83 (12H, t), 0.83 (12H, t), 1.22 (8H, qt), 1.22 (8H, tt), 1 .27 (8H, td), 1.28 (8H, qd), 1.74 (4H, ttt), 3.37 (8H, d), 6.55 (2H, d), 6.79 (2H, dd), 7.67 (2H, d), 7.93 (2H, d), 8.03 (2H, dd), 8.41 (2H, d), 8.79 (2H, s)

Synthesis example 5
Bis (3-amino-4-hydroxyphenyl) dimethylmethane (manufactured by Changzhou Yoko Pharmaceutical Raw Materials Co., Ltd.) 5.96 parts, 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 11.6 parts, 1.97 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 114 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.24 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed. And stirred at 120 ° C. for 3 hours. To this reaction solution, 5.67 parts of 4- (dibutylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.), 0.988 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.) and ethyl cyanoacetate (Tokyo Chemical Industry ( 2.59 parts manufactured by the same company) was added and stirred at 120 ° C. for 12 hours. The reaction solution was cooled to room temperature, added to 1750 parts of hexane, and the precipitated crystals were obtained as a residue of suction filtration. To this residue was added 413 parts of tetrahydrofuran, and the mixture was stirred at 60 ° C., cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. To this residue, 308 parts of acetonitrile was added, stirred at 80 ° C., cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. This residue was dried under reduced pressure at 60 ° C. to obtain 14.5 parts of a compound represented by the formula (I-170). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-170)>
¹ H-NMR (500 MHz, CDCl ₃ ): 0.98 (12H, t), 1.37 (8H, qt), 1.61 (8H, tt), 1.80 (6H, s), 3.35 (8H, t), 6.50 (2H, d), 6.63 (2H, dd), 7.11 (2H, dd), 7.39 (2H, d), 7.42 (2H, d) , 7.81 (2H, d), 8.59 (2H, 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 for 20 hours while removing water produced at 150 to 155 ° C. After allowing to cool, the reaction mixture was dissolved in 433 parts of toluene, and this toluene solution was washed 3 times with 1000 parts of warm water. 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.) 3.20 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.), 90.0 of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) Parts and 8.59 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) were 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. This residue was purified by column chromatography to obtain 20.6 parts of a compound represented by the formula (I-157). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-157)>
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
1.94 parts of bis (3-amino-4-hydroxyphenyl) dimethylmethane (manufactured by Changzhou Yoko Pharmaceutical Raw Materials Co., Ltd.), 5.03 parts of a compound represented by the formula (pt3), benzoic acid (Tokyo Chemical Industry Co., Ltd.) )) 0.635 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 36.0 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.74 parts, mixed at 120 ° C. 3 Stir for hours. In this solution, 2.52 parts of the compound represented by the formula (pt3), 0.325 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) And 0.865 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) was added, and it stirred at 120 degreeC for 12 hours. The reaction solution was cooled to room temperature and added to 603 parts of methanol. A precipitate was obtained by removing the supernatant. To this precipitate, 7.10 parts of acetone was added and stirred at 55 ° C. to prepare a solution. To this solution, 73.6 parts of methanol was added and stirred at 55 ° C. After cooling the mixture to room temperature, a precipitate was obtained by removing the supernatant. To this precipitate, 6.20 parts of acetone was added and stirred at 55 ° C. to prepare a solution. To this solution, 65.2 parts of methanol was added and stirred at 55 ° C. After cooling the mixture to room temperature, a precipitate was obtained by removing the supernatant. To this precipitate, 30.1 parts of N, N-dimethylformamide was added and dissolved. This solution was added to 360 parts of 18% brine and stirred, and the precipitated crystals were obtained as a residue of suction filtration. To this residue, 350 parts of water was added and stirred to obtain insoluble matter as a residue of suction filtration. This residue was dried under reduced pressure at 60 ° C. to obtain 4.10 parts of a compound represented by the formula (I-178). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-178)>
¹ H-NMR (500 MHz, DMSO-d ₆ ): 0.86 (6H, t), 0.87 (6H, t), 0.88 (6H, t), 1.20 to 1.40 (28H) , 1.57 (4H, tt), 1.76 (2H, ttt), 1.81 (6H, s), 3.34 (4H, d), 3.43 (4H, t), 6.55 ( 2H, d), 6.78 (2H, dd), 7.22 (2H, dd), 7.56 (2H, d), 7.62 (2H, d), 7.65 (2H, d), 8.67 (2H, s)

Synthesis Example 8
64.5 parts of 2-ethylhexylamine was added to 138 parts of resorcinol, and this mixture was stirred for 18 hours while removing water formed at 150 ° C to 155 ° C. After allowing to cool, 250 parts of toluene was added to the reaction mixture, and the mixture was washed 3 times with 500 parts of warm water. 20.0 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 113 parts of a residue containing the compound represented by the formula (pt4) as a main component.

<Identification of compound represented by formula (pt4)>
(Mass Spectrometry) ionization mode = ESI +: m / z = [M + H] + 222.2
Exact Mass: 221.2

28.5 parts of water was added to 58.5 parts of the residue containing the compound represented by the formula (pt4) as a main component, and the liquid temperature was adjusted to 60 ° C. while stirring. At this temperature, 39.3 parts of diethyl sulfate and 10.6 parts of 48% aqueous sodium hydroxide solution were added and stirred for 9 hours. Then, it stirred at 60 degreeC for 5 hours. After allowing to cool, the reaction mixture was neutralized with a 10% aqueous sodium hydroxide solution, and 300 parts of toluene was added. This toluene solution was washed three times with 500 parts of warm water. 20.0 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 67.5 parts of a residue containing the compound represented by the formula (pt5) as a main component.

<Identification of compound represented by formula (pt5)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 250.2
Exact Mass: 249.2

To 67.5 parts of the residue containing the compound represented by the formula (pt5) as a main component, 323 parts of N, N-dimethylformamide was added. While maintaining the temperature of this mixed solution at -6 ° C to 4 ° C, 105 parts of phosphorus oxychloride was added. The temperature of the reaction solution was returned to room temperature and stirred for 1 hour, and then the temperature of the reaction solution was raised to 60 ° C. and stirred for 3 hours. After allowing to cool, the reaction mixture was added to 1500 parts of ice water, and neutralized by adding a 48% aqueous sodium hydroxide solution while stirring. 500 parts of toluene was added to this, and the toluene layer was extracted. This toluene solution was washed with 1000 parts of water. Next, this toluene solution was washed with 1500 parts of a saturated aqueous sodium chloride solution. To this toluene solution, 25.0 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. The filtrate was evaporated to give a residue. This residue was purified by column chromatography to obtain 36.7 parts of a compound represented by the formula (pt6).

<Identification of compound represented by formula (pt6)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 278.2
Exact Mass: 277.2

15.7 parts of bis (3-amino-4-hydroxyphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 31.0 parts of a compound represented by the formula (pt6), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 4.66 parts, 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 270 parts and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd. 12.6 parts) were mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 31.1 parts of a compound represented by the formula (pt6), 4.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.0 of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) Parts and 12.6 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. for 12 hours. The reaction solution was cooled to room temperature, added to 2100 parts of methanol, and the precipitated crystals were obtained as a residue of suction filtration. This residue was purified by column chromatography to obtain 26.6 parts of a compound represented by the formula (I-158).

<Identification of Compound Represented by Formula (I-158)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 899.4
Exact Mass: 898.4

Synthesis Example 9
8.56 parts of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.0 parts of the compound represented by the formula (pt3), benzoic acid (Tokyo Chemical Industry Co., Ltd.) 1.87 parts of 1) -pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.09 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed at 120 ° C. Stir for hours. In this reaction solution, 15.0 parts of the compound represented by the formula (pt3), 1.88 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 Parts and 5.09 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. for 12 hours. The reaction solution was cooled to room temperature, added to 860 parts of methanol, and the precipitated crystals were obtained as a residue of suction filtration. This residue was purified by column chromatography to obtain 13.7 parts of a compound represented by the formula (I-242).

<Identification of compound represented by formula (I-242)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 1111.6
Exact Mass: 1110.6

Synthesis Example 10
160 parts of bromine in a solution of 103 parts of bis (3-aminophenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 208 parts of potassium thiocyanate (manufactured by Sigma Aldrich Japan Co., Ltd.) in 510 parts of glacial acetic acid Was dissolved in 27.1 parts of glacial acetic acid dropwise over 1 hour under stirring conditions. Stirring was continued for another 2 hours after the completion of dropping, and then left overnight. 1740 parts of water was added thereto, heated to the boiling point, then cooled and filtered. Sodium hydrogen carbonate was added to the filtrate, and the resulting precipitate was filtered, washed with water, and dried. This precipitate was purified by column chromatography to obtain 30.1 parts of a compound represented by the formula (pt7).

<Identification of Compound Represented by Formula (pt7)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 363.0
Exact Mass: 362.0

Under an argon atmosphere, to a compound (60.0 parts) represented by the formula (pt7), a 3.00M aqueous potassium hydroxide solution was added at room temperature in an amount of 53.8 mL per gram of the compound represented by the formula (pt7). It was. To this mixture, 141 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred for 30 hours while refluxing. The reaction solution was cooled to room temperature and then neutralized with 2.00N hydrochloric acid. 1740 parts of ethyl acetate was added thereto, and the ethyl acetate layer was extracted. The solvent was distilled off to obtain a residue. To this residue, 688 parts of N, N-dimethylformamide was added to obtain a solution. To this solution, a solution prepared by dissolving 64.2 parts of DL-dithiothreitol in 729 parts of water was added and stirred at room temperature for 2 hours. To this reaction solution, an aqueous solution obtained by mixing a 0.500M acetic acid aqueous solution and a 0.500M sodium acetate aqueous solution in a volume ratio of 1: 2 was added in the same volume as the N, N-dimethylformamide added previously. Subsequently, 1310 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. To this aqueous layer, 1310 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. The ethyl acetate layers were combined and the solvent of the solution was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 5.04 parts of a compound represented by the formula (pt8).

<Identification of compound represented by formula (pt8)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 313.0
Exact Mass: 312.0

6.56 parts of the compound represented by the formula (pt8), 14.0 parts of the compound represented by the formula (pt3), 1.75 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo) 101 parts of Kasei Kogyo Co., Ltd. and 4.75 parts of ethyl cyanoacetate (Tokyo Kasei Kogyo Co., Ltd.) were mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 14.1 parts of a compound represented by the formula (pt3), 1.75 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.00 Parts and 4.74 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. for 12 hours. After cooling said reaction liquid to room temperature, the solvent was distilled off and the residue was obtained. This residue was purified by column chromatography to obtain 1.75 parts of the compound represented by the formula (I-320).

<Identification of Compound Represented by Formula (I-320)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 1043.5
Exact Mass: 1042.5

Synthesis Example 11
101 parts of 2,2-bis (3-aminophenyl) propane (synthesized according to the method described in Justus Liebigs Annalen der Chemie 1933, 507, 14 or Bulletin de la Societe Chimique de France 1974, 641) and thiocyanic acid A solution in which 224 parts of potassium (manufactured by Sigma Aldrich Japan Co., Ltd.) was dissolved in 549 parts of glacial acetic acid and 173 parts of bromine in 29.2 parts of glacial acetic acid was stirred for 1 hour under stirring conditions. It was dripped. Stirring was continued for another 2 hours after the completion of dropping, and then left overnight. 1870 parts of water was added thereto, heated to the boiling point, then cooled and filtered. Sodium hydrogen carbonate was added to the filtrate, and the resulting precipitate was filtered, washed with water, and dried. This precipitate was purified by column chromatography to obtain 22.0 parts of a compound represented by the formula (pt9).

<Identification of Compound Represented by Formula (pt9)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 341.1
Exact Mass: 340.1

Under an argon atmosphere, 35.0 parts of the compound represented by the formula (pt9) are mixed with a 3.00M potassium hydroxide aqueous solution at a room temperature of 57.3 mL per 1.00 g of the compound represented by the formula (pt9). Added in. To this mixture, 87.3 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred for 34 hours while refluxing. The reaction solution was cooled to room temperature and then neutralized with 2.00N hydrochloric acid. To this was added 1080 parts of ethyl acetate, and the ethyl acetate layer was extracted. The solvent was distilled off to obtain a residue. To this residue, 427 parts of N, N-dimethylformamide was added to obtain a solution. To this solution, a solution prepared by dissolving 39.8 parts of DL-dithiothreitol in 453 parts of water was added and stirred at room temperature for 2 hours. To this reaction solution, an aqueous solution obtained by mixing a 0.500M acetic acid aqueous solution and a 0.500M sodium acetate aqueous solution in a volume ratio of 1: 2 was added in the same volume as the N, N-dimethylformamide added previously. Subsequently, 812 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. To this aqueous layer, 812 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. The ethyl acetate layers were combined and the solvent of the solution was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 3.43 parts of a compound represented by the formula (pt10).

<Identification of Compound Represented by Formula (pt10)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 291.1
Exact Mass: 290.1

6.53 parts of the compound represented by the formula (pt10), 15.0 parts of the compound represented by the formula (pt3), 1.87 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo) 108 parts of Kasei Kogyo Co., Ltd. and 5.09 parts of ethyl cyanoacetate (Tokyo Kasei Kogyo Co., Ltd.) were mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 15.0 parts of the compound represented by the formula (pt3), 1.90 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 9.00 of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) Part and 5.10 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. for 12 hours. After cooling said reaction liquid to room temperature, the solvent was distilled off and the residue was obtained. This residue was purified by column chromatography to obtain 2.53 parts of a compound represented by the formula (I-341).

<Identification of Compound Represented by Formula (I-341)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 1021.6
Exact Mass: 1020.6

Synthesis Example 12
In a solution prepared by dissolving 100 parts of 3,3′-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 253 parts of potassium thiocyanate (manufactured by Sigma Aldrich Japan Co., Ltd.) in 620 parts of glacial acetic acid, 195 parts of bromine were added. A solution dissolved in 33.0 parts of glacial acetic acid was added dropwise over 1 hour under stirring conditions. Stirring was continued for another 2 hours after the completion of dropping, and then left overnight. 2110 parts of water was added thereto, heated to the boiling point, then cooled and filtered. Sodium hydrogen carbonate was added to the filtrate, and the resulting precipitate was filtered, washed with water, and dried. This precipitate was purified by column chromatography to obtain 20.1 parts of a compound represented by the formula (pt11).

<Identification of Compound Represented by Formula (pt11)>
(Mass Spectrometry) Ionization Mode = ESI +: m / z = [M + H] ⁺ 313.1
Exact Mass: 312.1

Under an argon atmosphere, 35.0 parts of the compound represented by the formula (pt11) is charged with 3.00M potassium hydroxide aqueous solution at an amount of 62.4 mL per 1.00 g of the compound represented by the formula (pt11) at room temperature. Added in. To this mixture, 95.1 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred for 36 hours while refluxing. The reaction solution was cooled to room temperature and then neutralized with 2.00N hydrochloric acid. To this, 1180 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. The solvent was distilled off to obtain a residue. To this residue, 466 parts of N, N-dimethylformamide was added to obtain a solution. A solution prepared by dissolving 43.4 parts of DL-dithiothreitol in 493 parts of water was added to this solution, and the mixture was stirred at room temperature for 2 hours. To this reaction solution, an aqueous solution obtained by mixing a 0.500M acetic acid aqueous solution and a 0.500M sodium acetate aqueous solution in a volume ratio of 1: 2 was added in the same volume as the N, N-dimethylformamide added previously. Subsequently, 885 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. To this aqueous layer, 885 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. The ethyl acetate layers were combined and the solvent of the solution was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 2.43 parts of a compound represented by the formula (pt12).

<Identification of compound represented by formula (pt12)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 263.1
Exact Mass: 262.1

3.93 parts of the compound represented by the formula (pt12), 10.1 parts of the compound represented by the formula (pt3), 1.25 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo) 80.0 parts of Kasei Kogyo Co., Ltd. and 3.39 parts of ethyl cyanoacetate (Tokyo Kasei Kogyo Co., Ltd.) were mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of the compound represented by the formula (pt3), 1.30 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 Parts and 3.40 parts of ethyl cyanoacetate (Tokyo Kasei Kogyo Co., Ltd.) were mixed and stirred at 120 ° C. for 12 hours. After cooling said reaction liquid to room temperature, the solvent was distilled off and the residue was obtained. This residue was purified by column chromatography to obtain 1.34 parts of a compound represented by the formula (I-448).

<Identification of Compound Represented by Formula (I-448)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 993.5
Exact Mass: 992.5

[Heat resistance evaluation]
Differential scanning of the compounds obtained in Synthesis Examples 1 to 12 and Coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA6200R manufactured by SII Nanotechnology). Calorimetry was performed. The amount of sample used for one measurement was 5 mg. The measurement temperature was started from 25 ° C., heated at a rate of 10 ° C. per minute, and measured to 600 ° C. Temperature T5 (under air) at which the weight reduction rate is 5% in air, temperature T10 (under air) at which the weight reduction rate is 10% in air, and temperature T5 at which the weight reduction rate is 5% in nitrogen atmosphere (Under nitrogen) and a temperature T10 (under nitrogen) at which the weight loss rate was 10% in a nitrogen atmosphere were determined. The results are shown in Table 30.

  From the results in Table 30, it can be seen that the compounds of the present invention have high thermal stability.

Synthesis Example 13
10.3 parts of o-amino-p-benzylphenol (Journal of the American Chemical Society (1935), 57, 1697-8), 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 Parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.16 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 125 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.85 parts Are mixed and stirred at 120 ° C. for 3 hours. In this solution, 10.0 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 12.5 parts) and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 5.85 parts are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-1).

Synthesis Example 14
12.9 parts of o-amino-p-phenylsulfonylphenol (see JP-A-49-126969), 10.0 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid (Tokyo) 2.16 parts of Kasei Kogyo Co., Ltd., 125 parts of 1-pentanol (Tokyo Kasei Kogyo Co., Ltd.) and 5.85 parts of ethyl cyanoacetate (Tokyo Kasei Kogyo Co., Ltd.) are mixed at 120 ° C. For 3 hours. In this solution, 10.0 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 12.5 parts) and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 5.85 parts are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-60).

Synthesis Example 15
3.57 parts of bis (3-amino-4-hydroxyphenyl) dimethylmethane (manufactured by Changzhou Yoko Pharmaceutical Raw Materials Co., Ltd.), 4- (bis (2-ethylhexyl) amino) salicylaldehyde (described in JP-T-2007-508275) 10.0 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) 1.15 parts, 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 66.7 parts and ethyl cyanoacetate 3.13 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of 4- (bis (2-ethylhexyl) amino) salicylaldehyde (synthesized according to the method described in JP-T-2007-508275), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.15 parts, 7.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. . After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-177).

Synthesis Example 16
4.66 parts of bis (3-amino-4-hydroxyphenyl) dimethylmethane (manufactured by Changzhou Yoko Pharmaceutical Raw Materials Co., Ltd.), 10.0 parts of the compound represented by the formula (pt6), benzoic acid (Tokyo Chemical Industry Co., Ltd.) )) 1.50 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 86.9 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.08 parts. Stir for hours. In this reaction solution, 10.0 parts of a compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.00 Parts and 4.08 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-179).

Synthesis Example 17
9.84 parts of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 125 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.86 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) Mix and stir at 120 ° C. for 3 hours. To this reaction solution, 10.0 parts of 4- (diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.), 2.16 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry ( 12.5 parts) and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 5.86 parts are mixed and stirred at 120 ° C. for 12 hours. After cooling said reaction liquid to room temperature, the solvent is distilled off with a rotary evaporator to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-233).

Synthesis Example 18
9,9-bis (3-amino-4-hydroxyphenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.) 7.63 parts, 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 Part, 1.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 96.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 54 parts are mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 10.0 parts) and 4.54 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-234).

Synthesis Example 19
9,9-bis (3-amino-4-hydroxyphenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.26 parts, 4- (bis (2-ethylhexyl) amino) salicylaldehyde (special table 2007-508275) 10.0 parts synthesized according to the described method), 1.15 parts benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 66.7 parts 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and cyano 3.13 parts of ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of 4- (bis (2-ethylhexyl) amino) salicylaldehyde (synthesized according to the method described in JP-T-2007-508275), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.15 parts, 7.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. . After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-241).

Synthesis Example 20
9.86 parts of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0 parts of the compound represented by the formula (pt6), benzoic acid (Tokyo Chemical Industry Co., Ltd.) 1.50 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.08 parts ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 120 ° C. For 3 hours. In this reaction solution, 10.0 parts of a compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.00 Parts and 4.08 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-243).

Synthesis Example 21
8.08 parts of the compound represented by the formula (pt8), 10.0 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) , 125 parts of 1-pentanol (Tokyo Chemical Industry Co., Ltd.) and 5.85 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. To this reaction solution, 10.0 parts of 4- (diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.), 2.16 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry ( 12.5 parts) and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 5.85 parts are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-311).

Synthesis Example 22
6.26 parts of the compound represented by the formula (pt8), 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.67 Part, 96.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 10.0 parts) and 4.54 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-312).

Synthesis Example 23
4.32 parts of the compound represented by the formula (pt8), 10.0 parts of 4- (bis (2-ethylhexyl) amino) salicylaldehyde (synthesized according to the method described in JP-T-2007-508275), benzo 1.15 parts of acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 66.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) Mix and stir at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of 4- (bis (2-ethylhexyl) amino) salicylaldehyde (synthesized according to the method described in JP-T-2007-508275), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.15 parts, 7.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. . After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-319).

Synthesis Example 24
5.63 parts of the compound represented by the formula (pt8), 10.0 parts of the compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo) 86.9 parts of Kasei Kogyo Co., Ltd. and 4.08 parts of ethyl cyanoacetate (Tokyo Kasei Kogyo Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of a compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.00 Parts and 4.08 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-321).

Synthesis Example 25
7.52 parts of a compound represented by the formula (pt10), 10.0 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) , 125 parts of 1-pentanol (Tokyo Chemical Industry Co., Ltd.) and 5.85 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. To this reaction solution, 10.0 parts of 4- (diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.), 2.16 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry ( 12.5 parts) and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 5.85 parts are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-332).

Synthesis Example 26
5.82 parts of a compound represented by the formula (pt10), 10.0 parts of 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.67 Part, 96.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 10.0 parts) and 4.54 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-333).

Synthesis Example 27
4.02 parts of the compound represented by the formula (pt10), 10.0 parts of 4- (bis (2-ethylhexyl) amino) salicylaldehyde (synthesized according to the method described in JP-T-2007-508275), benzo 1.15 parts of acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 66.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) Mix and stir at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of 4- (bis (2-ethylhexyl) amino) salicylaldehyde (synthesized according to the method described in JP-T-2007-508275), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.15 parts, 7.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. . After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-340).

Synthesis Example 28
5.24 parts of the compound represented by the formula (pt10), 10.0 parts of the compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo) 86.9 parts of Kasei Kogyo Co., Ltd. and 4.08 parts of ethyl cyanoacetate (Tokyo Kasei Kogyo Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of a compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.00 Parts and 4.08 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-342).

Synthesis Example 29
6.79 parts of the compound represented by the formula (pt12), 10.0 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) , 125 parts of 1-pentanol (Tokyo Chemical Industry Co., Ltd.) and 5.85 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. To this reaction solution, 10.0 parts of 4- (diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.), 2.16 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry ( 12.5 parts) and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) 5.85 parts are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-439).

Synthesis Example 30
5.26 parts of a compound represented by the formula (pt12), 10.0 parts of 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.67 Part, 96.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. 10.0 parts of 4- (dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 10.0 parts and 4.54 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-440).

Synthesis Example 31
3.63 parts of the compound represented by the formula (pt12), 10.0 parts of 4- (bis (2-ethylhexyl) amino) salicylaldehyde (synthesized according to the method described in JP-T-2007-508275), benzo 1.15 parts of acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 66.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) Mix and stir at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of 4- (bis (2-ethylhexyl) amino) salicylaldehyde (synthesized according to the method described in JP-T-2007-508275), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.15 parts, 7.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. . After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-447).

Synthesis Example 32
4.73 parts of the compound represented by the formula (pt12), 10.0 parts of the compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo) 86.9 parts of Kasei Kogyo Co., Ltd. and 4.08 parts of ethyl cyanoacetate (Tokyo Kasei Kogyo Co., Ltd.) are mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 10.0 parts of a compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.00 Parts and 4.08 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) are mixed and stirred at 120 ° C. for 12 hours. After cooling the reaction solution to room temperature, the solvent is distilled off to obtain a residue. The residue is purified by column chromatography to obtain the compound represented by the formula (I-449).

Synthesis Example 33
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] Decan-9-yl acrylate (content ratio is 50:50 in molar ratio) 171 parts dissolved in propylene glycol monomethyl ether acetate 40 parts using a dropping pump over about 5 hours And dripped. On the other hand, a solution prepared by dissolving 26 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in a flask over about 5 hours using another dropping pump. It was dripped. After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 43.5%. The obtained resin B1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mgKOH / g.

[Preparation of colored curable resin composition]
Example 1
Colorant (A): C.I. I. Pigment Green 7 (pigment) 53 parts,
24 parts of acrylic pigment dispersant,
Resin (B): 19 parts of resin B1 (solid content conversion) and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 10 parts of a compound represented by formula (I-148);
Resin (B): Resin B1 (solid content conversion) 10 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 29 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.7 parts;
Solvent (E): 13 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 490 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 2
Colorant (A): C.I. I. Pigment Green 7 (pigment) 37 parts,
17 parts of acrylic pigment dispersant,
Resin (B): Resin B1 (solid content conversion) 13 parts, and solvent (E): Propylene glycol monomethyl ether acetate 240 parts were mixed, and a pigment dispersion in which the pigment was sufficiently dispersed using a bead mill;
Colorant (A): 26 parts of a compound represented by formula (I-169);
Resin (B): Resin B1 (solid content conversion) 19 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 32 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.4 parts;
Solvent (E): 24 parts of propylene glycol monomethyl ether acetate;
Solvent (E): N-methylpyrrolidone 580 parts; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 3
Colorant (A): C.I. I. Pigment Green 7 (pigment) 52 parts,
23 parts of acrylic pigment dispersant,
Resin (B): 18 parts of resin B1 (in terms of solid content) and solvent (E): 340 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 11 parts of a compound represented by formula (I-149);
Resin (B): Resin B1 (solid content conversion) 11 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 29 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.8 parts;
Solvent (E): 14 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 500 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 4
Colorant (A): C.I. I. Pigment Green 7 (pigment) 49 parts,
22 parts acrylic pigment dispersant,
Resin (B): 17 parts of resin B1 (in terms of solid content), and solvent (E): 320 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 14 parts of a compound represented by formula (I-156);
Resin (B): Resin B1 (solid content conversion) 12 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 29 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.9 parts;
Solvent (E): 530 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 5
Colorant (A): C.I. I. Pigment Green 36 (pigment) 60 parts,
27 parts of acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content) and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 2.9 parts of a compound represented by formula (I-148);
Resin (B): Resin B1 (solid content conversion) 6.0 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.4 parts;
Solvent (E): propylene glycol monomethyl ether acetate 7.8 parts;
Solvent (E): 450 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 6
Colorant (A): C.I. I. Pigment Green 36 (pigment) 54 parts,
24 parts of acrylic pigment dispersant,
Resin (B): 19 parts of resin B1 (solid content conversion) and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 9.1 parts of a compound represented by formula (I-169);
Resin (B): Resin B1 (in terms of solid content) 9.4 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 28 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.7 parts;
Solvent (E): 12 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 490 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 7
Colorant (A): C.I. I. Pigment Green 36 (pigment) 60 parts,
27 parts of acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content) and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 3.3 parts of the compound represented by formula (I-149);
Resin (B): Resin B1 (solid content conversion) 6.2 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.4 parts;
Solvent (E): Propylene glycol monomethyl ether acetate 8.1 parts;
Solvent (E): 450 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 8
Colorant (A): C.I. I. Pigment Green 36 (pigment) 59 parts,
27 parts of acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content), and solvent (E): 380 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 4.1 parts of a compound represented by formula (I-156);
Resin (B): Resin B1 (solid content conversion) 6.7 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.5 parts;
Solvent (E): 470 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 9
Colorant (A): C.I. I. Pigment Green 58 (pigment) 61 parts,
28 parts of an acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content) and solvent (E): 400 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): Compound represented by formula (I-148) 1.7 parts;
Resin (B): Resin B1 (solid content conversion) 5.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.4 parts;
Solvent (E): 6.9 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 440 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 10
Colorant (A): C.I. I. Pigment Green 58 (pigment) 58 parts,
26 parts of an acrylic pigment dispersant,
Resin (B): 20 parts of resin B1 (in terms of solid content), and solvent (E): 380 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 5.2 parts of a compound represented by formula (I-169);
Resin (B): Resin B1 (solid content conversion) 7.2 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.5 parts;
Solvent (E): propylene glycol monomethyl ether acetate 9.4 parts;
Solvent (E): 460 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 11
Colorant (A): C.I. I. Pigment Green 58 (pigment) 61 parts,
27 parts of acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content) and solvent (E): 400 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 2.0 parts of the compound represented by formula (I-149);
Resin (B): Resin B1 (solid content conversion) 5.5 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.4 parts;
Solvent (E): propylene glycol monomethyl ether acetate 7.1 parts;
Solvent (E): 440 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 12
Colorant (A): C.I. I. Pigment Green 58 (pigment) 61 parts,
27 parts of acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content) and solvent (E): 400 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 2.5 parts of the compound represented by formula (I-156);
Resin (B): Resin B1 (in terms of solid content) 5.8 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.4 parts;
Solvent (E): 450 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 13
Colorant (A): C.I. I. Pigment Green 7 (pigment) 35 parts,
16 parts acrylic pigment dispersant,
Resin (B): 12 parts of resin B1 (in terms of solid content) and solvent (E): 230 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 28 parts of a compound represented by formula (I-170);
Resin (B): Resin B1 (solid content conversion) 20 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 32 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.4 parts;
Solvent (E): 26 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 600 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 14
Colorant (A): C.I. I. Pigment Green 36 (pigment) 53 parts,
24 parts of acrylic pigment dispersant,
Resin (B): 18 parts of resin B1 (in terms of solid content) and solvent (E): 340 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 10 parts of a compound represented by formula (I-170);
Resin (B): Resin B1 (solid content conversion) 10 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 29 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.7 parts;
Solvent (E): 13 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 490 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 15
Colorant (A): C.I. I. Pigment Green 58 (pigment) 57 parts,
26 parts of an acrylic pigment dispersant,
Resin (B): 20 parts of resin B1 (in terms of solid content), and solvent (E): 370 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 5.9 parts of a compound represented by formula (I-170);
Resin (B): Resin B1 (solid content conversion) 7.7 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 28 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.5 parts;
Solvent (E): 9.9 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 470 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 16
Colorant (A): C.I. I. Pigment Green 7 (pigment) 49 parts,
22 parts acrylic pigment dispersant,
Resin (B): 17 parts of resin B1 (in terms of solid content), and solvent (E): 320 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 14 parts of a compound represented by formula (I-157);
Resin (B): Resin B1 (solid content conversion) 12 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 29 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.9 parts;
Solvent (E): 530 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 17
Colorant (A): C.I. I. Pigment Green 36 (pigment) 59 parts,
26 parts of an acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content), and solvent (E): 380 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 4.3 parts of a compound represented by formula (I-157);
Resin (B): Resin B1 (solid content conversion) 6.7 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.5 parts;
Solvent (E): 470 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 18
Colorant (A): C.I. I. Pigment Green 58 (pigment) 60 parts,
27 parts of acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content) and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 2.6 parts of the compound represented by formula (I-157);
Resin (B): Resin B1 (in terms of solid content) 5.8 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.4 parts;
Solvent (E): 460 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 19
Colorant (A): C.I. I. Pigment Green 7 (pigment) 43 parts,
19 parts acrylic pigment dispersant,
Resin (B): 15 parts of resin B1 (in terms of solid content), and solvent (E): 280 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 20 parts of a compound represented by formula (I-178);
Resin (B): Resin B1 (solid content conversion) 16 parts;
Polymerizable compound (C): 31 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.);
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E): 570 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 20
Colorant (A): C.I. I. Pigment Green 36 (pigment) 56 parts,
25 parts of acrylic pigment dispersant,
Resin (B): 20 parts of resin B1 (in terms of solid content), and solvent (E): 370 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 6.8 parts of compound represented by formula (I-178);
Resin (B): Resin B1 (solid content conversion) 8.2 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 28 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.6 parts;
Solvent (E): 480 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 21
Colorant (A): C.I. I. Pigment Green 58 (pigment) 59 parts,
27 parts of acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content) and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 4.0 parts of compound represented by formula (I-178);
Resin (B): Resin B1 (solid content conversion) 6.6 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.5 parts;
Solvent (E): 460 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 22
Colorant (A): C.I. I. Pigment Green 7 (pigment) 51 parts,
23 parts of acrylic pigment dispersant,
Resin (B): 18 parts of resin B1 (in terms of solid content), and solvent (E): 330 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 12 parts of a compound represented by formula (I-158);
Resin (B): Resin B1 (solid content conversion) 11 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 29 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.8 parts;
Solvent (E): 14 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 500 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 23
Colorant (A): C.I. I. Pigment Green 36 (pigment) 60 parts,
27 parts of acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content) and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 3.5 parts of a compound represented by formula (I-158);
Resin (B): Resin B1 (in terms of solid content) 6.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.4 parts;
Solvent (E): Propylene glycol monomethyl ether acetate 8.2 parts;
Solvent (E): 450 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

Example 24
Colorant (A): C.I. I. Pigment Green 58 (pigment) 61 parts,
27 parts of acrylic pigment dispersant,
Resin (B): 21 parts of resin B1 (in terms of solid content) and solvent (E): 400 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 2.1 parts of a compound represented by formula (I-158);
Resin (B): Resin B1 (solid content conversion) 5.5 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.4 parts;
Solvent (E): 7.2 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 440 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) I got a thing.

[Preparation of colored pattern]
The colored curable resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer is formed and the quartz glass photomask is set to 200 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used, and 80 mJ / cm ^{2 in} an air atmosphere. The exposure amount (standard on 365 nm) was used. A photomask having a 100 μm line and space pattern was used. The colored composition layer after exposure is developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 70 seconds, washed with water, A colored pattern was obtained by post-baking at 20 ° C. for 20 minutes.

[Film thickness measurement]
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 31.

[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) was measured. The results are shown in Table 31.

[Preparation of colored curable resin composition for sublimation test]
Comparative Example 1
Colorant (A): C.I. I. Pigment Green 7 (pigment) 50 parts,
22 parts acrylic pigment dispersant,
Resin (B): 17 parts of resin B1 (in terms of solid content), and solvent (E): 320 parts of propylene glycol monomethyl ether acetate, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill;
Colorant (A): Coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) 13 parts;
Resin (B): Resin B1 (solid content conversion) 12 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 29 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 5.8 parts;
Solvent (E): 15 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 510 parts of N-methylpyrrolidone; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A curable resin composition was obtained.

[Preparation of resin composition for sublimation test]
Resin: Methacrylic acid / benzyl methacrylate (molar ratio: 30/70) copolymer (manufactured by Taoka Chemical Co., Ltd., average molecular weight 10700, acid value 70 mg KOH / g) 33.8% propylene glycol monomethyl ether acetate solution 40.2 Part;
Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts;
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Japan Ltd.) 0.58 parts;
Leveling agent: polyether-modified silicone (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.01 part;
Solvent: 46.6 parts of propylene glycol monomethyl ether; Solvent: 6.8 parts of propylene glycol monomethyl ether acetate were mixed to obtain a resin composition for sublimation test.

[Formation of colored coating film for sublimation test]
On the 2-inch square glass substrate (Eagle XG; manufactured by Corning), the colored curable resin composition obtained in Example 1 to Example 24 or Comparative Example 1 was applied by spin coating, respectively, and the temperature was 100 ° C. 3 Volatile components were volatilized in a minute to obtain a colored coating film for sublimation test.

[Formation of resin coating film for sublimation test]
The resin composition for sublimation test obtained above was applied onto a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by a spin coating method, and volatile components were volatilized at 100 ° C. for 3 minutes. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), light irradiation was performed with an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. A resin coating film for sublimation test (thickness: 2.2 μm) was formed by heating in an oven at 220 ° C. for 2 hours.

[Sublimation evaluation]
The colored coating film for sublimation test and the resin coating film for sublimation test were opposed to each other with an interval of 70 μm, and heated at 220 ° C. for 40 minutes. The color difference (ΔEab *) before and after heating of the resin coating film for sublimation test was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). A color difference (ΔEab *) of 5.0 or more indicates that the colorant has sublimability. The results are shown in Table 31. In Table 31, in each example, ◯ indicates that the colorant does not have sublimability, and x indicates that the colorant has sublimability.

  From the results in Table 31, it can be seen that the compounds of the present invention have low sublimation properties.

Examples 25-90
A colored photosensitive resin composition and a color filter are obtained in the same manner as in Example YYY except that compound XXX is used in place of the compound synthesized in Synthesis Example 1. The compound XXX or Example YYY represents the compound XXX or Example YYY shown in Tables 32-34, respectively.

  Since the compound of the present invention has high thermal stability, it can be used as a dye used in a color filter of a display device such as a liquid crystal display device.

Claims (17)

A compound represented by formula (I ′).

[In the formula (I ′),
L represents a C1-C20 bivalent hydrocarbon group. The methylene group constituting the divalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the divalent hydrocarbon group. The hydrogen atom may be replaced with a cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, chlorine atom, bromine atom, imidazol-1-yl group or amino group.
X represents an oxygen atom, a sulfur atom, or —N (R ¹⁰ ) —.
R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ³ are bonded to each other to form a carbon atom on an adjacent benzene ring. A ring is formed with an atom and an adjacent nitrogen atom, or R ² and R ⁴ are combined to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ^{5 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxy group, a hydroxy group, an amino group, or a monovalent group having 1 to 20 carbon atoms. Represents a hydrocarbon group, R ⁵ and R ⁶ combine to form a ring with adjacent carbon atoms, or R ⁷ and R ⁸ combine to form a ring with adjacent carbon atoms To do. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ¹⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ¹⁰ are present, they are the same or different from each other. ] The compound according to claim 1, wherein X is an oxygen atom or a sulfur atom. The compound according to claim 1 or 2 , wherein X is an oxygen atom. L is a methylene group or sulfonyl group which may have a substituent, The compound in any one of Claims 1-3 . L is a dimethylmethylene group or a sulfonyl group, The compound in any one of Claims 1-4 . R < ⁵ > -R < ⁹ > is all a hydrogen atom, The compound in any one of Claims 1-5 . Dye containing the compound in any one of Claims 1-6 . The colored photosensitive resin composition containing the compound in any one of Claims 1-6 , resin, a polymeric compound, a polymerization initiator, and a solvent. A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent containing a compound represented by the formula (I ′).

[In the formula (I ′),
L represents a C1-C20 bivalent hydrocarbon group. The methylene group constituting the divalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the divalent hydrocarbon group. The hydrogen atom may be replaced with a cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, chlorine atom, bromine atom, imidazol-1-yl group or amino group.
X represents an oxygen atom, a sulfur atom, or —N (R ¹⁰ ) —.
R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ³ are bonded to each other to form a carbon atom on an adjacent benzene ring. A ring is formed with an atom and an adjacent nitrogen atom, or R ² and R ⁴ are combined to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ^{5 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxy group, a hydroxy group, an amino group, or a monovalent group having 1 to 20 carbon atoms. Represents a hydrocarbon group, R ⁵ and R ⁶ combine to form a ring with adjacent carbon atoms, or R ⁷ and R ⁸ combine to form a ring with adjacent carbon atoms To do. The methylene group constituting the monovalent hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁰ ) —, a sulfonyl group or a carbonyl group, and is included in the monovalent hydrocarbon group. The hydrogen atom may be replaced by a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, imidazol-1-yl group or amino group.
R ¹⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ¹⁰ are present, they are the same or different from each other. ] The colored photosensitive resin composition according to claim 9 , wherein the colorant further contains a pigment. Pigments, colored photosensitive resin composition of claim 1 0 is at least one selected from the group consisting of halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment. Pigments, chlorinated copper phthalocyanine pigments, colored photosensitive resin composition according to claim 1 0 or 1 1 is at least one selected from the group consisting of brominated copper phthalocyanine pigment and brominated zinc phthalocyanine pigment. Pigments, colored photosensitive resin composition according to any one of claims 1 0 to 1 2 is a green pigment. The pigment is C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. Colored curable resin composition according to any one of claims 1 0 to 1 3 is at least one selected from the group consisting of Pigment Green 58. The pigment is C.I. I. Colored curable resin composition according to any one of claims 1 0-1 4 Pigment Green 7. A color filter formed from the colored curable resin composition according to any one of claims 8 to 15 . A liquid crystal display device comprising the color filter according to claim 16 .