WO2014208767A1

WO2014208767A1 - Colored curable resin composition

Info

Publication number: WO2014208767A1
Application number: PCT/JP2014/067299
Authority: WO
Inventors: 勝成織田; 拓麻藤田
Original assignee: 住友化学株式会社
Priority date: 2013-06-26
Filing date: 2014-06-23
Publication date: 2014-12-31
Also published as: CN105683298A; KR102228368B1; JP6452605B2; TW201506542A; KR20160024976A; TWI623813B; CN105683298B; JPWO2014208767A1

Abstract

A colored curable resin composition which comprises a colorant, a resin, a polymerizable compound, a polymerization initiator and a solvent, wherein the colorant includes a compound represented by formula (I). (In the formula, L is a sulphonyl group, etc., X is an oxygen atom, etc., R⁷ to R¹³ is each independently a hydrogen atom, etc., and Z is a group represented by formula (Z1) (In the formula, R¹ is an alkyl group having 1 to 20 carbon atoms, -CH₂- that constitutes the alkyl group capable of being substituted with an oxygen atom, R² to R⁶ is each independently a hydrogen atom, etc. and * is a bond.) or a group represented by formula (Z2) (In the formula, Ar¹ is phenyl group having an alkyl group having 1 to 8 carbon atoms in an ortho position, meta position or both, and * is a bond.).)

Description

Colored curable resin composition

The present invention relates to a colored curable resin composition.

For example, dyes are used for color display using reflected light or transmitted light in fields such as fiber materials, liquid crystal display devices, and inkjets. Patent Document 1 describes coumarin 6 represented by the following formula as such a dye.

JP 2006-154740 A (Example 8)

The present invention
<1> A colored curable resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent containing a compound represented by formula (I).

(In the formula, L represents a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a sulfonyl group (—SO ₂ —), and X represents oxygen R ⁷ to R ¹³ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (—CONH ₂ ), a sulfamoyl group (—SO ₂ NH ₂ ), — SO ₃ M, —CO ₂ M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, —CH ₂ — constituting the hydrocarbon group is an oxygen atom, sulfur ^atom, -N (R 14) ^-, may be replaced to a sulfonyl group or a carbonyl group, a hydrogen atom contained in the hydrocarbon group include a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO M, _-CO 2 M, hydroxy group, may be replaced to formyl group or an amino ^{group, R 14} represents a monovalent hydrocarbon group hydrogen atom or a C 1 ~ ^{20, R 14} there are a plurality of In this case, they may be the same or different, and M represents a hydrogen atom or an alkali metal atom, and when a plurality of M are present, they may be the same or different. Well,
Z represents the formula (Z1):

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, —CH ₂ — constituting the alkyl group may be replaced by an oxygen atom, and R ² to R ⁶ are each independently A hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. And —CH ₂ — constituting the hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ³⁰ ) —, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group It is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{_{group, -SO 3 M, -CO 2 M}} , hydroxy group, may be replaced to formyl group or an amino ^{group, R 30} Represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ³⁰ are present, they may be the same or different, and * represents a bond. .)
Or a group represented by formula (Z2):

(In the formula, Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, the meta position, or both, and * represents a bond.)
Represents a group represented by )
<2> The colored curable resin composition according to <1>, wherein L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
<3> The colored curable resin composition according to <1>, wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group.
<4> The colored curable resin composition according to any one of <1> to <3>, wherein Z is a group represented by the formula (Z1).
<5> The coloring according to any one of <1> to <4>, wherein R ¹ is an alkyl group having 1 to 16 carbon atoms, and —CH ₂ — constituting the alkyl group may be replaced with an oxygen atom. Curable resin composition.
<6> The colored curable resin composition according to <2>, wherein Z is a group represented by the formula (Z1), and R ¹ is an alkyl group having 1 to 8 carbon atoms.
<7> The colored curable resin composition according to <3>, wherein Z is a group represented by the formula (Z1), and R ¹ is an alkyl group having 6 to 10 carbon atoms.
<8> The colored curable resin composition according to any one of <1> to <3>, wherein Z is a group represented by the formula (Z2).
<9> Ar ¹ is a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, or a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position and the meta position. The colored curable resin composition according to any one of 2>, <3> and <8>.
<10> The colored curable resin composition according to <9>, wherein the alkyl group having 1 to 8 carbon atoms is a methyl group, an ethyl group, or an isopropyl group.
<11> The colored curable resin composition according to any one of <1> to <10>, wherein the colorant further contains a pigment.
<12> The colored curable 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 curable resin composition according to <11>, 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 curable 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> A color filter formed from the colored curable resin composition according to any one of <1> to <15>.
<17> A liquid crystal display device comprising the color filter according to <16>.
<18> A compound represented by formula (Ia-1).

(Wherein, ^{L a} is a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms (-SO ₂ - represents a), X represents an oxygen atom or a sulfur atom, ^{R 7} ~ ^{R 13} is Independently, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (—CONH ₂ ), a sulfamoyl group (—SO ₂ NH ₂ ), —SO ₃ M, —CO ₂ M, a hydroxy group, and a formyl group Represents an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — constituting the hydrocarbon group is an oxygen atom, a sulfur atom, —N (R ¹⁴ ) —, a sulfonyl group or a carbonyl group. It may be replaced based on the hydrogen atoms contained in the hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{group, -SO 3 M, -CO 2 M} , hydroxy group, Hol May be replaced in the group or amino group, R ¹⁴ represents a monovalent hydrocarbon group hydrogen atom or a C 1-20, if R ¹⁴ is plurally present, they may be the same M may represent a hydrogen atom or an alkali metal atom, and when a plurality of M are present, they may be the same or different,
Z ^a represents a group represented by the formula (Z1).

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, —CH ₂ — constituting the alkyl group may be replaced by an oxygen atom, and R ² to R ⁶ are each independently A hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. And —CH ₂ — constituting the hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ³⁰ ) —, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group It is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{_{group, -SO 3 M, -CO 2 M}} , hydroxy group, may be replaced to formyl group or an amino ^{group, R 30} Represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when there are a plurality of R ^{30 s} , they may be the same or different, and when there are a plurality of M And they may be the same or different, and * represents a bond.))
<19> The compound according to <18>, wherein R ¹ is an alkyl group having 1 to 16 carbon atoms, and —CH ₂ — constituting the alkyl group may be replaced with an oxygen atom.
<20> The compound according to <18>, wherein R ¹ is an alkyl group having 6 to 10 carbon atoms.
<21> A compound represented by the formula (Ia-2).

(Wherein, ^{L a} is a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms (-SO ₂ - represents a), X represents an oxygen atom or a sulfur atom, ^{R 7} ~ ^{R 13} is Independently, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (—CONH ₂ ), a sulfamoyl group (—SO ₂ NH ₂ ), —SO ₃ M, —CO ₂ M, a hydroxy group, and a formyl group Represents an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — constituting the hydrocarbon group is an oxygen atom, a sulfur atom, —N (R ¹⁴ ) —, a sulfonyl group or a carbonyl group. It may be replaced based on the hydrogen atoms contained in the hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{group, -SO 3 M, -CO 2 M} , hydroxy group, Hol May be replaced in the group or amino group, R ¹⁴ represents a monovalent hydrocarbon group hydrogen atom or a C 1-20, if R ¹⁴ is plurally present, they may be the same M may represent a hydrogen atom or an alkali metal atom, and when a plurality of M are present, they may be the same or different,
Z ^b represents a group represented by the formula (Z2).

(In the formula, Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, the meta position, or both, and * represents a bond.)
<22> As described in <21>, Ar ¹ is a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position or a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position and the meta position. Compound.
<23> The compound according to <22>, wherein the alkyl group having 1 to 8 carbon atoms is a methyl group, an ethyl group or an isopropyl group.
<24> A colorant comprising the compound according to any one of <18> to <23>.
<25> The colorant according to <24>, further comprising a pigment.
<26> A compound represented by the formula (IIa).

(Wherein, L ^a represents a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms, X represents an oxygen atom or a sulfur atom, R ¹¹ ~ R ¹³ are each independently hydrogen An atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The —CH ₂ — constituting the hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ¹⁴ ) —, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{_{group, -SO 3 M, -CO 2 M}} , hydroxy group, may be replaced to formyl group or an amino group, ^{R 1} Represents a monovalent hydrocarbon group hydrogen atom or a C 1-20, if R ¹⁴ there are a plurality, to which may be the same or different, M is a hydrogen atom or Represents an alkali metal atom, and when a plurality of M are present, they may be the same or different, and R ¹⁵ and R ¹⁶ each independently represents an alkyl group having 1 to 20 carbon atoms; Represents.)
<27> A compound represented by the formula (III).

(Wherein R ⁷ to R ⁹ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl group, Represents an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — constituting the hydrocarbon group is an oxygen atom, a sulfur atom, —N (R ¹⁴ ) —, a sulfonyl group or a carbonyl group; The hydrogen atom contained in the hydrocarbon group may be a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl group or an amino group. good .R ¹⁴ be replaced in groups, a monovalent hydrocarbon group hydrogen atom or a C 1-20, if R ¹⁴ there are a plurality, even they are the same M represents a hydrogen atom or an alkali metal atom, and when a plurality of M are present, they may be the same or different, and Z represents the formula (Z1) :

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, —CH ₂ — constituting the alkyl group may be replaced by an oxygen atom, and R ² to R ⁶ are each independently A hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. And —CH ₂ — constituting the hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R ³⁰ ) —, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group It is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{_{group, -SO 3 M, -CO 2 M}} , hydroxy group, may be replaced to formyl group or an amino ^{group, R 30} Represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when there are a plurality of R ^{30 s} , they may be the same or different, and M is a hydrogen atom or Represents an alkali metal atom, and when a plurality of M are present, they may be the same or different, and * represents a bond.
Or a group represented by formula (Z2):

(In the formula, Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, the meta position, or both, and * represents a bond.)
Represents a group represented by ); Etc.

The colored curable resin composition of the present invention includes a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent containing a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). including. Compound (I) includes tautomers and salts thereof.

<Compound (I)>
In the formula (I), L represents a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a sulfonyl group (—SO ₂ —).

Examples of the divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms include groups represented by formulas (L1) to (L12). From the viewpoint of availability of raw materials, formula (L1), formula ( It is preferably a group represented by L7), formula (L8), formula (L10) or formula (L11), represented by formula (L1), formula (L7), formula (L8) or formula (L11). And more preferably a group represented by the formula (L1). In the following formulas (L1) to (L12), ● represents a bond.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a 1,1-ethylene group, a 2,2-propylene group, and a fluorene-9,9-diyl group. A divalent hydrocarbon group having 1 to 16 carbon atoms is preferable.

From the viewpoint of thermal stability of the compound (I), L is preferably a divalent hydrocarbon group having 1 to 16 carbon atoms or a sulfonyl group. From the viewpoint of obtaining raw materials, the following formula (L21) to A group represented by any one of formulas (L24) is more preferred, a group represented by any one of formulas (L21) to (L23) is more preferred, and formula (L21) or formula (L The group represented by L22) is particularly preferred. In the following formula, ● represents a bond.

In formula (I), X represents an oxygen atom or a sulfur atom, preferably an oxygen atom. A color filter formed from a colored curable resin composition containing a colorant containing a compound (I) in which X is an oxygen atom tends to have high brightness.

In formula (I), R ⁷ to R ¹³ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M, —CO ₂ M, a hydroxy group, or formyl. Represents a group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — constituting the hydrocarbon group is an oxygen atom, a sulfur atom, —N (R ¹⁴ ) —, a sulfonyl group or A carbonyl group may be substituted, and the hydrogen atom contained in the hydrocarbon group includes a halogen atom, a cyano group, a nitro group, a carbamoyl group (—CONH ₂ ), a sulfamoyl group (—SO ₂ NH ₂ ), and —SO _3. M, _-CO 2 M, hydroxy group, may be replaced to formyl group or an amino ^{group, R 14} represents a monovalent hydrocarbon group hydrogen atom or a C 1 ~ 20, ^{R 1} If There there exist a plurality to which may be the same or may be different.

M represents a hydrogen atom or an alkali metal atom, and when a plurality of M are present, they may be the same or different. Examples of the alkali metal atom include a sodium atom and a potassium atom. M is preferably a hydrogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the monovalent hydrocarbon group having 1 to 20 carbon atoms,
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-1-butyl group 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, 3-pentyl group, neopentyl group, tert-pentyl group, 1-methyl-1-pentyl group, 2-methyl-1-pentyl group, 2-pentenyl group, 3-ethyl-1-pentyl group, hexyl group, isohexyl group, 5-methyl-1-hexyl group, 2-ethyl-1-hexyl group, heptyl group, 3-ethyl-1-heptyl group, An aliphatic hydrocarbon group such as an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an octadecyl 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, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,6-di (2-propyl) phenyl group, 1-naphthyl An aromatic hydrocarbon group such as a group, 2-naphthyl group, biphenyl group; and
Examples thereof include groups formed by combining two or more groups such as cyclohexylmethyl group, benzyl group and phenethyl group.

A group in which —CH ₂ — constituting the monovalent hydrocarbon group is replaced with an oxygen atom, a sulfur atom, —N (R ¹⁴ ) —, a sulfonyl group or a carbonyl group, and such a monovalent hydrocarbon group; Examples of the group in which the hydrogen atom contained is replaced with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl 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-1-hexyl) oxy group;
Aryloxy groups such as phenoxy groups;
An aralkyloxy group such as a benzyloxy group;
Acetyl group, ethylcarbonyl group, propylcarbonyl group, isopropylcarbonyl group, isopropenylcarbonyl group, 1-propenylcarbonyl group, 2-propenylcarbonyl group, butylcarbonyl group, isobutylcarbonyl group, sec-butylcarbonyl group, tert-butylcarbonyl Group, (1-ethyl-1-butyl) carbonyl group, (2-ethyl-1-butyl) carbonyl group, 2-butenylcarbonyl group, 1,3-butadienylcarbonyl group, pentylcarbonyl group, isopentylcarbonyl Group, 3-pentylcarbonyl group, neopentylcarbonyl group, tert-pentylcarbonyl group, (1-methyl-1-pentyl) carbonyl group, (2-methyl-1-pentyl) carbonyl group, 2-pentenylcarbonyl group, 1-ethyl-1 Pentyl) carbonyl group, (3-ethyl-1-pentyl) carbonyl group, hexylcarbonyl group, isohexylcarbonyl group, (5-methyl-1-hexyl) carbonyl group, (2-ethyl-1-hexyl) carbonyl group, Heptylcarbonyl group, (3-ethyl-1-heptyl) carbonyl group, octylcarbonyl group, nonylcarbonyl group, decylcarbonyl group, undecylcarbonyl group, dodecylcarbonyl group, cyclohexylmethylcarbonyl group, cyclopropylcarbonyl group, cyclobutylcarbonyl An acyl group such as a group, cyclopentylcarbonyl group, cyclohexylcarbonyl group;
An acyloxy group such as an acetoxy group or a benzoyloxy group;
Alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group;
Groups represented by the following formula (GL-1) to formula (GL-8) (in the following formula, ● represents a bond);

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-ethyl-1-propyl) carbamoyl group, N- (1,1-dimethyl-1-propyl) carbamoyl group, N- (1,2-dimethyl-1-propyl) ) Carbamoyl group, N- (2,2-dimethyl-1-propyl) carbamoyl group, N- (1-methyl-1-butyl) carbamoyl group, N- (2-methyl-1-butyl) carbamoyl group, N- (3-Methyl-1-butyl) carbamoyl group, N-cyclopentylcarbamoyl group, N-hexylcarba Yl group, N- (1,3-dimethyl-1-butyl) carbamoyl group, N- (3,3-dimethyl-1-butyl) carbamoyl group, N-heptylcarbamoyl group, N- (1-methyl-1- (Hexyl) carbamoyl group, N- (1,4-dimethylpentyl) carbamoyl group, N-octylcarbamoyl group, N- (2-ethyl-1-hexyl) carbamoyl group, N- (1,5-dimethyl-1-hexyl) ) Monosubstituted carbamoyl groups such as carbamoyl group, N- (1,1,2,2-tetramethyl-1-butyl) 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 Methylcarbamoyl group, N, N-butylethylcarbamoyl group, N, N-bis (1-methyl-1-propyl) carbamoyl group, N, N-heptylmethylcarbamoyl group, N, N-bis (2-ethyl-1) -Hexyl) disubstituted carbamoyl groups such as carbamoyl groups;

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-ethyl-1-propyl) sulfamoyl group, N- (1,1-dimethyl-1 -Propyl) sulfamoyl group, N- (1,2-dimethyl-1-propyl) sulfamoyl group, N- (2,2-dimethyl-1-propyl) sulfamoyl group, N- (1-methyl-1-butyl) sulfamoyl Group, N- (2-methylbutyl) sulfamoyl group, N- (3-methyl-1-butyl) sulfamoyl group, N-cyclopentylsulfa Yl group, N-hexylsulfamoyl group, N- (1,3-dimethyl-1-butyl) sulfamoyl group, N- (3,3-dimethyl-1-butyl) sulfamoyl group, N-heptylsulfamoyl group N- (1-methyl-1-hexyl) sulfamoyl group, N- (1,4-dimethyl-1-pentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethyl-1-hexyl) Monosubstituted sulfamoyl groups such as a sulfamoyl group, an N- (1,5-dimethyl-1-hexyl) sulfamoyl group, an N- (1,1,2,2-tetramethyl-1-butyl) 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-methyl-1-propyl) sulfamoyl group, N, N-heptylmethyl Disubstituted sulfamoyl groups such as a sulfamoyl group and an N, N-bis (2-ethyl-1-hexyl) 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-ethyl-1-propyl) amino group, N- (1,1-dimethyl-1-propyl) amino group, N- (1,2-dimethyl-1-propyl) ) Amino group, N- (2,2-dimethyl-1-propyl) amino group, N- (1-methyl-1-butyl) amino group, N- (2-methyl-1-butyl) amino group, N- (3-methyl-1-butyl) amino group, N-cyclopentylamino group, N-hexylamino group, N- (1,3-dimethyl-1-butyl) amino group, N- (3,3-dimethyl-1 -Butyl) amino group, N-he Tylamino group, N- (1-methyl-1-hexyl) amino group, N- (1,4-dimethyl-1-pentyl) amino group, N-octylamino group, N- (2-ethyl-1-hexyl) N-alkylamino groups such as amino group, N- (1,5-dimethyl-1-hexyl) amino group, N- (1,1,2,2-tetramethyl-1-butyl) 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 Amino group, N, N-butylethylamino group, N, N-bis (1-methyl-1-propyl) amino group, N, N-heptylmethylamino group, N, N-bis (2-ethyl-1- Hexyl) N, N-dialkylamino groups such as amino groups;

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-ethyl-1-propyl) aminomethyl group, N- (1,1-dimethyl-1-propyl) aminomethyl group, N -(1,2-dimethyl-1-propyl) aminomethyl group, N- (2,2-dimethyl-1-propyl) aminomethyl group, N- (1-methyl-1-butyl) aminomethyl group, N- (2-methyl-1-butyl) aminomethyl group, N- (3-methyl-1-butyl) aminomethyl group, N-cyclopentylaminomethyl group, N-hexylamino Til group, N- (1,3-dimethyl-1-butyl) aminomethyl group, N- (3,3-dimethyl-1-butyl) aminomethyl group, N-heptylaminomethyl group, N- (1-methyl) -1-hexyl) aminomethyl group, N- (1,4-dimethyl-1-pentyl) aminomethyl group, N-octylaminomethyl group, N- (2-ethyl-1-hexyl) aminomethyl group, N- N-alkylaminomethyl groups such as (1,5-dimethyl-1-hexyl) aminomethyl group and N- (1,1,2,2-tetramethyl-1-butyl) aminomethyl group;
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-methyl-1-propyl) aminomethyl group, N, N-heptylmethylaminomethyl group, N, N -N, N-dialkylaminomethyl group such as di (2-ethyl-1-hexyl) 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-methyl-1-pentyl) group, perfluoro (2-pentenyl) group, perfluoro Xyl group, perfluoroisohexyl group, perfluoro (5-methyl-1-hexyl) group, perfluoro (2-ethyl-1-hexyl) group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, perfluoroun An aliphatic hydrocarbon group having a fluorine atom such as a decyl group, a perfluorododecyl group, or a perfluorooctadecyl 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-methyl-1-pentyl)) methoxy group, (perfluoro (2-methylpentyl)) methoxy group, (perfluoro (2-pentenyl)) methoxy group, (perfluorohexyl) methoxy group, (perfluoro (isohexyl)) A methoxy group, Fluoro (5-methyl-1-hexyl)) methoxy group, (perfluoro (2-ethyl-1-hexyl)) methoxy group, (perfluoroheptyl) methoxy group, (perfluorooctyl) methoxy group, (perfluorononyl) methoxy group, A substituted oxy group having a fluorine atom such as (perfluorodecyl) methoxy group, (perfluoroundecyl) methoxy group, (perfluorododecyl) methoxy group, (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 ⁷ to R ¹¹ and R ¹³ are preferably hydrogen atoms.

R ¹² is preferably a hydrogen atom, —SO ₃ M or —CO ₂ M, more preferably a hydrogen atom or —SO ₃ M, and particularly preferably a hydrogen atom.

In formula (I), Z represents a group represented by the following formula (Z1) or a group represented by the following formula (Z2) (in the following formula, * represents a bond).

In formula (Z1), R ¹ represents an alkyl group having 1 to 20 carbon atoms, and —CH ₂ — constituting the alkyl group may be replaced with an oxygen atom. Such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-ethyl-1-butyl, pentyl, isopentyl, 3 -Pentyl group, neopentyl group, tert-pentyl group, 1-methyl-1-pentyl group, 2-methyl-1-pentyl group, 3-ethyl-1-pentyl group, hexyl group, isohexyl group, 5-methyl-1 -Hexyl group, 2-ethyl-1-hexyl group, heptyl group, 3-ethyl-1-heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group, etc. ~ 16 alkyl groups are preferred.

Examples of the group in which —CH ₂ — constituting the alkyl group is replaced by an oxygen atom include groups represented by the above formulas (GL-1) to (GL-8).

When L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), from the viewpoint of solubility of the compound (I) in the solvent, the formula R ¹ in (Z1) is preferably an alkyl group having 1 to 16 carbon atoms or a group represented by any of formulas (GL-1) to (GL-8), more preferably 1 to 8 or a group represented by any of formulas (GL-1) to (GL-8), more preferably an alkyl group having 2 to 8 carbon atoms (for example, an ethyl group, a butyl group, 2 -Ethyl-1 hexyl group, 1-octyl group, etc.) or a group represented by any of formulas (GL-1) to (GL-6), particularly preferably an alkyl group having 2 to 4 carbon atoms or It is a group represented by any one of formula (GL-1) to formula (GL-4).

When L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group and Z is a group represented by the formula (Z1), from the viewpoint of solubility of the compound (I) in a solvent, R ¹ in the formula (Z1) is preferably an alkyl group having 1 to 16 carbon atoms or a group represented by any one of the formulas (GL-1) to (GL-8), more preferably 4 carbon atoms. Or a group represented by any of formula (GL-1) to formula (GL-8), more preferably an alkyl group having 6 to 10 carbon atoms (for example, 2-ethyl-1hexyl). Group, 1-octyl group, etc.) or a group represented by any of the formulas (GL-3) to (GL-8), particularly preferably an alkyl group having 6 to 10 carbon atoms or the formula (GL-3). ) To a group represented by any of formulas (GL-6).

In formula (Z1), R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M, —CO ₂ M, a hydroxy group, or formyl. Represents a group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — constituting the hydrocarbon group is an oxygen atom, a sulfur atom, —N (R ³⁰ ) —, a sulfonyl group or A carbonyl group may be substituted, and the hydrogen atom contained in the hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M, —CO ₂ M, a hydroxy group, or a formyl group. Or it may be replaced by an amino group. R ³⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ³⁰ are present, they may be the same or different, and M is hydrogen An atom or an alkali metal atom is represented, and when a plurality of M are present, they may be the same or different.
Examples of R ² to R ⁶ include the same as R ⁷ to R ¹³ . R ³⁰ may be the same as R ¹⁴ .

When L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), from the viewpoint of solubility of the compound (I) in the solvent, the formula R ² in (Z1) is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom, A methyl group, an ethyl group, a 2-propyl group or a tert-butyl group, particularly preferably a hydrogen atom or a methyl group. A color filter formed from a colored curable resin composition containing a colorant containing compound (I) in which R ² is any of these groups tends to have high brightness.

When L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), from the viewpoint of solubility of the compound (I) in the solvent, the formula R ⁴ in (Z1) is preferably a hydrogen atom, —SO ₃ M, —CO ₂ M, or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, 1-butyl group, tert-butyl group, 1-hexyl group, 2-ethyl-1-hexyl group, 1-octyl group, etc.), more preferably a hydrogen atom, —SO ₃ M, —CO ₂ M or carbon It is an alkyl group having a number of 1 to 4, more preferably a hydrogen atom or a methyl group.

When L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), R ⁶ is preferably a hydrogen atom or 1 to 10 carbon atoms. An aliphatic hydrocarbon group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom, a methyl group, an ethyl group, a 2-propyl group or a tert-butyl group, A hydrogen atom or a methyl group is preferable. A color filter formed from a colored curable resin composition containing a colorant containing compound (I) in which R ⁶ is any of these groups tends to have high brightness.

When L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), R ³ and R ⁵ are preferably hydrogen atoms.

When L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group and Z is a group represented by the formula (Z1), from the viewpoint of solubility of the compound (I) in a solvent, R ² in formula (Z1) is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group. , An ethyl group or a 2-propyl group, particularly preferably a methyl group. A color filter formed from a colored curable resin composition containing a colorant containing compound (I) in which R ² is any of these groups tends to have high brightness.

When L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group and Z is a group represented by the formula (Z1), from the viewpoint of solubility of the compound (I) in a solvent, R ⁴ in formula (Z1) is preferably a hydrogen atom, —SO ₃ M, —CO ₂ M, or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group) 1-butyl group, tert-butyl group, 1-hexyl group, 2-ethyl-1-hexyl group, 1-octyl group and the like, more preferably a hydrogen atom, —SO ₃ M, —CO ₂ M or An alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.

When L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group, and Z is a group represented by the formula (Z1), R ⁶ is preferably a hydrogen atom, having 1 to 10 carbon atoms. An aliphatic hydrocarbon group, —SO ₃ M or —CO ₂ M, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or —SO ₃ M, and particularly preferably a hydrogen atom or carbon number 1. It is an alkyl group of ~ 4.

When L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group, and Z is a group represented by the formula (Z1), R ³ and R ⁵ are preferably hydrogen atoms.

The following formula in formula (Z1)

Specific examples of the group represented by the formulas include groups represented by the following formulas (PHK-1) to (PHK-31). In the following formula, ● represents a bond.

In the formula (Z2), Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, the meta position, or both. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethyl-1-butyl group, and pentyl group. , Isopentyl group, 3-pentyl group, neopentyl group, tert-pentyl group, 1-methyl-1-pentyl group, 2-methyl-1-pentyl group, 3-ethyl-1-pentyl group, hexyl group, isohexyl group, Examples thereof include a 5-methyl-1-hexyl group, a 2-ethyl-1-hexyl group, a heptyl group, and an octyl group. An alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
The phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position means a phenyl group having an alkyl group having 1 to 8 carbon atoms in at least one of two ortho positions. The phenyl group having an alkyl group having 1 to 8 carbon atoms in the meta position means a phenyl group having an alkyl group having 1 to 8 carbon atoms in at least one of the two meta positions. A phenyl group having an alkyl group having 1 to 8 carbon atoms in both ortho and meta positions means a phenyl group having an alkyl group having 1 to 8 carbon atoms in at least one of two ortho positions and at least one of two meta positions. Means group.

Ar ¹ is preferably a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, or a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position and the meta position.

Ar ¹ may have a substituent other than an alkyl group having 1 to 8 carbon atoms. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), cyano group, nitro group, carbamoyl group, sulfamoyl group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl group and include amino group, -SO ₃ M and -CO ₂ M is preferred.

Specific examples of Ar ¹ include groups represented by the following formulas (PHK-1) to (PHK-10) and formulas (PHK-13) to (PHK-29). In the following formula, ● represents a bond.

As the compound (I), compounds represented by the formula (IA) shown in the following Tables 1 to 3 or alkali metal salts thereof, compounds represented by the formula (IB) shown in the following Tables 4 to 5 or alkalis thereof A metal salt, a compound represented by the formula (IAA) shown in the following Tables 6 to 19 or an alkali metal salt thereof, and a compound represented by the formula (IAB) shown in the following Tables 20 to 28 or an alkali metal salt thereof. Can be mentioned.

In Tables 1 to 5, “L1” represents a group represented by the formula (L1), “O” represents an oxygen atom, “S” represents a sulfur atom, and “Me” represents a methyl group. "Et" represents an ethyl group, "Bu" represents a butyl group, "Hex" represents a hexyl group, "EHx" represents a 2-ethyl-1-hexyl group, and "Oct" represents an octyl group. “GL1” represents a group represented by the formula (GL-1), “GL2” represents a group represented by the formula (GL-2), and “GL3” represents a formula (GL-3). in represents a group represented by the "GL5" represents a group represented by the formula (GL5), "H" represents a hydrogen atom, "SA" represents -SO ₃ H, "CA" is —CO ₂ H, and “PHK-1” to “PHK-16” are represented by the formulas (PHK-1) to (PHK-16), respectively. ) Represents a group represented by

In Tables 6 to 19, “L21” represents a group represented by Formula (L21), “L22” represents a group represented by Formula (L22), and “L23” represents a group represented by Formula (L23). “L24” represents a group represented by the formula (L24), “O” represents an oxygen atom, “S” represents a sulfur atom, “Me” represents a methyl group, “Et” represents an ethyl group, “Bu” represents a butyl group, “Hex” represents a hexyl group, “EHx” represents a 2-ethyl-1-hexyl group, “Oct” represents an octyl group, “MB” represents a 3-methyl-1-butyl group, “DC” represents a dodecyl group, “GL1” represents a group represented by the formula (GL-1), and “GL2” represents a formula (GL— 2) represents a group represented by "GL3" represents a group represented by the formula (GL-3). , “GL5” represents a group represented by the formula (GL-5), “H” represents a hydrogen atom, “SA” represents —SO ₃ H, and “CA” represents —CO ₂ H.

In Tables 20 to 28 below, “L21” represents a group represented by Formula (L21), “L22” represents a group represented by Formula (L22), and “L23” represents Formula (L23). "L24" represents a group represented by the formula (L24), "O" represents an oxygen atom, "S" represents a sulfur atom, and "H" represents a hydrogen atom. , “SA” represents —SO ₃ H, “CA” represents —CO ₂ H, and “PHK-1” to “PHK-16” are represented by formulas (PHK-1) to (PHK-16), respectively. Represents the group represented.

Examples of the compound (I) include compounds represented by the formula (IA ′) shown in the following Table 29 or alkali metal salts thereof.

In Table 29 below, “L1” represents a group represented by the formula (L1), “O” represents an oxygen atom, “Me” represents a methyl group, “Et” represents an ethyl group, “Bu” represents a butyl group, “Hex” represents a hexyl group, “EHx” represents a 2-ethyl-1-hexyl group, “Oct” represents an octyl group, and “GL1” represents the formula (GL— 1) represents a group represented by formula (GL-2), “GL3” represents a group represented by formula (GL-3), and “GL5” represents a group represented by formula (GL-3). The group represented by the formula (GL-5) is represented, and “H” represents a hydrogen atom.

For example, compound (I-2) is a compound represented by the following formula (I-2).

For example, compound (IA-1) is a compound represented by the following formula (IA-1).

For example, compound (IB-1) is a compound represented by the following formula (IB-1).

Among the compounds (I) in which L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, the solubility of the compound (I) in the solvent and the brightness of the color filter formed from the colored curable resin composition From the viewpoint, compound (I-1), compound (I-2), compound (I-5), compound (I-6), compound (I-9), compound (I-10), compound (I-13) ), Compound (I-14), Compound (I-17), Compound (I-18), Compound (I-21), Compound (I-22), Compound (I-25), Compound (I-26) , Compound (I-29), Compound (I-30), Compound (I-65), Compound (I-66), Compound (I-67), Compound (I-68), Compound (I-69), Compound (I-70), Compound (I-71), Compound (I-72), Compound (I-73), Compound ( I-74), Compound (I-75), Compound (I-76), Compound (I-77), Compound (I-78), Compound (I-79), Compound (I-80), Compound (I -81) to Compound (I-100), Compound (I-141), Compound (I-144), Compound (I-145) to Compound (I-166), Compound (I-4), Compound (I- 8), Compound (I-12), Compound (I-16), Compound (I-20), Compound (I-24), Compound (I-28), Compound (I-32) and Compound (I-142) Is preferred,
Compound (I-1), Compound (I-2), Compound (I-5), Compound (I-6), Compound (I-13), Compound (I-14), Compound (I-17), Compound (I-18), Compound (I-21), Compound (I-22), Compound (I-25), Compound (I-26), Compound (I-45), Compound (I-46), Compound ( I-49), Compound (I-50), Compound (I-65), Compound (I-66), Compound (I-69), Compound (I-70), Compound (I-73), Compound (I -74), Compound (I-77), Compound (I-78) and Compound (I-81) to Compound (I-92), Compound (I-141), Compound (I-144), Compound (I- 145) to Compound (I-148), Compound (I-151) to Compound (I-158), Compound (I-161) Compound (I-166), Compound (I-4), Compound (I-8), Compound (I-16), Compound (I-20), Compound (I-24), Compound (I-28) and Compound (I-142) is more preferable,
Compound (I-1), Compound (I-2), Compound (I-5), Compound (I-6), Compound (I-21), Compound (I-22), Compound (I-25), Compound (I-26), Compound (I-65), Compound (I-66), Compound (I-73), Compound (I-74), Compound (I-81), Compound (I-82), Compound ( I-141), Compound (I-144), Compound (I-145) to Compound (I-148), Compound (I-153) to Compound (I-158), Compound (I-4), Compound (I -8), compound (I-24), compound (I-28) and compound (I-142) are more preferred,
Compound (I-1) and compound (I-2) are particularly preferred.

Among the compounds (I) in which L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group and Z is a group represented by the formula (Z1), the solubility of the compound (I) in a solvent and From the viewpoint of the brightness of the color filter formed from the colored curable resin composition, Compound (IA-1), Compound (IA-2), Compound (IA-5), Compound (IA-6), Compound (IA-) 9), Compound (IA-10), Compound (IA-13), Compound (IA-14), Compound (IA-17), Compound (IA-18), Compound (IA-21), Compound (IA-22) ), Compound (IA-25), Compound (IA-26), Compound (IA-29), Compound (IA-30), Compound (IA-33), Compound (IA-34), Compound (IA-37) , Compound (IA-38), Compound (IA-41) , Compound (IA-42), Compound (IA-45), Compound (IA-46), Compound (IA-49), Compound (IA-50), Compound (IA-53), Compound (IA-54), Compound (IA-57), Compound (IA-58), Compound (IA-61), Compound (IA-62), Compound (IA-65), Compound (IA-66), Compound (IA-69), Compound (IA-70), Compound (IA-73), Compound (IA-74), Compound (IA-77), Compound (IA-78), Compound (IA-81), Compound (IA-82), Compound ( IA-85), Compound (IA-86), Compound (IA-89), Compound (IA-90), Compound (IA-93), Compound (IA-94), Compound (IA-97), Compound (IA) -98), compound (IA-101), Compound (IA-102), Compound (IA-105), Compound (IA-106), Compound (IA-109), Compound (IA-110), Compound (IA-113), Compound (IA-114), Compound (IA-117), Compound (IA-118), Compound (IA-121), Compound (IA-122), Compound (IA-125), Compound (IA-126), Compound (IA-257), Compound ( IA-259), Compound (IA-261), Compound (IA-262), Compound (IA-264), Compound (IA-266), Compound (IA-267), Compound (IA-269), Compound (IA) -271), Compound (IA-272), Compound (IA-274), Compound (IA-276), Compound (IA-277), Compound (IA-279), Compound (IA-281) , Compound (IA-282), Compound (IA-284), Compound (IA-286), Compound (IA-287), Compound (IA-289), Compound (IA-291), Compound (IA-292), Compound (IA-294), Compound (IA-296), Compound (IA-301), Compound (IA-302), Compound (IA-305), Compound (IA-306), Compound (IA-309), Compound (IA-310), compound (IA-313), compound (IA-314) and compound (IA-333) to compound (IA-404) are preferred,
Compound (IA-9), Compound (IA-10), Compound (IA-13), Compound (IA-14), Compound (IA-17), Compound (IA-18), Compound (IA-25), Compound (IA-26), Compound (IA-29), Compound (IA-30), Compound (IA-41), Compound (IA-42), Compound (IA-45), Compound (IA-46), Compound ( IA-49), Compound (IA-50), Compound (IA-57), Compound (IA-58), Compound (IA-61), Compound (IA-62), Compound (IA-73), Compound (IA) -74), Compound (IA-77), Compound (IA-78), Compound (IA-81), Compound (IA-82), Compound (IA-89), Compound (IA-90), Compound (IA- 93), compound (IA-94), compound ( A-105), Compound (IA-106), Compound (IA-109), Compound (IA-110), Compound (IA-113), Compound (IA-114), Compound (IA-121), Compound (IA) -122), Compound (IA-125), Compound (IA-126), Compound (IA-257), Compound (IA-259), Compound (IA-261), Compound (IA-262), Compound (IA- H.264), Compound (IA-266), Compound (IA-267), Compound (IA-269), Compound (IA-271), Compound (IA-272), Compound (IA-274), Compound (IA-276) ), Compound (IA-277), Compound (IA-279), Compound (IA-281), Compound (IA-282), Compound (IA-284), Compound (IA-286), Compound (IA-287), Compound (IA-289), Compound (IA-291), Compound (IA-292), Compound (IA-294), Compound (IA-296), Compound (IA-301), Compound (IA-302), Compound (IA-305), Compound (IA-306), Compound (IA-309), Compound (IA-310), Compound (IA-313), Compound (IA-314) and Compound ( IA-333) to Compound (IA-404) are more preferable,
Compound (IA-13), Compound (IA-14), Compound (IA-17), Compound (IA-18), Compound (IA-45), Compound (IA-46), Compound (IA-49), Compound (IA-50), Compound (IA-77), Compound (IA-78), Compound (IA-81), Compound (IA-82), Compound (IA-109), Compound (IA-110), Compound ( IA-113), Compound (IA-114), Compound (IA-257), Compound (IA-259), Compound (IA-261), Compound (IA-262), Compound (IA-264), Compound (IA) -266), Compound (IA-277), Compound (IA-279), Compound (IA-281), Compound (IA-282), Compound (IA-284), Compound (IA-286) and Compound (IA- 01) - Compound (IA-330) and compound (IA-333) - Compound (IA-404) are more preferred,
Compound (IA-13), Compound (IA-14), Compound (IA-17), Compound (IA-18), Compound (IA-45), Compound (IA-46), Compound (IA-49) and Compound (IA-50) is particularly preferred.

Among the compounds (I) in which L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group and Z is a group represented by the formula (Z2), the solubility of the compound (I) in a solvent and From the viewpoint of the brightness of the color filter formed from the colored curable resin composition, the compound (IB-1), the compound (IB-2), the compound (IB-3), the compound (IB-4), and the compound (IB- 5), Compound (IB-6), Compound (IB-7), Compound (IB-8), Compound (IB-9), Compound (IB-10), Compound (IB-11), Compound (IB-12) ), Compound (IB-13), Compound (IB-14), Compound (IB-15), Compound (IB-16), Compound (IB-17), Compound (IB-18), Compound (IB-19) , Compound (IB-20), Compound (IB-31), Compound (IB-32), Compound (IB-33), Compound (IB-34), Compound (IB-35), Compound (IB-36), Compound (IB-37), Compound (IB-38), Compound ( IB-39), Compound (IB-40), Compound (IB-41), Compound (IB-42), Compound (IB-43), Compound (IB-44), Compound (IB-45), Compound (IB) -46), compound (IB-47), compound (IB-48), compound (IB-49) and compound (IB-50) are preferred, compound (IB-1), compound (IB-2), compound ( IB-3), Compound (IB-4), Compound (IB-5), Compound (IB-6), Compound (IB-7), Compound (IB-8), Compound (IB-9), Compound (IB) -10), compound (IB-11), compound (IB-1) ), Compound (IB-31), Compound (IB-32), Compound (IB-33), Compound (IB-34), Compound (IB-35), Compound (IB-36), Compound (IB-37) , Compound (IB-38), Compound (IB-39), Compound (IB-40), Compound (IB-41) and Compound (IB-42) are more preferable,
More preferred are compound (IB-1), compound (IB-2), compound (IB-31) and compound (IB-32).

Compound (I) wherein L is a divalent hydrocarbon group or sulfonyl group having 1 to 20 carbon atoms, and Z is a group represented by formula (Z1) or a group represented by formula (Z2) That is, a compound represented by the following formula (Ia-1) (hereinafter sometimes referred to as compound (Ia-1)) and a compound represented by the following formula (Ia-2) (hereinafter referred to as compound (Ia-1)) -2) is a novel compound, has high thermal stability, and is suitable as a colorant component of a colored curable resin composition.

(In the formula (Ia-1), ^{L a} is a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms (-SO ₂ - represents a), X and ^{R 7} ~ ^{R 13} are the same meaning as described above Z ^a represents a group represented by the formula (Z1).)

(In formula (Ia-2), L ^a , X and R ⁷ to R ¹³ represent the same meaning as described above, and Z ^b represents a group represented by formula (Z2).)

Among the compounds (Ia-1), R ¹ is an alkyl group having 1 to 16 carbon atoms, and —CH ₂ — constituting the alkyl group is preferably a compound (Ia-1) which may be replaced with an oxygen atom. Compound (Ia-1) in which R ¹ is an alkyl group having 6 to 10 carbon atoms is more preferred.
Among the compounds (Ia-2), Ar ¹ is a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, or a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position and the meta position. A certain compound (Ia-2) is preferable, and Ar ¹ is a phenyl group having a methyl group, an ethyl group or an isopropyl group at the ortho position, or a phenyl group having a methyl group, an ethyl group or an isopropyl group at the ortho position and the meta position. The compound (Ia-2) which is is more preferable.

Compound (I) is a compound represented by formula (II) (hereinafter sometimes referred to as compound (II)) and a compound represented by formula (III) (hereinafter referred to as compound (III)). May be produced by reacting in the presence of a base. The compound (II) in which L is a divalent hydrocarbon group or sulfonyl group having 1 to 20 carbon atoms, that is, the compound represented by the following formula (IIa) and the compound (III) are both novel. A compound.

(In the formula, L, L ^a , X, Z, R ⁷ to R ⁹ and R ¹¹ to R ¹³ represent the same meaning as described above, and R ¹⁵ and R ¹⁶ each independently represent 1 to Represents 20 alkyl groups.)

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹⁵ and R ¹⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. An alkyl group having 1 to 6 carbon atoms is preferable. R ¹⁵ and R ¹⁶ are preferably the same group.

Examples of the base include organic bases such as triethylamine and piperidine, and the amount used is usually 0.1 to 20 mol with respect to 1 mol of compound (II).
The amount of compound (III) to be used is generally 2 to 10 mol, preferably 2 to 4 mol, per 1 mol of compound (II).

The reaction between compound (II) and compound (III) is usually carried out in the presence of a solvent. Examples of the solvent include nitrile solvents such as acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, Alcohol solvents such as 1-octanol, ether solvents such as tetrahydrofuran, ketone solvents such as acetone, ester solvents such as ethyl acetate, aliphatic hydrocarbon solvents such as hexane, aromatic hydrocarbon solvents such as toluene, methylene chloride, chloroform, etc. And amide solvents such as N, N-dimethylformaldehyde and N-methylpyrrolidone, nitrile solvents, alcohol solvents and aromatic hydrocarbon solvents are preferable, and acetonitrile, methanol and toluene are more preferable. . The amount to be used is usually 1 part by mass to 50 parts by mass with respect to 1 part by mass of compound (II).
The reaction temperature is usually 0 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C. The reaction time is usually 0.5 hours to 36 hours.
After completion of the reaction, for example, the compound (I) can be taken out by mixing a solvent in which the compound (I) is difficult to dissolve with the obtained reaction mixture and filtering.

Compound (III) can be produced by reacting a compound represented by formula (IV) (hereinafter sometimes referred to as compound (IV)) with a formylating agent.

(In the formula, Z and R ⁷ to R ⁹ represent the same meaning as described above.)

An example of the formylating agent is phosphoryl chloride. The amount used is usually 1 to 5 mol per 1 mol of compound (IV).
The reaction of compound (IV) with a formylating agent is usually carried out in the presence of a solvent, and examples of the solvent include N, N-dimethylformamide. The amount to be used is usually 1 part by mass to 10 parts by mass with respect to 1 part by mass of compound (IV).
The reaction temperature is usually from 0 ° C to 100 ° C, and the reaction time is usually from 0.5 hours to 24 hours.
After completion of the reaction, for example, the reaction mixture is neutralized, extracted with an organic solvent insoluble in water such as ethyl acetate, and the resulting organic layer is concentrated to extract compound (III).

Compound (IV) is produced by reacting a compound represented by formula (V) (hereinafter sometimes referred to as compound (V)) with boron tribromide, followed by hydrolysis. Can do.

(In the formula, Z and R ⁷ to R ⁹ represent the same meaning as described above, and R ¹⁷ represents an alkyl group having 1 to 4 carbon atoms.)

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

The amount of boron tribromide to be used is usually 1 to 5 mol per 1 mol of compound (V).
The reaction of compound (V) with boron tribromide is usually carried out in a solvent, and examples of the solvent include halogenated hydrocarbon solvents such as dichloromethane. The amount of the solvent to be used is generally 1-50 parts by mass with respect to 1 part by mass of compound (V).
The reaction temperature is usually −78 ° C. to 50 ° C., and the reaction time is usually 1 to 24 hours.
After completion of the reaction, for example, the reaction mixture and water are mixed and then separated, and the resulting organic layer can be concentrated to take out the compound (IV).

The compound (V) in which Z is the formula (Z1) is, for example, a compound represented by the formula (VI) (hereinafter sometimes referred to as the compound (VI)) and a compound represented by the formula (VII). (Hereinafter, may be referred to as compound (VII)) in the presence of a palladium catalyst and a base.

The compound (V) in which Z is the formula (Z1) is, for example, a compound represented by the formula (VIII) (hereinafter sometimes referred to as the compound (VIII)) and a compound represented by the formula (IX). (Hereinafter sometimes referred to as compound (IX)) can also be produced by reacting in the presence of a base.

(Wherein R ¹ to R ⁹ and R ¹⁷ represent the same meaning as described above, and X ² and X ³ each independently represent a halogen atom, a methanesulfonyloxy group, a toluenesulfonyloxy group, or trifluoromethanesulfonyloxy. Represents a group.)

Examples of the halogen atom represented by X ² and X ³ include a chlorine atom, a bromine atom and an iodine atom.

The reaction between compound (VI) and compound (VII) can be carried out according to a known method for amination of an aromatic halide (for example, J. Org. Chem. 2003, 68, 1163-1164, etc.). . Specifically, a palladium catalyst such as palladium (II) acetate and a phosphorus-based ligand (for example, 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo [3 3.3] undecane, etc.), a base such as potassium tert-butoxide, compound (VI), compound (VII), and a solvent such as toluene can be mixed to carry out the reaction. The reaction temperature is usually 50 ° C. to 150 ° C., and the reaction time is usually 0.5 to 24 hours. After completion of the reaction, for example, the compound (V) can be taken out by mixing the reaction mixture and water, separating the organic layer, and concentrating the obtained organic layer.

The reaction of compound (VIII) and compound (IX) can be carried out according to a known alkylation method of an amine compound (for example, J. Org. Chem. 2011, 76, 8015-8021 etc.). Specifically, a base such as triethylamine, sodium hydride, sodium methoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, a compound (VIII), a compound (IX), a solvent such as dimethyl sulfoxide, The reaction can be carried out by mixing. The reaction temperature is usually 0 ° C. to 100 ° C., and the reaction time is usually 0.5 to 72 hours. After completion of the reaction, for example, the reaction mixture, water and, if necessary, an organic solvent insoluble in water are mixed, the organic layer is separated, and the obtained organic layer is concentrated to obtain the compound (V). It can be taken out.

The compound (V) in which Z is the formula (Z2) is, for example, a compound represented by the formula (XV) (hereinafter sometimes referred to as the compound (XV)) and a compound represented by the formula (XVI). (Hereinafter, it may be described as the compound (XVI)).

(In the formula, Ar ¹ , R ⁷ to R ⁹ and R ¹⁷ represent the same meaning as described above, and X ³ represents a halogen atom, a methanesulfonyloxy group, a toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group. )

Examples of the halogen atom represented by X ³ include a chlorine atom, a bromine atom and an iodine atom.

The reaction between the compound (XV) and the compound (XVI) is carried out according to a known coupling reaction between an aromatic amine and an aromatic halide (for example, J. Mater. Chem. 1997, 7, 2343-2354, etc.). Can be implemented. Specifically, the reaction can be carried out by mixing copper, a base such as potassium carbonate, compound (XV), compound (XVI), and a solvent such as dichlorobenzene. The reaction may be carried out in the presence of a phase transfer catalyst such as 18-crown-6. The amount of compound (XVI) to be used is generally 2 to 5 mol per 1 mol of compound (XV). The reaction temperature is usually 50 ° C. to 200 ° C., and the reaction time is usually 0.5 to 96 hours. After completion of the reaction, for example, the reaction mixture is filtered, washed with an acid to obtain an organic layer, and the resulting organic layer is concentrated to extract the compound (V).

Compound (II) is a compound represented by formula (X) (hereinafter sometimes referred to as compound (X)) and a compound represented by formula (XI) (hereinafter referred to as compound (XI)). And a compound represented by formula (XII) (hereinafter sometimes referred to as compound (XII)) in a solvent.

(Wherein R ¹¹ to R ¹³ , R ¹⁵ , R ¹⁶ , L and X represent the same meaning as described above, and R ²⁰ represents an alkyl group having 1 to 4 carbon atoms.)

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ²⁰ include a methyl group, an ethyl group, a propyl group, and a butyl group.

The amount of compound (XI) to be used is generally 1 to 2.5 mol, preferably 1 to 1.5 mol, per 1 mol of compound (X). The amount of compound (XII) to be used is generally 1 to 2.5 mol, preferably 1 to 1.5 mol, per 1 mol of compound (X). Compound (XI) and compound (XII) are preferably the same compound, and the amount used is usually 2 to 5 mol, preferably 2 to 3 mol, per 1 mol of compound (X).
Examples of the solvent include alcohol solvents such as methanol, and the amount used is usually 1 to 100 parts by mass with respect to 1 part by mass of compound (X).
The reaction temperature is usually −20 ° C. to 100 ° C., and the reaction time is usually 1 to 72 hours.

After completion of the reaction, for example, if necessary, the reaction mixture and water are mixed, and then extracted with an organic solvent insoluble in water such as ethyl acetate, and the obtained organic layer is concentrated to give compound (II). Can be taken out. Moreover, after completion | finish of reaction, after mixing a reaction mixture, water, or methanol as needed, for example, compound (II) can also be taken out by filtering.

Compound (XI) and Compound (XII) are, for example, J. Med. Chem. It can be produced according to a known method such as the method described in 2012, 55, 3398-3413.

<Colorant>
The colored curable resin composition of the present invention contains a colorant, and the colorant contains compound (I). The colorant (hereinafter sometimes referred to as “colorant (A)”) contains compound (I) as an active ingredient. The colorant (A) may be composed only of the compound (I) or may contain a dye or pigment other than the compound (I). The colorant (A) preferably contains a pigment in addition to the compound (I). The content ratio of the compound (I) in the colorant (A) is usually 1 to 100% by mass, preferably 3 to 100% by mass, more preferably 3 to 70% by mass. More preferably, it is 60 mass%.

As dyes other than Compound (I), Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, Reactive, Direct ( Examples include compounds classified as Direct, Disperse, or Vat. Specific examples include dyes having the following color index (CI) numbers.
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 etc.

Examples of the pigment include known pigments, for example, pigments classified as pigments by Color Index (published by The Society of Dyer's and Colorists).
Specifically, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. A brown pigment such as CI Pigment Brown 23 and 25; and C.I. I. And black pigments such as CI Pigment Black 1 and 7.

Among these, phthalocyanine pigments are preferable, and at least one selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferable. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. Particularly preferred is at least one selected from the group consisting of CI Pigment Green 58. These pigments are suitable as green colorants, and by using a colorant containing these pigments, it is easy to optimize the transmission spectrum, and it is possible to form a color filter with good light resistance and chemical resistance. it can.

If necessary, the pigment is 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, etc., sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. The particle diameter of the pigment is preferably substantially uniform. 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.
Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Corporation), EFKA (manufactured by CIBA), Ajisper (Ajinomoto Fine Techno Co., Ltd.), Disperbyk (Bic Chemie Co., Ltd.) 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, there is a tendency that a pigment dispersion with a more uniform dispersion state is obtained.

<Colored curable resin composition>
In addition to the colorant (A), the colored curable resin composition of the present invention includes a resin (hereinafter sometimes referred to as “resin (B)”), a polymerizable compound (hereinafter referred to as “polymerizable compound ( C) ”, a polymerization initiator (hereinafter sometimes referred to as“ polymerization initiator (D) ”) and a solvent (hereinafter sometimes referred to as“ solvent (E) ”). The colored curable resin composition of the present invention may contain a leveling agent in addition to these components. The colored curable resin composition of the present invention may contain a polymerization initiation assistant in addition to these components.

The content of the colorant (A) in the colored curable resin composition is usually 1% by mass or more and 70% by mass or less, preferably 1% by mass or more and 60% by mass or less, based on the total amount of the solid content. More preferably, it is 5 mass% or more and 60 mass% or less, Most preferably, it is 5 mass% or more and 50 mass% or less. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be easily obtained. In addition, in this specification, "the total amount of solid content" means the total amount of the component remove | excluding the solvent 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 and gas chromatography, for example.

<Resin (B)>
The resin (B) contained in the colored curable resin composition of the present invention is preferably an alkali-soluble resin and has a structure derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. More preferred are addition polymers having units. Examples of such a resin include the following resins [K1] to [K6].
Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”) Resin [K2]: (a), (b), (a) A copolymer with a monomer (c) copolymerizable with (but different from (a) and (b)) (hereinafter sometimes referred to as “(c)”) Resin [K3]: (a ) And (c) Copolymer Resin [K4]: Resin obtained by reacting (b) with copolymer of (a) and (c) Resin [K5]: (b) and (c Resin [K6]: a resin obtained by reacting a copolymer with (a) with a copolymer with (a) It reacted, resin obtained by further reacting a carboxylic acid anhydride.

As (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, 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 [2.2.1] bicyclounsaturated compounds containing a carboxy group such as 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 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] ;
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 and maleic anhydride are preferred from the viewpoints of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.

(B) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, an oxirane ring, an oxetane ring, a tetrahydrofuran ring, etc.) and an ethylenically unsaturated bond. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group. In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid, and the notation of “(meth) acryloyl” and “(meth) acrylate” is also used. Indicate the same meaning.

(B) includes a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a monomer having an oxetanyl group and an ethylenically unsaturated bond. (B2) (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”).

(B1) may be a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) ) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).
As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6- An example is tris (glycidyloxymethyl) styrene.
(B1-2) includes vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, formula ( Examples thereof include a compound represented by 1) and a compound represented by formula (2).

(Wherein, R ^a and R ^b each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X ^a and ^{X b} are each independently a single ^{^{bond, -R c -, * - R}} c -O -, * - R c -S- or ^* -R represents the c -NH- .R ^c is the number of carbon atoms Represents an alkanediyl group of 1 to 6. * represents a bond to O.)

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and 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 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 each independently preferably ^a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
Examples of the alkanediyl group having 1 to 6 carbon atoms include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5. -Diyl group and hexane-1,6-diyl group are mentioned.
X ^a and X ^b are each independently a single bond, a methylene group, an ethylene group, * —CH ₂ —O— or * —CH ₂ CH ₂ —O—, preferably a single bond or * —CH _2. More preferably, it is CH ₂ —O—. In the above formula, * represents a bond with O.

Examples of the compound represented by the formula (1) include compounds represented by the formula (1-1) to the formula (1-15), among which the formula (1-1) and the formula (1-3) And compounds represented by formula (1-5), formula (1-7), formula (1-9) and formula (1-11) to formula (1-15) are preferred, and formula (1-1), The compounds represented by formula (1-7), formula (1-9) and formula (1-15) are more preferred.

Examples of the compound represented by the formula (2) include compounds represented by the formula (2-1) to the formula (2-15). Among them, the formula (2-1) and the formula (2-3) And compounds represented by formula (2-5), formula (2-7), formula (2-9) and formula (2-11) to formula (2-15) are preferred, and formula (2-1), The compounds represented by formula (2-7), formula (2-9) and formula (2-15) are more preferred.

The compound represented by the formula (1) and the compound represented by the formula (2) may be used alone, or the compound represented by the formula (1) and the compound represented by the formula (2) May be used in combination. When these are used in combination, the ratio of the compound represented by formula (1) and the compound represented by formula (2) (compound represented by formula (1): compound represented by formula (2)) is mol. The standard is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still 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 and 3-ethyl-3-acryloyloxyethyl oxetane.

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

(B) is preferably (b1), and the storage stability of the colored curable resin composition is excellent in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. In this respect, (b1) is preferably (b1-2).

As (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} ] Decan-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”) .), Torisiku [5.2.1.0 ^{2, 6]} (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Decene-8-yl (meth) acrylate, dicyclopentanyl Such as oxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid ester;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. 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 compounds such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene and 2,3-dimethyl-1,3-butadiene.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N -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 to 60 mol%
Structural unit derived from (b): 40 to 98 mol%
It is preferable that
Structural unit derived from (a): 10 to 50 mol%
Structural unit derived from (b): 50 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 obtained color filter are more improved. It tends to be excellent.

Resin [K1] is, for example, the method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on 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 and 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.) Any solvent may be used as long as it dissolves each monomer. Examples of the solvent for the colored curable resin composition of the present invention include the solvents described later.

As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. 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 to 45 mol%
Structural unit derived from (b): 2 to 95 mol%
Structural unit derived from (c): 1 to 65 mol%
It is preferable that
Structural unit derived from (a): 5 to 40 mol%
Structural unit derived from (b): 5 to 80 mol%
Structural unit derived from (c): 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, 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 to 60 mol%
Structural unit derived from (c): 40 to 98 mol%
It is preferable that
Structural unit derived from (a): 10 to 50 mol%
Structural unit derived from (c): 50 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 (b) has a carboxylic acid and / or carboxylic acid anhydride having (b) a cyclic ether moiety having 2 to 4 carbon atoms. It can be manufactured by adding to a product. Specifically, it can be produced as follows. First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the 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, a cyclic ether compound having 2 to 4 carbon atoms 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 catalyst for the reaction of the carboxylic acid or carboxylic anhydride with the cyclic ether compound (for example, A resin [K4] is produced by placing tris (dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) in a flask and reacting, for example, at 60-130 ° C. for 1-10 hours. 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). The colored curable resin composition containing a resin obtained by adjusting the amount of (b) used in this range is storage stability, developability when forming a pattern, solvent resistance of the resulting pattern, heat resistance Tend to have a better balance of properties, mechanical strength and sensitivity. Since the reactivity of the cyclic ether moiety is high and unreacted (b) hardly remains, (b) used in the resin [K4] is preferably (b1) and more preferably (b1-1).

The amount of the 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 of each reagent, the reaction temperature, and the reaction 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 the total number of moles of all structural units constituting the copolymer, respectively.
Structural unit derived from (b): 5 to 95 mol%
Structural unit derived from (c): 5 to 95 mol%
It is preferable that
Structural unit derived from (b): 10 to 90 mol%
Structural unit derived from (c): 10 to 90 mol%
It is more preferable that

Furthermore, the carboxylic acid or carboxylic acid which (a) has in the cyclic ether part derived from (b) which the copolymer of (b) and (c) has on the same conditions as the manufacturing method of resin [K4] Resin [K5] can be obtained by reacting an anhydride.

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 moiety is high and unreacted (b) hardly remains, (b) used in the resin [K5] is preferably (b1) and more preferably (b1-1).

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 a cyclic ether moiety 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 and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of carboxylic acid anhydride used is preferably 0.5 to 1 mole per mole of (a) used.

Examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meta ) Resin such as 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-epoxy tricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer , Benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer, etc. resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer to glycidyl (meth) Resin with acrylate added, Resin with glycidyl (meth) acrylate added to 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 added resin; resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / styrene / Resin such as a resin obtained by reacting a copolymer of glycidyl (meth) acrylate with (meth) acrylic acid [K5]; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) acrylic acid And a resin [K6] such as a resin obtained by further reacting tetrahydrophthalic anhydride with the resin reacted with.

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 polystyrene equivalent weight average molecular weight of the resin (B) is usually 3,000 to 100,000, preferably 5,000 to 50,000, more preferably 5,000 to 35,000, Preferably it is 5,000 to 30,000, and particularly preferably 6,000 to 30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed 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 preferably 20 to 170 mg-KOH / g, more preferably 30 to 170 mg-KOH / g, of which 40 to 170 mg-KOH / g is preferred, of which 50 to 170 mg-KOH / g is preferred, of which 50-150 mg-KOH / g is preferred, of which 60-150 mg-KOH / g is preferred, of which 60-135 mg-KOH / g is more preferred. ~ 135 mg-KOH / g is 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 to 65% by mass, preferably 10 to 60% by mass, and more preferably 13 to 60% by mass, based on the total solid content. Of these, the content is preferably 17 to 55% by mass. When the content of the resin (B) is in the above range, a colored pattern can be easily formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from a polymerization initiator, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, and a (meth) acrylic acid ester Compounds having a structure are preferred. The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds.

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, N-vinylpyrrolidone, (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 (meta). ) Acrylate, bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Examples of the polymerizable compound having three or more ethylenically unsaturated bonds 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 di Intererythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) An acrylate is mentioned.
Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The content of the polymerizable compound (C) in the colored curable resin composition of the present invention is usually 5 to 65% by mass, preferably 7 to 65% by mass with respect to the total solid content, and more The amount is preferably 10 to 60% by mass, more preferably 13 to 60% by mass, and particularly preferably 17 to 55% by mass. The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, preferably 35:65, based on mass. ~ 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 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-ethi -6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine And at least one selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, and N-benzoyloxy-1- (4- More preferred is phenylsulfanylphenyl) octane-1-one-2-imine.

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

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

Examples of the compound having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy ) Phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyl Examples include dimethyl ketal.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d2).

Examples of the biimidazole compound include a compound represented by the formula (d5).

(In the formula, 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 tolyl group, a xylyl group, an ethylphenyl group and a naphthyl group, preferably a phenyl group. Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, Preferably it is a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferable.

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, etc.), 2,2'-bis (2-chlorophenyl) -4,4', 5,5 '-Tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole (for example, , JPS 48-38403-B, JPS 62-174204-A, etc.) and imidazole compounds in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group (for example, JPH07-10913-A) Reference). Of these, compounds represented by the following formula and mixtures thereof are preferred.

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) ete Le] -1,3,5-triazine and 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.

Other polymerization initiators include 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-4 ′. -Benzophenone compounds such as methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2- Examples include quinone compounds such as ethyl anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant described below (particularly an amine polymerization initiation assistant).

The polymerization initiator (D) preferably contains 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 O-acyloxy. Compound.

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

<Polymerization initiation aid>
The polymerization initiation assistant is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiation assistant, it is usually used in combination with a polymerization initiator (D).
Examples of the polymerization initiation assistant include amine polymerization initiation assistants, alkoxyanthracene polymerization initiation assistants, thioxanthone polymerization initiation assistants, and carboxylic acid polymerization initiation assistants.

Examples of the amine polymerization initiation assistant include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone and 4,4 '-Bis (ethylmethylamino) benzophenone is mentioned, and 4,4'-bis (diethylamino) benzophenone is particularly preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

As an alkoxyanthracene polymerization initiation assistant, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, Examples include 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

Carboxylic acid polymerization initiators include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenyl And sulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When a polymerization initiation assistant is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiation assistant 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 limited, The solvent normally used in the said field | area can be used. Specifically, 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 (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O -, -CO- and -COO- free solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, pyruvin Examples include methyl acid, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

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

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

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

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

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

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

These solvents may be used 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, di- Propylene glycol methyl ether acetate, ethyl lactate, 3-methyl Carboxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and N- methylpyrrolidone is more preferred.

The content of the solvent (E) is usually 70 to 95% by mass, preferably 75 to 92% by mass, and more preferably 75 to 90% by mass with respect to the total amount of the colored curable resin composition. . 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>
Examples of the leveling agent 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 surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) It is done.

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

Examples of the silicone 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, and F443 (manufactured by DIC Corporation) can be mentioned.

The content of the leveling agent is usually from 0.0005% by mass to 0.6% by mass, preferably from 0.001% by mass to 0.5% by mass, based on the total amount of the colored curable resin composition. More preferably, it is 0.001 mass% or more and 0.2 mass% or less, More preferably, it is 0.002 mass% or more and 0.1 mass% or less, Especially preferably, it is 0.005 mass% or more and 0.07 mass%. % Or less. When the leveling agent 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 (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and, if necessary, It can be prepared by mixing a leveling agent, a polymerization initiation aid and other components. In addition to the colorant (A), pigments and dyes can also be mixed. The pigment is preferably mixed in advance with a part or all of the solvent (E) and used in the state of a pigment dispersion dispersed using a bead mill or the like until the average particle size 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.
It is preferable to prepare a solution by dissolving Compound (I) in part or all of the solvent (E) in advance. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film 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 can be appropriately adjusted according to the purpose and application, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm.

As a 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, an aluminum, silver, silver / copper / palladium alloy thin film or the like is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

The 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 a spin coating method, a slit coating method, and a slit and spin coating method. The temperature for performing heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Further, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When drying under reduced pressure, it is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp. Use an exposure device such as a mask aligner or stepper because it can irradiate parallel light uniformly over the entire exposure surface and perform precise alignment between the photomask and 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. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide. The concentration of the alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass. The developer may contain a surfactant. The development method may be any of paddle method, dipping method and spray method. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

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

The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used for 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 part 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 model, MASS: Agilent LC / MSD6130 model).

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: Tetrahydrofuran Flow rate: 1.0 mL / min Analysis sample solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard materials: 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
10.1 parts of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 51.0 parts of methanol are mixed and stirred at 5 ° C. or lower with ethyl 3-ethoxy-3-iminopropionate 12.6. Part was added. The reaction mixture was then stirred at 10 ° C. or lower for only 5 hours, at room temperature for only 24 hours, and at 60 ° C. for only 24 hours. After cooling the reaction mixture to room temperature, 300 parts of water and 270 parts of ethyl acetate were added, and the ethyl acetate layer was separated. To the aqueous layer was added 135 parts of ethyl acetate, and the ethyl acetate layer was separated. To the aqueous layer was added 135 parts of ethyl acetate, and the ethyl acetate layer was separated. The ethyl acetate layers were combined, washed three times with 300 parts of water, dried over magnesium sulfate, and filtered. The filtrate was evaporated to give a residue. This residue was purified by column chromatography to obtain 14.5 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] + 559.1
Exact Mass: 558.1

Under a nitrogen atmosphere, 75.0 parts of dimethyl sulfoxide and 8.45 parts of potassium hydroxide were mixed and stirred at room temperature for 0.5 hour. To this mixture, 25.0 parts of 3-methoxydiphenylamine was added and stirred at room temperature for 0.5 hour. To this mixture, 21.5 parts of iodoethane was added and stirred at room temperature for 2 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added and stirred at room temperature for 1 hour, and then 10.8 parts of iodoethane was added and stirred at room temperature for 12 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added and stirred at room temperature for 1 hour, and then 10.8 parts of iodoethane was added and stirred at room temperature for 2 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added and stirred at room temperature for 1 hour, and then 10.8 parts of iodoethane was added and stirred at room temperature for 13 hours. To the obtained mixture, 158 parts of water and 135 parts of ethyl acetate were added, and the ethyl acetate layer was separated. 90 parts of ethyl acetate was added to the aqueous layer, and the ethyl acetate layer was separated. The ethyl acetate layers were combined and washed 3 times with 100 parts of water. The ethyl acetate solution was dried over magnesium sulfate and filtered. The solvent of this filtrate was distilled off to obtain 28.4 parts of a compound represented by the formula (pt3-1).

<Identification of Compound Represented by Formula (pt3-1)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 228.1
Exact Mass: 227.1

Under a nitrogen atmosphere, 28.4 parts of the compound represented by the formula (pt3-1) and 302 parts of methylene chloride were mixed. While maintaining this mixture at 4 to 10 ° C., 44.8 parts of boron tribromide was added, followed by stirring at room temperature for 12 hours. The obtained mixture was added to a mixture of 341 parts of water and 302 parts of methylene chloride while keeping the temperature of the mixture of 341 parts of water and 302 parts of methylene chloride at 4 to 19 ° C. The mixture was stirred at room temperature for 2 hours, and the methylene chloride layer was separated. This methylene chloride solution was washed four times with 227 parts of 10 wt% brine, dried over magnesium sulfate, and filtered. The solvent of this filtrate was distilled off to obtain 23.3 parts of a compound represented by the formula (pt4-1).

<Identification of compound represented by formula (pt4-1)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 214.1
Exact Mass: 213.1

Under a nitrogen atmosphere, 25.1 parts of phosphoryl chloride was added to 47.7 parts of N, N-dimethylformamide while maintaining the temperature at 6-15 ° C. A mixture of 23.3 parts of the compound represented by the formula (pt4-1) and 31.4 parts of N, N-dimethylformamide was added to the mixture while maintaining the temperature of the mixture at 6 to 25 ° C. The mixture was stirred at 40 ° C. for 2 hours and then cooled to room temperature. The obtained mixture was added to a mixture of 109 parts of a 48 wt% aqueous sodium hydroxide solution and 410 parts of water while maintaining the temperature at 14-19 ° C. and stirred for 1 hour. While maintaining the temperature at 12 to 17 ° C., 67.2 parts of 35 wt% hydrochloric acid was added to the obtained mixture. To the resulting mixture, 210 parts of ethyl acetate and celite were added and filtered. The obtained filtrate was washed twice with 233 parts of 10 wt% brine, dried over magnesium sulfate, and filtered. The solvent of the obtained filtrate was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 23.9 parts of a compound represented by the formula (pt5-1).

<Identification of Compound Represented by Formula (pt5-1)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 242.1
Exact Mass: 241.1

Under a nitrogen atmosphere, 10.9 parts of the compound represented by the formula (pt5-1), 12.0 parts of the compound represented by the formula (pt1), 0.915 parts of piperidine, and 83.8 parts of toluene were mixed. The mixture was stirred at 100 ° C. for 19 hours. The solvent of this mixed solution was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 10.6 parts of a compound represented by the formula (I-1).

<Identification of Compound Represented by Formula (I-1)>
¹ H-NMR (CDCl ₃ , 270 MHz) δ 1.31 (6H), 3.84 (4H), 6.58-6.61 (4H), 7.16-7.24 (4H), 7.31 -7.39 (6H), 7.46-7.52 (4H), 7.55 (2H), 7.99 (2H), 8.63 (2H)

Synthesis example 2
2,2.4 parts of 2,4-dimethylaniline, 35.4 parts of triethylamine and 132 parts of N, N-dimethylformamide were mixed and stirred at 50 ° C. While maintaining the temperature of this mixture at 50 to 60 ° C., 56.8 parts of iodoethane were added, and then stirred at 60 ° C. for 65 hours. The mixture was allowed to cool to room temperature, 1000 parts of water and 433 parts of toluene were added, and the toluene layer was separated. The toluene layer was washed three times with 1000 parts of a saturated aqueous sodium chloride solution, and then the solvent was distilled off with a rotary evaporator. The obtained residue was purified by column chromatography to obtain 18.8 parts of a compound represented by the formula (pt2-2).

<Identification of Compound Represented by Formula (pt2-2)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 150.1
Exact Mass: 149.1

Under a nitrogen atmosphere, 29.8 parts of the compound represented by the formula (pt2-2), 37.4 parts of 3-bromoanisole, 1.35 parts of palladium (II) acetate, 33.7 parts of potassium tert-butoxide, 2 , 8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (1.0 M toluene solution) 3.42 parts and toluene 520 parts, Stir at 100 ° C. for 6 hours. The mixture was allowed to cool to room temperature and then added to 1000 parts of water. After filtering this liquid mixture, the toluene layer was fractionated. The toluene solution was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, and then filtered. The solvent of this filtrate was distilled off using a rotary evaporator, and the resulting residue was purified by column chromatography to obtain 41.9 parts of a compound represented by the formula (pt3-2).

<Identification of compound represented by formula (pt3-2)>
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 256.2
Exact Mass: 255.2

The synthesis was performed in the same manner as in Synthesis Example 1 except that the compound represented by the formula (pt3-1) was replaced with the compound represented by the formula (pt3-2) in Synthesis Example 1, and the formula (pt4-2) The compounds represented by formula (pt5-2) and formula (I-2) were obtained.

<Identification of each compound>
Compound (mass spectrometry) ionization mode represented by formula (pt4-2) = ESI +: m / z = [M + H] ⁺ 242.2
Exact Mass: 241.2
Compound represented by formula (pt5-2) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 270.2
Exact Mass: 269.1
Compound represented by formula (I-2)
¹ H-NMR (CDCl ₃ , 270 MHz) δ 1.30 (6H), 2.09 (6H), 2.39 (6H), 3.59 (2H), 3.86 (2H), 6.42 ( 4H), 7.00 (2H), 7.12 (2H), 7.18 (2H), 7.30-7.37 (4H), 7.54 (2H), 7.98 (2H), 8 .62 (2H)

Synthesis example 3
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and 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.

Synthesis example 4
Under a nitrogen atmosphere, m-anisidine 24.0 parts, 4-iodo-m-xylene 99.7 parts, potassium carbonate 117 parts, copper powder 27.3 parts, 18-crown-6 4.64 parts, o-di 511 parts of chlorobenzene was mixed and stirred at 175 ° C. for 19 hours. Thereafter, 35.1 parts of potassium carbonate, 8.19 parts of copper powder, 1.39 parts of 18-crown-6, and 22.0 parts of o-dichlorobenzene were added and stirred at 175 ° C. for 17 hours. The mixture was allowed to cool to room temperature and filtered. 450 parts of ethyl acetate was added to the filtrate and washed 3 times with 450 parts of 2N hydrochloric acid and 3 times with 470 parts of an 18 wt% sodium chloride aqueous solution. The resulting ethyl acetate solution was dried over magnesium sulfate and filtered. The solvent of the filtrate was distilled off with a rotary evaporator, and then the obtained residue was purified by column chromatography to obtain 64.1 parts of a compound represented by the formula (pt3-3).

<Identification of Compound Represented by Formula (pt3-3)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 332.2
Exact Mass: 331.2

The synthesis was performed in the same manner as in Synthesis Example 1 except that the compound represented by the formula (pt3-1) was replaced with the compound represented by the formula (pt3-3) in the synthesis example 1, and the formula (pt4-3) The compounds represented by formula (pt5-3) and formula (I-82) were obtained.

<Identification of each compound>
Compound represented by formula (pt4-3) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 318.2
Exact Mass: 317.2
Compound represented by formula (pt5-3) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 346.2
Exact Mass: 345.2
Compound (mass spectrometry) ionization mode represented by formula (I-82) = ESI +: m / z = [M + H] ⁺ 1121.4
Exact Mass: 1120.4

Synthesis example 5
The same procedure as in Synthesis Example 1 was performed except that iodoethane was replaced with 2-ethoxyethyl bromide in Synthesis Example 1, and the formula (pt3-4), formula (pt4-4), formula (pt5-4), and formula A compound represented by (I-141) was obtained.

<Identification of each compound>
Compound represented by formula (pt3-4) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 272.2
Exact Mass: 271.2
Compounds of formula (pt4-4) (Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 258.1
Exact Mass: 257.1
Compound represented by formula (pt5-4) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 286.1
Exact Mass: 285.1
Compound (mass spectrometry) ionization mode represented by formula (I-141) = ESI +: m / z = [M + H] ⁺ 1001.3
Exact Mass: 1000.3

Synthesis Example 6
The same procedure as in Synthetic Example 2 was performed except that 2,4-dimethylaniline was replaced with 2,4,6-trimethylaniline in Synthesis Example 2, and the formula (pt2-5), formula (pt3-5), The compounds represented by formula (pt4-5), formula (pt5-5) and formula (I-146) were obtained.

<Identification of each compound>
Compound (mass spectrometry) ionization mode represented by formula (pt2-5) = ESI +: m / z = [M + H] ⁺ 164.1
Exact Mass: 163.1
Compound represented by formula (pt3-5) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 270.2
Exact Mass: 269.2
Compound represented by formula (pt4-5) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 256.2
Exact Mass: 255.2
Compound represented by formula (pt5-5) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 284.2
Exact Mass: 283.2
Compound (mass spectrometry) ionization mode represented by formula (I-146) = ESI +: m / z = [M + H] ⁺ 997.3
Exact Mass: 996.3

Synthesis example 7
The same procedure as in Synthetic Example 4 was performed except that 4-iodo-m-xylene was replaced with 2-iodo-1,3,5-trimethylbenzene in Synthesis Example 4, and formula (pt3-6), formula ( The compounds represented by pt4-6), formula (pt5-6) and formula (I-86) were obtained.

<Identification of each compound>
Compound represented by formula (pt3-6) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 360.2
Exact Mass: 359.2
Compound represented by formula (pt4-6) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 346.2
Exact Mass: 345.2
Compound (mass spectrometry) ionization mode represented by formula (pt5-6) = ESI +: m / z = [M + H] ⁺ 374.2
Exact Mass: 373.2
Compound represented by formula (I-86) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 1177.4
Exact Mass: 1176.4

Example 1
4.98 parts of bis (3-amino-4-hydroxyphenyl) sulfone and 28.1 parts of methanol were mixed. To the resulting mixture, 8.18 parts of ethyl 3-ethoxy-3-iminopropionate hydrochloride was gradually added at 10 ° C. or lower with stirring. The resulting mixture was stirred at 10 ° C. or lower for 7 hours, at room temperature for 24 hours, and at 60 ° C. for 24 hours. The obtained reaction mixture was cooled to room temperature, and the precipitated crystals were taken out by filtration. The taken out crystal was washed with methanol and dried under reduced pressure at 60 ° C. to obtain 6.77 parts of a compound represented by the formula (pt1-1a).

<Identification of Compound Represented by Formula (pt1-1a)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 473.1
Exact Mass: 472.1

2,2.4 parts of 2,4-dimethylaniline, 35.4 parts of triethylamine and 132 parts of N, N-dimethylformamide were mixed and stirred at 50 ° C. While maintaining the temperature of the mixture at 50 to 60 ° C., 70.2 parts of 1-bromo-2-ethylhexane was added, and then the mixture was stirred at 60 ° C. for 65 hours. The mixture was allowed to cool to room temperature, 1000 parts of water and 433 parts of toluene were added, and the toluene layer was separated. The toluene layer was washed three times with 1000 parts of a saturated aqueous sodium chloride solution, and then the solvent was distilled off with a rotary evaporator. The obtained residue was purified by column chromatography to obtain 50.6 parts of a compound represented by the formula (pt2-1a).

<Identification of Compound Represented by Formula (pt2-1a)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 234.2
Exact Mass: 233.2

Under a nitrogen atmosphere, 46.7 parts of the compound represented by the formula (pt2-1a), 37.4 parts of 3-bromoanisole, 1.35 parts of palladium (II) acetate, 33.7 parts of potassium tert-butoxide, 2 , 8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (1.0 M toluene solution) 3.42 parts and toluene 520 parts, Stir at 100 ° C. for 6 hours. The resulting mixture was allowed to cool to room temperature and then added to 1000 parts of water. After the obtained mixture was filtered, the toluene layer was separated. The tolueneso layer was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, and then filtered. The filtrate was evaporated using a rotary evaporator, and the resulting residue was purified by column chromatography to obtain 30.9 parts of a compound represented by the formula (pt3-1a).

<Identification of Compound Represented by Formula (pt3-1a)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 340.3
Exact Mass: 339.3

Under a nitrogen atmosphere, 17.0 parts of the compound represented by the formula (pt3-1a) and 199 parts of dichloromethane were mixed. While maintaining this mixed liquid at 15 to 23 ° C., boron tribromide (1.0 M dichloromethane solution) was added in an amount equal to the number of moles of the compound represented by the formula (pt3-1a). Thereafter, the mixture was stirred at room temperature for 8 hours. The obtained mixture was added to 250 parts of ice water, and the dichloromethane layer was separated. The dichloromethane layer was washed with 250 parts of water, dried over magnesium sulfate and filtered. The obtained filtrate was evaporated using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 13.9 parts of a compound represented by the formula (pt4-1a).

<Identification of compound represented by formula (pt4-1a)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 326.3
Exact Mass: 325.2

13.9 parts of the compound represented by the formula (pt4-1a) and 26.4 parts of N, N-dimethylformamide were mixed. While maintaining this mixture at 23 to 55 ° C., 13.1 parts of phosphoryl chloride was added. The mixture was then stirred at 60 ° C. for 6 hours. The mixture was allowed to cool to room temperature, added to 150 parts of ice water, and neutralized with a 48% aqueous sodium hydroxide solution. To this mixture, 300 parts of ethyl acetate was added and filtered, and the ethyl acetate layer was separated from the obtained filtrate. This ethyl acetate solution was washed with 300 parts of water, dried over magnesium sulfate, and filtered. The obtained filtrate was evaporated using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 11.6 parts of a compound represented by the formula (pt5-1a).

<Identification of Compound Represented by Formula (pt5-1a)>
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 354.2
Exact Mass: 353.2

Under a nitrogen atmosphere, 9.65 parts of the compound represented by the formula (pt5-1a), 6.14 parts of the compound represented by the formula (pt1-1a), 0.553 parts of piperidine and 51.1 parts of toluene were mixed. did. The mixture was stirred at 100 ° C. for 19 hours. This mixture was added to 231 parts of methanol. The generated precipitate was taken out by removing the supernatant. After adding 231 parts of methanol to the precipitate and stirring, the mixture was suction filtered. The obtained residue was washed with 20 parts of methanol and obtained as a residue of suction filtration. This residue was purified by column chromatography to obtain 9.10 parts of a compound represented by the formula (IA-13).

<Identification of Compound Represented by Formula (IA-13)>
¹ H-NMR (CDCl ₃ , 270 MHz) δ 0.82-0.92 (12H), 1.26-1.52 (16H), 1.77 (2H), 2.05 (6H), 2.38 (6H), 3.32-3.42 (2H), 3.71-3.78 (2H), 6.42-6.45 (4H), 7.02 (2H), 7.11 (2H) 7.15 (2H), 7.33 (2H), 7.66 (2H), 7.96 (2H), 8.39 (2H), 8.62 (2H)

Example 2
The same procedure as in Example 1 was conducted except that 1-bromo-2-ethylhexane was replaced with 1-bromooctane in Example 1, and the formula (pt2-2a), formula (pt3-2a), formula ( The compounds represented by pt4-2a), formula (pt5-2a) and formula (IA-17) were obtained.

<Identification of each compound>
Compound represented by formula (pt2-2a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 234.2
Exact Mass: 233.2
Compound represented by formula (pt3-2a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 340.3
Exact Mass: 339.3
Compound represented by formula (pt4-2a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 326.3
Exact Mass: 325.2
Compound (mass spectrometry) ionization mode represented by formula (pt5-2a) = ESI +: m / z = [M + H] ⁺ 354.2
Exact Mass: 353.2
Compound represented by formula (IA-17)
¹ H-NMR (CDCl ₃ , 270 MHz) δ 0.88 (6H), 1.28-1.32 (20H), 1.72 (4H), 2.07 (6H), 2.38 (6H), 3.44 (2H), 3.77 (2H), 6.39 (4H), 6.99 (2H), 7.12 (2H), 7.17 (2H), 7.34 (2H), 7 .66 (2H), 7.96 (2H), 8.39 (2H), 8.62 (2H)

Example 3
The same procedure as in Example 1 was performed except that 1-bromo-2-ethylhexane was replaced by 1-bromo-3-methylbutane in Example 1, and the formula (pt2-3a) and the formula (pt3-3a) The compound represented by formula (pt4-3a), formula (pt5-3a) and formula (IA-297) was obtained.

<Identification of each compound>
Compound (mass spectrometry) ionization mode represented by formula (pt2-3a) = ESI +: m / z = [M + H] ⁺ 192.2
Exact Mass: 191.2
Compound represented by formula (pt3-3a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 298.2
Exact Mass: 297.2
Compound (mass spectrometry) ionization mode represented by formula (pt4-3a) = ESI +: m / z = [M + H] ⁺ 284.2
Exact Mass: 283.2
Compound represented by formula (pt5-3a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 312.2
Exact Mass: 311.2
Compound represented by formula (IA-297)
¹ H-NMR (CDCl ₃ , 270 MHz) δ 0.96 (12H), 1.57-1.69 (6H), 2.08 (6H), 2.39 (6H), 3.47 (2H), 3.80 (2H), 6.39 (4H), 6.99 (2H), 7.12 (2H), 7.17 (2H), 7.34 (2H), 7.66 (2H), 7 .96 (2H), 8.39 (2H), 8.62 (2H)

Example 4
Under a nitrogen atmosphere, 39.9 parts (0.200 mol) of 3-methoxydiphenylamine, 13.5 parts (0.240 mol) of potassium hydroxide and 550 parts of dimethyl sulfoxide were mixed and stirred at room temperature for 2 hours. To this mixture, 42.5 parts (0.220 mol) of 1-bromo-2-ethylhexane was added and stirred at room temperature for 6 hours. To this mixture were added 42.5 parts (0.220 mol) of 1-bromo-2-ethylhexane and 20.2 parts (0.360 mol) of potassium hydroxide, and the mixture was stirred at room temperature for 14 hours. To this mixture, 63.7 parts (0.330 mol) of 1-bromo-2-ethylhexane and 20.2 parts (0.360 mol) of potassium hydroxide were added and stirred at room temperature for 24 hours. To this mixture, 1000 parts of water and 450 parts of toluene were added, and the toluene layer was separated. This toluene solution was washed twice with 1500 parts of a saturated aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, and filtered. The solvent of the obtained filtrate was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 59.8 parts of a compound represented by the formula (pt3-4a).

<Identification of compound represented by formula (pt3-4a)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 312.2
Exact Mass: 311.2

The same procedure as in Example 1 was performed except that the compound represented by the formula (pt3-1a) was replaced with the formula (pt3-4a) in Example 1, and the formula (pt4-4a) and the formula (pt5- The compound represented by 4a) and formula (IA-15) was obtained.

<Identification of each compound>
Compound represented by formula (pt4-4a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 298.2
Exact Mass: 297.2
Compound (mass spectrometry) ionization mode represented by formula (pt5-4a) = ESI +: m / z = [M + H] ⁺ 326.2
Exact Mass: 325.2
Compound represented by formula (IA-15)
¹ H-NMR (CDCl ₃ , 270 MHz) δ 0.82-0.88 (12H), 1.22-1.52 (16H), 1.80 (2H), 3.69 (4H), 6.58 -6.63 (4H), 7.21-7.24 (4H), 7.31-7.37 (4H), 7.45-7.50 (4H), 7.67 (2H), 7. 97 (2H), 8.40 (2H), 8.63 (2H)

Example 5
The same procedure as in Example 4 was performed except that 1-bromo-2-ethylhexane was replaced with 1-bromododecane in Example 4, and the formula (pt3-5a), formula (pt4-5a), formula ( pt5-5a) and the compound represented by formula (IA-299) were obtained.

<Identification of each compound>
Compound represented by formula (pt3-5a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 368.3
Exact Mass: 367.3
Compound represented by formula (pt4-5a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 354.3
Exact Mass: 353.3
Compound represented by formula (pt5-5a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 382.3
Exact Mass: 381.3
Compound represented by formula (IA-299)
¹ H-NMR (CDCl ₃ , 270 MHz) δ 0.87 (6H), 1.25-1.30 (36H), 1.72 (4H), 3.72 (4H), 6.54-6.58 (4H), 7.20-7.23 (4H), 7.33-7.39 (4H), 7.46-7.51 (4H), 7.67 (2H), 7.97 (2H) , 8.40 (2H), 8.63 (2H)

Example 6
The same procedure as in Example 1 was performed except that 1-bromo-2-ethylhexane was replaced with 2-ethoxyethyl bromide in Example 1, and the formula (pt2-6a), formula (pt3-6a), formula The compounds represented by (pt4-6a), formula (pt5-6a) and formula (IA-306) were obtained.

<Identification of each compound>
Compound represented by formula (pt2-6a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 194.2
Exact Mass: 193.1
Compound (mass spectrometry) ionization mode represented by formula (pt3-6a) = ESI +: m / z = [M + H] ⁺ 300.2
Exact Mass: 299.2
Compound represented by formula (pt4-6a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 286.2
Exact Mass: 285.2
Compound (mass spectrometry) ionization mode represented by formula (pt5-6a) = ESI +: m / z = [M + H] ⁺ 314.2
Exact Mass: 313.2
Compound (mass spectrometry) ionization mode represented by formula (IA-306) = ESI +: m / z = [M + H] ⁺ 971.3
Exact Mass: 970.3

Example 7
10.0 parts of 2,2-bis (3-amino-4-hydroxyphenyl) propane and 51.0 parts of methanol are mixed and stirred at 5 ° C. or lower with ethyl 3-ethoxy-3-iminopropionate hydrochloride 18 .2 parts were added. The reaction mixture was then stirred at 13 ° C. or lower for only 13 hours, at room temperature for only 24 hours, and at 60 ° C. for only 24 hours. The above reaction mixture was cooled to room temperature. The reaction mixture was evaporated using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 6.46 parts of the compound represented by the formula (pt1-7a).

<Identification of Compound Represented by Formula (pt1-7a)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 451.2
Exact Mass: 450.2

In Example 1, except that the compound represented by the formula (pt1-1a) was replaced with the compound represented by the formula (pt1-7a) and 1-bromo-2-ethylhexane was replaced with 1-bromooctane, The reaction was carried out in the same manner as in Example 1 to obtain the compound represented by the formula (IA-49).

<Identification of Compound Represented by Formula (IA-49)>
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 1029.6
Exact Mass: 1028.5

Example 8
Mixing 5.09 parts of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene and 30.0 parts of methanol and stirring, ethyl 3-ethoxy-3-iminopropionate hydrochloride at 5 ° C. or less 10 parts were added. The reaction mixture was then stirred at 10 ° C. or lower for only 14 hours, at room temperature for only 24 hours, and at 60 ° C. for only 24 hours. The above reaction mixture was cooled to room temperature. The reaction mixture was evaporated using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 2.33 parts of a compound represented by the formula (pt1-8a).

<Identification of Compound Represented by Formula (pt1-8a)>
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 573.2
Exact Mass: 572.2

In Example 1, except that the compound represented by the formula (pt1-1a) was replaced with the compound represented by the formula (pt1-8a) and 1-bromo-2-ethylhexane was replaced with 1-bromooctane, The reaction was carried out in the same manner as in Example 1 to obtain the compound represented by the formula (IA-81).

Identification of Compound Represented by Formula (IA-81)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 1151.6
Exact Mass: 1150.6

Example 9
The same procedure as in Example 1 was performed except that 2,4-dimethylaniline was replaced with 2,4,6-trimethylaniline and 1-bromo-2-ethylhexane was replaced with 1-bromooctane. Thus, the compounds represented by formula (pt2-9a), formula (pt3-9a), formula (pt4-9a), formula (pt5-9a) and formula (I-308) were obtained.

<Identification of each compound>
Compound represented by formula (pt2-9a) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 248.2
Exact Mass: 247.2
Compound (mass spectrometry) ionization mode represented by formula (pt3-9a) = ESI +: m / z = [M + H] ⁺ 354.3
Exact Mass: 353.3
Compound (mass spectrometry) ionization mode represented by formula (pt4-9a) = ESI +: m / z = [M + H] ⁺ 340.3
Exact Mass: 339.3
Compound (mass spectrometry) ionization mode represented by formula (pt5-9a) = ESI +: m / z = [M + H] ⁺ 368.3
Exact Mass: 367.3
Compound (mass spectrometry) ionization mode represented by formula (IA-308) = ESI +: m / z = [M + H] ⁺ 1079.5
Exact Mass: 1078.5

Example 10
In Example 1, the compound represented by the formula (pt1-1a) was replaced with the compound represented by the formula (pt1-7a), and 2,4-dimethylaniline was replaced with 2,4,6-trimethylaniline. The compound represented by the formula (IA-311) was obtained in the same manner as in Example 1 except that 1-bromooctane was replaced with 1-bromooctane.

<Identification of Compound Represented by Formula (IA-311)>
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 1057.6
Exact Mass: 1056.6

<Heat resistance evaluation>
Using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA6200R manufactured by SII Nanotechnology), the formulas (IA-13), (IA-17), and (IA-297) obtained in Examples 1 to 10 were used. ), Formula (IA-15), formula (IA-299), formula (IA-306), formula (IA-49), formula (IA-81), formula (IA-308) and formula (IA-311) Differential scanning calorimetry of the compound represented by the formula and Coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) 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. The temperature T ₅ (under air) at which the weight reduction rate is 5% in air, the temperature T ₁₀ (under air) at which the weight reduction rate is 10% in air, and the weight reduction rate is 5% in a nitrogen atmosphere. The temperature T ₅ (under nitrogen) and the temperature T ₁₀ (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 of Table 30, it can be seen that the compound (Ia-1) of the present invention has high thermal stability.

Example 11
4.98 parts of bis (3-amino-4-hydroxyphenyl) sulfone and 28.1 parts of methanol are mixed, and gradually 8.18 parts of ethyl 3-ethoxy-3-iminopyropionate hydrochloride is added at 10 ° C. or lower with stirring. Added to. The reaction mixture was then stirred at 10 ° C. or lower for only 7 hours, at room temperature for 24 hours, and at 60 ° C. for 24 hours. The reaction mixture was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. This residue was washed with methanol and dried under reduced pressure at 60 ° C. to obtain 6.77 parts of a compound represented by the formula (pt1-1b).

<Identification of Compound Represented by Formula (pt1-1b)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 473.1
Exact Mass: 472.1

Under a nitrogen atmosphere, m-anisidine 24.0 parts, 4-iodo-m-xylene 99.7 parts, potassium carbonate 117 parts, copper powder 27.3 parts, 18-crown-6 4.64 parts, o-di 511 parts of chlorobenzene was mixed and stirred at 175 ° C. for 19 hours. Thereafter, 35.1 parts of potassium carbonate, 8.19 parts of copper powder, 1.39 parts of 18-crown-6, and 22.0 parts of o-dichlorobenzene were added and stirred at 175 ° C. for 17 hours. The mixture was allowed to cool to room temperature and filtered. 450 parts of ethyl acetate was added to the filtrate and washed 3 times with 450 parts of 2N hydrochloric acid and 3 times with 470 parts of an 18 wt% sodium chloride aqueous solution. The resulting ethyl acetate solution was dried over magnesium sulfate and filtered. The solvent of the filtrate was distilled off with a rotary evaporator, and then the resulting residue was purified by column chromatography to obtain 64.1 parts of a compound represented by the formula (pt2-1b).

<Identification of Compound Represented by Formula (pt2-1b)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 332.2
Exact Mass: 331.2

31.7 parts of the compound represented by the formula (pt2-1b) and 190 parts of dehydrated dichloromethane were mixed at 0 ° C. under a nitrogen atmosphere. Subsequently, 199 parts of a 17 wt% boron tribromide dichloromethane solution was added and stirred for 1 hour. Then, it stirred at room temperature for 12 hours. After this mixture was added to 1100 parts of ice water, 740 parts of chloroform was added, and the chloroform layer was extracted. The obtained chloroform solution was washed twice with 470 parts of an 18 wt% aqueous sodium chloride solution, dried over magnesium sulfate, and filtered. After the solvent of the filtrate was distilled off with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 30.0 parts of a compound represented by the formula (pt3-1b).

<Identification of Compound Represented by Formula (pt3-1b)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 318.2
Exact Mass: 317.2

7.46 parts of the compound represented by the formula (pt3-1b) and 14.4 parts of N, N-dimethylformamide were mixed at 5 to 10 ° C. under a nitrogen atmosphere. While maintaining the temperature of this mixture at 5 to 10 ° C., 7.21 parts of phosphoryl chloride was added. Thereafter, the mixture was stirred at 10 ° C. or lower for 1 hour, at room temperature for 1 hour, and at 80 ° C. for 1 hour. The reaction mixture was allowed to cool to room temperature, 100 parts of ice water was added, and the mixture was neutralized with a 48% aqueous sodium hydroxide solution. To this mixture was added 180 parts of ethyl acetate, followed by celite and stirring. The mixture was filtered and the ethyl acetate layer was extracted. The ethyl acetate layer was dried over magnesium sulfate and filtered. The solvent of this filtrate was distilled off with a rotary evaporator, and then the obtained residue was purified by column chromatography to obtain 6.26 parts of a compound represented by the formula (pt4-1b).

<Identification of compound represented by formula (pt4-1b)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 346.2
Exact Mass: 345.2

6.01 parts of the compound represented by the formula (pt4-1b), 4.04 parts of the compound represented by the formula (pt1-1b), 0.357 parts of piperidine and 33.4 parts of toluene were mixed, For 6 hours. The mixture was allowed to cool to room temperature and then added to 153 parts of methanol. The precipitate was obtained as a residue of suction filtration. The obtained residue was purified by column chromatography to obtain 7.76 parts of a compound represented by the formula (IB-2).

<Identification of Compound Represented by Formula (IB-2)>
¹ H-NMR (CDCl ₃ , 270 MHz) δ 2.13 (12H), 2.34 (12H), 6.38 (2H), 6.52 (2H), 6.92-7.02 (8H), 7.10 (4H), 7.37 (2H), 7.67 (2H), 7.98 (2H), 8.40 (2H), 8.64 (2H)

Example 12
18. 10.0 parts of 2,2-bis (3-amino-4-hydroxyphenyl) propane and 51.0 parts of methanol are mixed and stirred with ethyl 3-ethoxy-3-iminopyropionate at 5 ° C. or lower. Two parts were added. The reaction mixture was then stirred at 13 ° C. or lower for only 13 hours, at room temperature for only 24 hours, and at 60 ° C. for only 24 hours. The above reaction mixture was cooled to room temperature. The reaction mixture was evaporated using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 6.46 parts of the compound represented by the formula (pt1-2b).

<Identification of compound represented by formula (pt1-2b)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 451.2
Exact Mass: 450.2

Example 11 was carried out in the same manner as in Example 11 except that the compound represented by the formula (pt1-1b) was replaced with the compound represented by the formula (pt1-2b), and the compound represented by the formula (IB-32) The compound represented by these was obtained.

<Identification of Compound Represented by Formula (IB-32)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 1013.4
Exact Mass: 1012.4

Example 13
Mixing 5.09 parts of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene and 30.0 parts of methanol and stirring, ethyl 3-ethoxy-3-iminopropionate hydrochloride at 5 ° C. or less 10 parts were added. The reaction mixture was then stirred at 10 ° C. or lower for only 14 hours, at room temperature for only 24 hours, and at 60 ° C. for only 24 hours. The above reaction mixture was cooled to room temperature. The reaction mixture was evaporated using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 2.33 parts of a compound represented by the formula (pt1-3b).

<Identification of Compound Represented by Formula (pt1-3b)>
(Mass Spectrometry) ionization mode ^{= ESI +: m / z =} [M + H] + 573.2
Exact Mass: 572.2

Example 11 was carried out in the same manner as in Example 11 except that the compound represented by the formula (pt1-1b) was replaced with the compound represented by the formula (pt1-3b), and the compound represented by the formula (IB-62) The compound represented by these was obtained.

<Identification of Compound Represented by Formula (IB-62)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 1135.4
Exact Mass: 1134.4

Example 14
The same procedure as in Example 11 was performed except that 4-iodo-m-xylene was replaced with 2-iodo-1,3,5-trimethylbenzene in Example 11, and the formula (pt2-4b) and the formula ( The compounds represented by pt3-4b), formula (pt4-4b) and formula (IB-6) were obtained.

<Identification of each compound>
Compound (mass spectrometry) ionization mode represented by formula (pt2-4b) = ESI +: m / z = [M + H] ⁺ 360.2
Exact Mass: 359.2
Compound (mass spectrometry) ionization mode represented by formula (pt3-4b) = ESI +: m / z = [M + H] ⁺ 346.2
Exact Mass: 345.2
Compound represented by formula (pt4-4b) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 374.2
Exact Mass: 373.2
Compound represented by formula (IB-6) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 1091.4
Exact Mass: 1090.4

Example 15
In Example 11, the compound represented by the formula (pt1-1b) was replaced with the compound represented by the formula (pt1-2b), and 4-iodo-m-xylene was replaced with 2-iodo-1,3,5-trimethyl. Except having replaced with benzene, it implemented similarly to Example 11 and obtained the compound represented by a formula (IB-36).

<Identification of Compound Represented by Formula (IB-36)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 1069.5
Exact Mass: 1068.5

<Heat resistance evaluation>
Using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA6200R manufactured by SII Nanotechnology), the formulas (IB-2), (IB-32), and (IB-62) obtained in Examples 11 to 15 were used. ), Differential scanning calorimetry of the compound represented by formula (IB-6) and formula (IB-36) and coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.). 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. The temperature T ₅ (under air) at which the weight reduction rate is 5% in air, the temperature T ₁₀ (under air) at which the weight reduction rate is 10% in air, and the weight reduction rate is 5% in a nitrogen atmosphere. The temperature T ₅ (under nitrogen) and the temperature T ₁₀ (under nitrogen) at which the weight loss rate was 10% in a nitrogen atmosphere were determined. The results are shown in Table 31.

From the results of Table 31, it can be seen that the compound (Ia-2) of the present invention has high thermal stability.

<Preparation of colored curable resin composition>
Example 16
Pigment: C.I. I. Pigment Green 7 (pigment) 27 parts,
12 parts acrylic pigment dispersant,
Resin (B): Resin B1 (solid content conversion) 9.5 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 180 parts were mixed, and a pigment dispersion in which the pigment was sufficiently dispersed using a bead mill;
Colorant (A): 3.0 parts of compound represented by formula (I-1);
Resin (B): Resin B1 (solid content conversion) 40 parts;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 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) 9.8 parts;
Solvent (E): 670 parts of propylene glycol monomethyl ether acetate; and leveling agent): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 part is mixed to give a colored curable resin composition Got.

Example 17 to Example 33
In Example 16, C.I. I. Pigment Green 7 (pigment) was replaced with the pigment shown in Table 32, and the compound represented by formula (I-1) was replaced with the compound shown in Table 32. A functional resin composition was obtained.

Examples 34-63
In Example 16, C.I. I. Pigment Green 7 (pigment) was replaced with the pigment shown in Table 33, and the compound represented by the formula (I-1) was replaced with the compound shown in Table 33. A functional resin composition was obtained.

Examples 64-78
In Example 16, C.I. I. Pigment Green 7 (pigment) was replaced with the pigment shown in Table 34, and the compound represented by the formula (I-1) was replaced with the compound shown in Table 34. A functional resin composition was obtained.

<Film thickness measurement>
The film thickness was measured using DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.

<Preparation of resin composition for sublimation test (SJS)>
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 propylene glycol monomethyl ether;
Solvent: 6.8 parts of propylene glycol monomethyl ether acetate were mixed to obtain a resin composition for sublimation test (SJS).

<Formation of resin coating film for sublimation test (SJSM)>
On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the resin composition for sublimation test (SJS) obtained above was applied by spin coating, 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 (SJSM) (thickness: 2.2 μm) was formed by heating in an oven at 220 ° C. for 2 hours.

Example 79 <Preparation of colored pattern and evaluation of sublimation>
The colored curable resin composition obtained in Example 16 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. Formed. 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 in an air atmosphere at 80 mJ / cm ² 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 the exposure was 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, and washed with water. The film thickness was measured. The results are shown in Table 35.
This colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with a space of 70 μm between them, and post-baking at 220 ° C. for 40 minutes to obtain a colored pattern. . The color difference (ΔEab *) before and after heating of the resin coating film for sublimation test (SJSM) 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 35. In Table 35, in each example, ◯ indicates that the colorant does not have sublimability, and x indicates that the colorant has sublimability.

Example 80 to Example 142
In Example 79, a colored pattern was carried out in the same manner as in Example 79 except that the colored curable resin composition obtained in Example 16 was replaced with the colored curable resin composition shown in Tables 35 to 37. Similarly, the sublimation property was evaluated. The results are shown in Tables 35 to 37.

Comparative Example 1
Colorant: Coumarin 6 3.6 parts;
Resin (B): Resin (B1) (solid content conversion) 180 parts;
Solvent (E): 230 parts of propylene glycol monomethyl ether acetate;
Solvent (E): N, N-dimethylformamide 590 parts; and leveling agent: polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.063 parts are mixed to obtain a colored resin composition. It was.
The colored resin composition obtained above 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. The film thickness was measured to be 1.9 μm using DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.
The colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with a space of 70 μm between them, and post-baked at 220 ° C. for 40 minutes. The color difference (ΔEab *) before and after heating of the resin coating film for sublimation test (SJSM) was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). As a result, the color difference (ΔEab *) was 5.0 or more, and it was confirmed that coumarin 6 as a colorant has sublimability.

From the above results, it was found that the colored curable resin composition of the present invention can form a color filter without the colorant sublimating.

According to the present invention, a color filter can be formed without sublimation of the colorant. Therefore, the color filter is suitably used for a display device such as a liquid crystal display device.

Claims

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and a solvent containing a compound represented by formula (I).

(In the formula, L represents a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a sulfonyl group (—SO 2 —), and X represents oxygen R 7 to R 13 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (—CONH 2 ), a sulfamoyl group (—SO 2 NH 2 ), — SO 3 M, —CO 2 M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, —CH 2 — constituting the hydrocarbon group is an oxygen atom, sulfur atom, -N (R 14) -, may be replaced to a sulfonyl group or a carbonyl group, a hydrogen atom contained in the hydrocarbon group include a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO M, -CO 2 M, hydroxy group, may be replaced to formyl group or an amino group, R 14 represents a monovalent hydrocarbon group hydrogen atom or a C 1 ~ 20, R 14 there are a plurality of In this case, they may be the same or different, and M represents a hydrogen atom or an alkali metal atom, and when a plurality of M are present, they may be the same or different. Well,
Z represents the formula (Z1):

(Wherein R 1 represents an alkyl group having 1 to 20 carbon atoms, —CH 2 — constituting the alkyl group may be replaced by an oxygen atom, and R 2 to R 6 are each independently A hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO 3 M, —CO 2 M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. And —CH 2 — constituting the hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R 30 ) —, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group It is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO 3 M, -CO 2 M , hydroxy group, may be replaced to formyl group or an amino group, R 30 Represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when there are a plurality of R 30 s , they may be the same or different, and M is a hydrogen atom or Represents an alkali metal atom, and when a plurality of M are present, they may be the same or different, and * represents a bond.
Or a group represented by formula (Z2):

(In the formula, Ar 1 represents a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, the meta position, or both, and * represents a bond.)
Represents a group represented by )
2. The colored curable resin composition according to claim 1, wherein L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
2. The colored curable resin composition according to claim 1, wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group.
The colored curable resin composition according to any one of claims 1 to 3, wherein Z is a group represented by the formula (Z1).
5. The colored curable resin composition according to claim 1, wherein R 1 is an alkyl group having 1 to 16 carbon atoms, and —CH 2 — constituting the alkyl group may be replaced by an oxygen atom. .
The colored curable resin composition according to claim 2, wherein Z is a group represented by the formula (Z1), and R 1 is an alkyl group having 1 to 8 carbon atoms.
The colored curable resin composition according to claim 3, wherein Z is a group represented by the formula (Z1), and R 1 is an alkyl group having 6 to 10 carbon atoms.
The colored curable resin composition according to any one of claims 1 to 3, wherein Z is a group represented by the formula (Z2).
Ar 1 is a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, or a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position and the meta position. The colored curable resin composition according to any one of 8.
The colored curable resin composition according to claim 9, wherein the alkyl group having 1 to 8 carbon atoms is a methyl group, an ethyl group or an isopropyl group.
The colored curable resin composition according to any one of claims 1 to 10, wherein the colorant further contains a pigment.
The colored curable resin composition according to claim 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.
The colored curable resin composition according to claim 11, 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.
The colored curable resin composition according to any one of claims 11 to 13, wherein the pigment is a green pigment.
The pigment is C.I. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. 15. The colored curable resin composition according to claim 11, wherein the colored curable resin composition is at least one selected from the group consisting of CI Pigment Green 58.
A color filter formed from the colored curable resin composition according to any one of claims 1 to 15.
A liquid crystal display device comprising the color filter according to claim 16.
A compound represented by formula (Ia-1).

(Wherein, L a is a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms (-SO 2 - represents a), X represents an oxygen atom or a sulfur atom, R 7 ~ R 13 is Independently, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (—CONH 2 ), a sulfamoyl group (—SO 2 NH 2 ), —SO 3 M, —CO 2 M, a hydroxy group, and a formyl group Represents an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH 2 — constituting the hydrocarbon group is an oxygen atom, a sulfur atom, —N (R 14 ) —, a sulfonyl group or a carbonyl group. It may be replaced based on the hydrogen atoms contained in the hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO 3 M, -CO 2 M , hydroxy group, Hol May be replaced in the group or amino group, R 14 represents a monovalent hydrocarbon group hydrogen atom or a C 1-20, if R 14 is plurally present, they may be the same M may represent a hydrogen atom or an alkali metal atom, and when a plurality of M are present, they may be the same or different,
Z a represents a group represented by the formula (Z1).

(Wherein R 1 represents an alkyl group having 1 to 20 carbon atoms, —CH 2 — constituting the alkyl group may be replaced by an oxygen atom, and R 2 to R 6 are each independently A hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO 3 M, —CO 2 M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. And —CH 2 — constituting the hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R 30 ) —, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group It is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO 3 M, -CO 2 M , hydroxy group, may be replaced to formyl group or an amino group, R 30 Represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when there are a plurality of R 30 s , they may be the same or different, and M is a hydrogen atom or Represents an alkali metal atom, and when a plurality of M are present, they may be the same or different, and * represents a bond.))
19. The compound according to claim 18, wherein R 1 is an alkyl group having 1 to 16 carbon atoms, and —CH 2 — constituting the alkyl group may be replaced with an oxygen atom.
The compound according to claim 18, wherein R 1 is an alkyl group having 6 to 10 carbon atoms.
A compound represented by formula (Ia-2).

(Wherein, L a is a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms (-SO 2 - represents a), X represents an oxygen atom or a sulfur atom, R 7 ~ R 13 is Independently, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (—CONH 2 ), a sulfamoyl group (—SO 2 NH 2 ), —SO 3 M, —CO 2 M, a hydroxy group, and a formyl group Represents an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH 2 — constituting the hydrocarbon group is an oxygen atom, a sulfur atom, —N (R 14 ) —, a sulfonyl group or a carbonyl group. It may be replaced based on the hydrogen atoms contained in the hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO 3 M, -CO 2 M , hydroxy group, Hol May be replaced in the group or amino group, R 14 represents a monovalent hydrocarbon group hydrogen atom or a C 1-20, if R 14 is plurally present, they may be the same M may represent a hydrogen atom or an alkali metal atom, and when a plurality of M are present, they may be the same or different,
Z b represents a group represented by the formula (Z2).

(In the formula, Ar 1 represents a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, the meta position, or both, and * represents a bond.)
The compound according to claim 21, wherein Ar 1 is a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, or a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position and the meta position.
The compound according to claim 22, wherein the alkyl group having 1 to 8 carbon atoms is a methyl group, an ethyl group or an isopropyl group.
A colorant comprising the compound according to any one of claims 18 to 23.
The colorant according to claim 24, further comprising a pigment.
A compound represented by the formula (IIa).

(Wherein, L a represents a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms, X represents an oxygen atom or a sulfur atom, R 11 ~ R 13 are each independently hydrogen An atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO 3 M, —CO 2 M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The —CH 2 — constituting the hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R 14 ) —, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO 3 M, -CO 2 M , hydroxy group, may be replaced to formyl group or an amino group, R 1 Represents a monovalent hydrocarbon group hydrogen atom or a C 1-20, if R 14 there are a plurality, to which may be the same or different, M is a hydrogen atom or Represents an alkali metal atom, and when a plurality of M are present, they may be the same or different, and R 15 and R 16 each independently represents an alkyl group having 1 to 20 carbon atoms; Represents.)
A compound represented by formula (III).

(Wherein R 7 to R 9 are each independently a hydrogen atom, halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, —SO 3 M, —CO 2 M, hydroxy group, formyl group, Represents an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and —CH 2 — constituting the hydrocarbon group is an oxygen atom, a sulfur atom, —N (R 14 ) —, a sulfonyl group or a carbonyl group; The hydrogen atom contained in the hydrocarbon group may be a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO 3 M, —CO 2 M, a hydroxy group, a formyl group or an amino group. good .R 14 be replaced in groups, a monovalent hydrocarbon group hydrogen atom or a C 1-20, if R 14 there are a plurality, even they are the same M represents a hydrogen atom or an alkali metal atom, and when a plurality of M are present, they may be the same or different, and Z represents the formula (Z1) :

(Wherein R 1 represents an alkyl group having 1 to 20 carbon atoms, —CH 2 — constituting the alkyl group may be replaced by an oxygen atom, and R 2 to R 6 are each independently A hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO 3 M, —CO 2 M, a hydroxy group, a formyl group, an amino group, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. And —CH 2 — constituting the hydrocarbon group may be replaced by an oxygen atom, a sulfur atom, —N (R 30 ) —, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the hydrocarbon group It is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO 3 M, -CO 2 M , hydroxy group, may be replaced to formyl group or an amino group, R 30 Represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when there are a plurality of R 30 s , they may be the same or different, and M is a hydrogen atom or Represents an alkali metal atom, and when a plurality of M are present, they may be the same or different, and * represents a bond.
Or a group represented by formula (Z2):

(In the formula, Ar 1 represents a phenyl group having an alkyl group having 1 to 8 carbon atoms in the ortho position, the meta position, or both, and * represents a bond.)
Represents a group represented by )