WO2021005997A1

WO2021005997A1 - Composition containing coloring agent

Info

Publication number: WO2021005997A1
Application number: PCT/JP2020/023967
Authority: WO
Inventors: 昭妍朴
Original assignee: 住友化学株式会社
Priority date: 2019-07-10
Filing date: 2020-06-18
Publication date: 2021-01-14
Also published as: KR20220034155A; CN114080567A; TW202111012A; JP2021014568A

Abstract

According to the present invention, a composition which contains, as a coloring agent (A), a compound represented by formula (1a) or the like, and as a resin (B), a resin (B1) containing a constituent unit (b1-1) represented by formula (1b), wherein the content of the coloring agent (A) is from 35% by weight to 70% by weight with respect to the total solid content in the composition, is produced in advance, and a curable coloring composition is subsequently produced using the above-described composition. Consequently, thickening of the curable coloring composition is able to be suppressed. (In the formula, the symbols are as defined in the description.)

Description

Compositions containing colorants

The present invention relates to a composition containing a colorant. The composition of the present invention is useful for producing a color curable composition.

Color curable compositions are used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays, and various compositions have been developed. For example, Patent Document 1 describes a solvent, a reactive diluent, a photopolymerization initiator, a colorant, and the formula (1):

[Definition of symbols in formula (1) is as described in Patent Document 1. ]
A resin composition for a color filter containing a copolymer containing a structural unit represented by is described.

WO 2018/11007 A1

The color-curable composition containing the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D) and the solvent (E) is stored depending on the type of the colorant (A) used. The present inventor has found that there is a problem that the viscosity sometimes increases. The present invention has been made in view of such circumstances, and an object of the present invention is to suppress thickening of a color curable composition containing a specific colorant.

The present invention that can achieve the above object is as follows.
[1] A composition containing a colorant (A), a resin (B) and a solvent (E).
The colorant (A) has the formula (1a) :.

[In the formula (1a), R ^41a and R ^42a may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents a good aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41a and R ^42a are bonded to each other. Forming a 3 to 10-membered nitrogen-containing heterocycle with the nitrogen atom
R ^43a and R ^44a each independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 14 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R ^43a and R ^44a are bonded and bonded to each other. Forming a nitrogen-containing heterocycle,
R ^47a ~ ^{R 54a} are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - have _-SO 2 -R ^f or a substituent, Represents a good alkyl group with 1 to 8 carbon atoms
R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.
Ring T ^1a represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - -SO 2 - R ^f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
Substituents which may be the aralkyl group have the carbon number of 7 to 30, a halogen atom, a nitro group, hydroxy group, formyl _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - -SO 2 -R f, And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
Aromatic hydrocarbon ring substituent that have the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - -SO 2 - R ^f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
Wherein said 5 to 10-membered aromatic heterocyclic ring substituent which may have of a halogen atom, a nitro group, hydroxy group, formyl _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - -SO 2 -R f , And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH _2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-. May be
When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH _2- contained in the alkyl group may be replaced with -O- or -CO-.
r represents an integer of 1 or more
^{Mr +} represents a hydrogen ion, an r-valent metal ion or N ⁺ (R ^55a ) ₄ , and the four R ^55a may be the same or different.
R ^55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
k is the formula (1a-A):

[In the formula (1a-A), the rings T ^1a , R ^41a to R ^44a and R ^47a to R ^54a are synonymous with the above, respectively. ]
In -SO ₃ anion has represented ^- and _-SO 2 ^-N - represents the total number of _-SO 2 -R ^f, a and an integer of 2 or more,
When r is an integer of 2 or more, the plurality of anions represented by the formula (1a-A) may be the same or different, and when k-1 is an integer of 2 or more, a plurality of M's may be present. ^{r +} may be the same or different. ]
Compound represented by,
Equation (2a):

[In the formula (2a), R ^41b and R ^42b may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents a good aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41b and R ^42b are bonded to each other. Forming a 3 to 10-membered nitrogen-containing heterocycle with the nitrogen atom
R ^43b and R ^44b independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 14 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R ^43b and R ^44b are bonded and bonded to each other. Forming a nitrogen-containing heterocycle,
R ^47b to R ^54b each independently represent an alkyl group having 1 to 8 carbon atoms which may have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a substituent.
Ring T ^1b represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The substituents that the aromatic hydrocarbon group having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms. At least one selected from the group consisting of alkyl groups of
The substituents that the aralkyl group having 7 to 30 carbon atoms may have are a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent. At least one selected from the group consisting of
The substituents that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms. At least one selected from the group consisting of alkyl groups of
The substituents that the 5- to 10-membered aromatic heterocycle may have are a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl having 1 to 8 carbon atoms that may have a substituent. At least one selected from the group of groups,
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH _2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-. May be
When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH _2- contained in the alkyl group may be replaced with -O- or -CO-.
m represents an integer of 1 or more
[Y] ^m- represents an m-valent anion, and when m is an integer of 2 or more, the formula (2a-C):

[In the formula (2a-C), rings T ^1b , R ^41b to R ^44b and R ^47b to R ^54b are synonymous with the above, respectively. ]
The plurality of cations represented by may be the same or different. ]
The compound represented by, and formula (3a):

[In the formula (3a), R ¹ and R ² may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. A good aromatic hydrocarbon group with 6 to 10 carbon atoms or -R ^12- Si (R ¹³ ) ₃ is represented, or R ¹ and R ² are bonded and 3 to 10 members together with the nitrogen atom to which they are bonded. Forming a nitrogen-containing heterocycle,
R ³ and R ⁴ independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 10 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group or a group represented by -R ^12- Si (R ¹³ ) ₃ , or contains 3 to 10 members together with the nitrogen atom to which R ³ and R ⁴ are bonded. Forming a nitrogen heterocycle,
R ⁵ _{^{_{^{^{is, -OH, -SO 3 -, -SO}}}}} 3 - Z +, -SO 3 R 8, -CO 2 - Z +, -CO 2 R 8, or represents _-SO 2 ^NR 9 ^{R 10,}
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
p represents an integer of 0 to 5, and when p is an integer of 2 or more, a plurality of R ^5s may be the same or different.
q represents 0 or 1 and represents
X represents a halogen atom
Z ⁺ stands for N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ^11s may be the same or different.
R ⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a halogen atom.
R ⁹ and R ¹⁰ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, or R ⁹ and R ¹⁰ are bonded to each other. Together with the nitrogen atoms they bind to, they form a 3-10 member nitrogen-containing heterocycle,
R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
R ¹² represents an alkanediyl group having 1 to 10 carbon atoms.
R ¹³ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the three R ^13s may be the same or different, respectively.
The substituents that the saturated hydrocarbon groups having 1 to 20 carbon atoms of R ¹ to R ⁴ may have are aromatic hydrocarbon groups having 6 to 10 carbon atoms, halogen atoms, hydroxy groups, formyl groups and carboxy groups. At least one selected from the group of groups,
The substituents that may have the aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ may have a halogen atom, a hydroxy group, a formyl group, and a halogen atom. saturated hydrocarbon group of ^{_{^{_{~ 20, -OR 8, -SO 3}}}} -, -SO 3 - Z +, -SO 3 R 8, -CO 2 - Z +, -CO 2 R 8 and _-SO 2 ^NR 9 ^{R 10} At least one selected from the group consisting of
When the saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH _2- contained in the saturated hydrocarbon group is -O-, -CO- or ^{-NR 11} - may be replaced to,
The substituents of the saturated hydrocarbon groups having 1 to 20 carbon atoms of R ⁹ and R ¹⁰ may have at least one selected from the group consisting of a hydroxy group, a formyl group and a halogen atom.
When the saturated hydrocarbon group having 1 to 20 carbon atoms of R ⁹ and R ¹⁰ is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH _2- contained in the saturated hydrocarbon group is -O-, -CO- or -NR ⁸ - may be replaced to,
When the alkanediyl group having 1 to 10 carbon atoms of R ^{12 is} an alkanediyl group having 2 to 20 carbon atoms, -CH _2- contained in the alkanediyl group is -O-, -CO- or -NR. ⁸ - may be replaced in, and -SO ₃ in the form of ions in the compound represented by formula (3a) ^- if there is, the number is one. ]
Containing at least one selected from the group consisting of compounds represented by
The resin (B) is the formula (1b):

[In formula (1b), R ^1B represents a hydrogen atom or a methyl group.
R ^2B to R ^4B independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
n represents an integer from 1 to 10, and * represents the bond position.
However, at least one of R ^2B to R ^4B is an alkoxy group having 1 to 6 carbon atoms. ]
A composition containing a resin (B1) containing the structural unit (b1-1) represented by, and having a content of the colorant (A) of 35 to 70% by weight based on the total solid content of the composition. ..
[2] The composition according to the above [1], wherein the content of the colorant (A) is 40 to 70% by weight based on the total solid content of the composition.

[3] The ring T ^1a in the formula (1a) is the formula (1t):

[In the formula (1t), R ^45a and R ^46a may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents a good aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^45a and R ^46a are bonded to each other. Forming a 3 to 10-membered nitrogen-containing heterocycle with the nitrogen atom
R ^56a is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have a group.
L ^1a represents a sulfur atom, an oxygen atom or -NR ^57a- .
R ^57a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - -SO 2 - R ^f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
Substituents which may be the aralkyl group have the carbon number of 7 to 30, a halogen atom, a nitro group, hydroxy group, formyl _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - -SO 2 -R f, And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms, and * represents a bond position with a carbocation. ]
The composition according to the above [1] or [2], which is a ring represented by.

[4] The composition according to any one of the above [1] to [3], wherein ^r is 2 and ^{Mr +} is a divalent metal ion in the formula (1a).

[5] In the formula (1a), R ^41a and R ^43a are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R ^42a and R ^44a are each independently an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- at least one of which may have a substituent phenyl group selected from the group consisting of,
R ^47a ~ ^{R 54a} are each independently a hydrogen atom, an alkyl group or -SO ₃ having 1 to 8 carbon atoms ^- and ring ^{T 1a} has the formula (1t):

[In the formula (1t), R ^45a is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^46a is an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- at least one of which may have a substituent phenyl group selected from the group consisting of,
R ^56a is a halogen atom, an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- at least one of which may have a substituent phenyl group selected from the group consisting of,
L ^1a is a sulfur atom, and * represents a bond position with a carbocation. ]
It is a ring represented by
r is 2,
k is, -SO ₃ having the anion represented by the formula (1a-A) ^- represents the total number of a and 2,
The composition according to the above [1] or [2], wherein the two anions represented by the formula (1a-A) are the same, and ^{Mr +} is a barium ion.

[6] The ring T ^1b in the formula (2a) is the formula (2t):

[In the formula (2t), R ^45b and R ^46b may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents a good aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^45b and R ^46b are bonded to each other. Forming a 3 to 10-membered nitrogen-containing heterocycle with the nitrogen atom
R ^56b is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have a group.
L ^1b represents a sulfur atom, an oxygen atom or -NR ^57b-
R ^57b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The substituent which may have the aromatic hydrocarbon group having 6 to 14 carbon atoms is a halogen atom, a nitro group, a hydroxy group, a formyl group and a substituent having 1 to 8 carbon atoms which may have a substituent. At least one selected from the group consisting of alkyl groups,
The substituent which the aralkyl group having 7 to 30 carbon atoms may have is from a halogen atom, a nitro group, a hydroxy group, a formyl group and an alkyl group having 1 to 8 carbon atoms which may have a substituent. At least one selected from the group
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group, and * is a carbocation. Represents the connection position of. ]
The composition according to any one of the above [1] to [5], which is a ring represented by.

[7] The composition according to any one of the above [1] to [6], wherein [Y] ^m− in the formula (2a) is a polyacid anion containing a tungsten atom.
[8] [Y] ^m- in equation (2a) is [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [SiW ₁₂ ]. O ₄₀ ] ^4- , [SiW ₁₂ O ₄₀ ] ^4- , [SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P] ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , [SiW ₉ O ₃₄ ] ^10- , [SiW ₁₀ O ₃₆ ] ^8- , [SiW ₁₁ O ₃₉ ] ^8- , [SiW ₁₁ ] O ₃₉ ] The composition according to any one of the above [1] to [6], which is ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- or [WO ₄ ] ^2- . ..

[9] In the formula (2a), R ^41b , R ^43b and R ^47b to R ^54b are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R ^42b and R ^44b are phenyl groups which may independently have an alkyl group having 1 to 8 carbon atoms.
Ring T ^1b is the equation (2t):

[In formula (2t), R ^45b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^46b is a phenyl group which may have an alkyl group having 1 to 8 carbon atoms.
R ^56b is a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms.
L ^1b is a sulfur atom, and * represents a bond position with a carbocation. ]
It is a ring represented by
m is 3,
Any one of the above [1] to [5], wherein the three cations represented by the formula (2a-C) are the same, and [Y] ^m- is [PW ₁₂ O ₄₀ ] ^3-. The composition according to.

[10] In the formula (3a), R ¹ and R ³ are independently hydrogen atoms; alkyl groups having 1 to 8 carbon atoms which may have a carboxy group; alkyl groups having 1 to 8 carbon atoms. And a phenyl group which may have at least one substituent selected from the group consisting of -SO ₂ NR ⁹ R ¹⁰ ; or -R ^12- Si (R ¹³ ) ₃ .
R ² and R ⁴ each independently consist of an alkyl group having 1 to 8 carbon atoms which may have a carboxy group; an alkyl group having 1 to 8 carbon atoms and -SO ₂ NR ⁹ R ^10. A phenyl group which may have at least one substituent of choice; or -R ^12- Si (R ¹³ ) ₃
R ⁵ is, -SO ₃ ^- and is,
R ⁶ and R ⁷ are both hydrogen atoms,
R ⁹ and R ¹⁰ are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R ¹² is an alkanediyl group having 1 to 6 carbon atoms.
All three R ^13s are alkoxy groups having 1 to 4 carbon atoms.
The composition according to any one of the above [1] to [9], wherein p is 1 and q is 0.

[11] The total content of the compound represented by the formula (1a), the compound represented by the formula (2a) and the compound represented by the formula (3a) is 50 with respect to the total amount of the colorant (A). The composition according to any one of the above [1] to [10], which is ~ 100% by weight.
[12] At least one selected from the group consisting of the compound represented by the formula (1a), the compound represented by the formula (2a) and the compound represented by the formula (3a) is represented by the formula (1a). The compound according to any one of the above [1] to [5], wherein the content of the compound represented by the formula (1a) is 50 to 100% by weight based on the total amount of the colorant (A). Composition.
[13] At least one selected from the group consisting of the compound represented by the formula (1a), the compound represented by the formula (2a) and the compound represented by the formula (3a) is represented by the formula (2a). The above-mentioned [1], [2] and [6] to [9], which are compounds and the content of the compound represented by the formula (2a) is 50 to 100% by weight based on the total amount of the colorant (A). ] The composition according to any one of.

[14] The resin (B1) has a co-weight containing a structural unit (b1-1), a structural unit derived from a polymerizable unsaturated compound having an acidic group (b1-2), and other structural units (b1-3). The above [1] to [13], wherein the amount of the structural unit (b1-1) is 1 to 50 mol% when the total of all the structural units in the copolymer is 100 mol%. The composition according to any one.
[15] The composition according to any one of the above [1] to [14], wherein the resin (B1) has a weight average molecular weight of 1,000 to 50,000.
[16] The composition according to any one of the above [1] to [15], wherein the content of the resin (B1) is 10 to 100 parts by weight with respect to 100 parts by weight of the colorant (A).
[17] The composition according to any one of the above [1] to [15], wherein the content of the resin (B1) is 10 to 60 parts by weight with respect to 100 parts by weight of the colorant (A).

First, the composition of the present invention is produced in advance, and then the color-curable composition is produced using the composition of the present invention, whereby thickening of the color-curable composition can be suppressed.

The composition of the present invention contains a colorant (A), a resin (B) and a solvent (E). In the composition of the present invention, the colorant (A) is selected from the group consisting of a compound represented by the formula (1a), a compound represented by the formula (2a), and a compound represented by the formula (3a). The composition comprises at least one, the resin (B) contains the resin (B1) containing the structural unit (b1-1) represented by the formula (1b), and the content of the colorant (A) is the composition. It is characterized in that it is 35 to 70% by weight with respect to the total amount of solid content. Here, the "total amount of solids in the composition" refers to the amount obtained by subtracting the content of the solvent (H) from the total amount of the composition. The total amount of solids and the content of each component can be measured by a known analytical means such as liquid chromatography or gas chromatography.

In the present specification, "compound represented by formula (1a)" may be abbreviated as "compound (1a)". In addition, compounds represented by other formulas, anions and cations may be abbreviated in the same manner. Further, unless otherwise specified, only one kind may be used for each component of the composition of the present invention, each component of the color curable composition, the raw material for producing each component, and the like. Seeds or more may be used together.

The present invention is characterized in that a specific colorant (ie, at least one selected from the group consisting of compound (1a), compound (2a) and compound (3a)) is used. The present inventor has found that there is a problem that the viscosity of a color curable composition containing a specific colorant increases during storage. As a result of diligent studies by the present inventor in order to solve this problem, first, a colorant (A) containing a specific colorant and a structural unit (b1-1) represented by the formula (1b) are included. A composition is produced by mixing a resin (B) containing a resin (B1) and a solvent (E), and the obtained composition, a polymerizable compound (C), a polymerization initiator (D), and the like. It has been found that thickening of the color-curable composition can be suppressed by producing a color-curable composition by mixing it with other components as needed. Hereinafter, the present invention will be described in order.

<Definition>
First, the definition of the group used in the present specification will be described. Unless otherwise stated, groups have the following definitions:
In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the present specification, the saturated hydrocarbon group may be linear, branched or cyclic. Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a hexadecyl group. , Icosyl group, isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other alkyl groups with 1 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tri Examples thereof include an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclodecyl group.

In the present specification, the alkyl group may be either linear or branched. Examples of alkyl groups having 1 to 10 carbon atoms include those having 1 to 10 carbon atoms in the above-mentioned examples of alkyl groups having 1 to 20 carbon atoms. The same applies to the examples of other alkyl groups having different carbon atoms. The same applies to groups other than alkyl groups, although they have different carbon atoms. For example, examples of saturated hydrocarbon groups having 2 to 20 carbon atoms include those having 2 to 20 carbon atoms in the above-mentioned examples of saturated hydrocarbon groups having 1 to 20 carbon atoms.

In the present specification, the alkanediyl group may be either linear or branched. Examples of the arcandyl group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, an isobutylene group, a 2-methyltrimethylene group and an isopentylene. Examples thereof include a group, an isohexylene group, an isooctylene group and a 2-ethylhexylene group.

In the present specification, the fluoroalkyl group may be either linear or branched. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a monofluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a perfluoroethyl group. Monofluoropropyl group, difluoropropyl group, trifluoropropyl group, tetrafluoropropyl group, pentafluoropropyl group, hexafluoropropyl group, perfluoropropyl group, monofluorobutyl group, difluorobutyl group, trifluorobutyl group, tetrafluorobutyl Examples thereof include a group, a pentafluorobutyl group, a hexafluorobutyl group, a heptafluorobutyl group, an octafluorobutyl group, and a perfluorobutyl group.

In the present specification, the alkoxy group may be either linear or branched. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an isopropoxy group, an isobutoxy group, an isopentyloxy group and a neopentyloxy group. Can be mentioned.

In the present specification, examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group. Can be mentioned.

In the present specification, examples of the aralkyl group having 7 to 30 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group and a 3-phenylpropyl group.

In the present specification, the nitrogen-containing heterocycle may be either a monocyclic ring or a condensed ring. Examples of the 3- to 10-membered nitrogen-containing heterocycle include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.

In the present specification, the aromatic hydrocarbon ring may be either a monocyclic ring or a condensed ring. The aromatic hydrocarbon ring having 6 to 14 carbon atoms may be any of a benzene ring, a naphthalene ring, a phenanthrene ring and an anthracene ring.

In the present specification, the aromatic heterocycle may be either a monocyclic ring or a condensed ring. Examples of the 5- to 10-membered aromatic heterocycle include a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, a furan ring, a thiophene ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and an indole ring. Examples thereof include a benzimidazole ring, a benzothiazole ring, a quinoline ring, and a benzofuran ring.

<Colorant (A)>
The colorant (A) comprises at least one selected from the group consisting of compound (1a), compound (2a) and compound (3a).

First, the groups and the like in the following formula (1a) will be described in order.

R ^41a and R ^42a in the formula (1a) may independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41a and R ^42a are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with a nitrogen atom.

The substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (1a) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

When the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (1a) is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH _2- contained in the saturated hydrocarbon group is -O- or-. It may be replaced with CO-. Here, -CH _2- does not include -CH ₂ -bonded to a nitrogen atom and -CH _2- in the methyl group at the end of the saturated hydrocarbon group. Further, -CH _2- CH _2- contained in the saturated hydrocarbon group is not replaced with -O-O- or -CO-CO-.

Aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14 in the formula (1a) is a halogen atom, a nitro group, hydroxy group, formyl _group, ^_-SO 3 _-, ^-SO 2 -N ^It is at least one selected from the group consisting of --SO _2- R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.

Substituents which may have an aralkyl group having 7 to 30 carbon atoms in the formula (1a) is a halogen atom, a nitro group, hydroxy group, formyl _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - -SO _It is at least one selected from the group consisting of _2- R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.
R ^f in the formula (1a) represents a fluoroalkyl group having 1 to 12 carbon atoms.

The substituent which the alkyl group having 1 to 8 carbon atoms in the formula (1a) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

When the alkyl group having 1 to 8 carbon atoms in the formula (1a) is an alkyl group having 2 to 8 carbon atoms, -CH _2- contained in the alkyl group is replaced with -O- or -CO-. May be good. Wherein the -CH 2 _- The, -CH 2 in a methyl group is the terminal of the alkyl group _- is not included. Further, -CH _2- CH _2- contained in the alkyl group is not replaced with -OO- or -CO-CO-.

R ^41a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
R ^42a is preferably an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- one as at least one substituent a phenyl group which may have a, more preferably substituent selected from the group consisting or 2 It has a number of alkyl group having 1 to 8 carbon atoms, and -SO ₃ ^- a phenyl group optionally having a, more preferably one or two alkyl groups having 1 to 4 carbon atoms as a substituent a, and -SO ₃ ^- is a phenyl group which may have a.

R ^43a and R ^44a in the formula (1a) may independently have a hydrogen atom and a substituted hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or nitrogen in which R ^43a and R ^44a are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the atoms.

R ^43a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
R ^44a is preferably an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- one as at least one substituent a phenyl group which may have a, more preferably substituent selected from the group consisting or 2 It has a number of alkyl group having 1 to 8 carbon atoms, and -SO ₃ ^- a phenyl group optionally having a, more preferably one or two alkyl groups having 1 to 4 carbon atoms as a substituent a, and -SO ₃ ^- is a phenyl group which may have a.

^R 47a ^{~ R 54a} in formula (1a) are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - -SO 2 -R f , or substituted, Represents an alkyl group having 1 to 8 carbon atoms which may have a group. R ^47a ~ ^{R 54a} are each independently preferably a hydrogen atom, an alkyl group or -SO ₃ having 1 to 8 carbon atoms ^- a ^-, more preferably a hydrogen atom or -SO _3.

The ring T ^1a in the formula (1a) is an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or an aromatic heterocycle having 5 to 10 members which may have a substituent. Represents.

Aromatic hydrocarbon ring substituent which may be possessed by the carbon number of 6 to 14 in the formula (1a) is a halogen atom, a nitro group, hydroxy group, formyl _group, ^_-SO 3 _-, ^-SO 2 -N ^It is at least one selected from the group consisting of --SO _2- R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.

5-10 membered aromatic heterocyclic ring substituent which may have a in the formula (1a) is a halogen atom, a nitro group, hydroxy group, formyl _{^{_{group, -SO 3 -, -SO 2 -N}}} - - It is at least one selected from the group consisting of SO _2- R ^f and an alkyl group having 1 to 8 carbon atoms which may have a substituent.

Ring T ^1a is preferably of formula (1t):

It is a ring represented by.
R ^45a and R ^46a in the formula (1t) may independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^45a and R ^46a are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with a nitrogen atom.

The substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (1t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

Aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14 in the formula (1t) is a halogen atom, a nitro group, hydroxy group, formyl _group, ^_-SO 3 _-, ^-SO 2 -N ^It is at least one selected from the group consisting of --SO _2- R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.

Substituents which may have an aralkyl group having 7 to 30 carbon atoms in the formula (1t) is a halogen atom, a nitro group, hydroxy group, formyl _{^{_{^{group, -SO 3 -, -SO 2 -N}}}} - -SO _It is at least one selected from the group consisting of _2- R ^f , and an alkyl group having 1 to 8 carbon atoms which may have a substituent.

The substituent which the alkyl group having 1 to 8 carbon atoms in the formula (1t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

R ^45a is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
R ^46a is preferably an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- one as at least one substituent a phenyl group which may have a, more preferably substituent selected from the group consisting or 2 It has a number of alkyl group having 1 to 8 carbon atoms, and -SO ₃ ^- a phenyl group optionally having a, more preferably one or two alkyl groups having 1 to 4 carbon atoms as a substituent a, and -SO ₃ ^- is a phenyl group which may have a.

R ^56a in the formula (1t) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic having 6 to 14 carbon atoms which may have a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have a hydrocarbon group or a substituent.

R ^56a is preferably a halogen atom, an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- 1 least one substituent a phenyl group which may have a selected from the group consisting of, more preferably a substituent It has a number or two halogen atoms, and -SO ₃ ^- a phenyl group which may have a, more preferably has one or two fluorine atom as a substituent, and -SO ₃ ^- and It is a phenyl group that may have.

L ^1a in the formula (1t) represents a sulfur atom, an oxygen atom or -NR ^57a- . R ^57a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L ^1a is preferably a sulfur atom.

* In the formula (1t) represents the binding position with the carbocation. In other words, − * in equation (1t) represents a bond. -* In other equations also represents a bond.

R in equation (1a) represents an integer of 1 or more. r is preferably 2. When r is an integer of 2 or more, the equation (1a-A):

[In the formula (1a-A), the rings T ^1a , R ^41a to R ^44a and R ^47a to R ^54a are synonymous with the above, respectively. ]
The plurality of anions represented by may be the same or different. The plurality of anions (1a-A) are preferably the same.

K in the formula (1a) is, -SO ₃ having anion (1a-A) is ^- and _-SO 2 ^-N - represents the total number of _-SO 2 -R ^f, a and an integer of 2 or more. k is preferably 2.

^{Mr +} in the formula (1a) represents a hydrogen ion, an r-valent metal ion or N ⁺ (R ^55a ) ₄ , and the four R ^55a may be the same or different. R ^55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. When k-1 in the formula (1a) is an integer of 2 or more, the plurality of ^{Mr +} may be the same or different.

^{Mr +} is preferably an r-valent metal ion. Examples of the r-valent metal ion include alkali metal ions such as lithium ion, sodium ion and potassium ion; alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion and barium ion; titanium ion and zirconium. Transition metal ions such as ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions and copper ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions and bismuth ions. Can be mentioned.

^{Mr +} is more preferably a divalent metal ion, more preferably an alkaline earth metal ion, and particularly preferably a barium ion (Ba ²⁺ ).

As compound (1a),
R ^41a and R ^43a are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R ^42a and R ^44a are each independently an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- at least one of which may have a substituent phenyl group selected from the group consisting of,
R ^47a ~ ^{R 54a} are each independently a hydrogen atom, an alkyl group or -SO ₃ having 1 to 8 carbon atoms ^- and ring ^{T 1a} is a ring represented by formula (1t) [wherein (1t ), R ^45a is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^46a is an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- at least one of which may have a substituent phenyl group selected from the group consisting of,
R ^56a is a halogen atom, an alkyl group and -SO ₃ having 1 to 8 carbon atoms ^- at least one of which may have a substituent phenyl group selected from the group consisting of,
L ^1a is a sulfur atom, and * represents a bond position with a carbocation. ],
r is 2,
k is, -SO ₃ having anion (1a-A) is ^- represents the total number of a and 2,
A compound in which the two anions (1a-A) are the same and ^{Mr +} is Ba ²⁺ (hereinafter, may be referred to as "compound (1a')") is preferable.

In the compound (1a'), R ^41a and R ^43a are more preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, still more preferably alkyl groups having 1 to 4 carbon atoms, and R ^42a and R ^44a are each independently more preferably has one or two alkyl groups having 1 to 8 carbon atoms as a substituent, and -SO ₃ ^- a phenyl group which may have a as more preferably substituent has one or two alkyl groups having 1 to 4 carbon atoms, and -SO ₃ ^- a phenyl group optionally having ^a, R 47a ^{~ R 54a} is more preferably a hydrogen atom or -SO ₃ ⁻ , R ^45a is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, and R ^46a is more preferably one substituent. or having two alkyl groups having 1 to 8 carbon atoms, and -SO ₃ ^- a phenyl group which may have a, more preferably one or two alkyl of 1 to 4 carbon atoms as a substituent It has a group, and -SO ₃ ^- a phenyl group optionally having, as well as ^{R 56a} is more preferably has one or two halogen atoms as substituents, and -SO ₃ ^- a phenyl group which may have a, more preferably has one or two fluorine atom as a substituent, and -SO ₃ ^- is a phenyl group which may have a.

Among the compounds (1a), the compound represented by the following formula (1a-1) is particularly preferable. In the following formulas (1a-1), the two ^- the description of, -SO ₃ as the anion substituent "-SO _3" ^- has, and -SO ₃ in each anion ^- Total number of There 2 (i.e., -SO ₃ in two anion ^- total number of 4) meant to be.

Compound (1a) can be used in known methods (for example, the method described in Journal of Organic Chemistry, (1994), vol. 59, # 11, pp. 3232-3236, the method described in JP-A-2018-127596). It can be manufactured according to the above.

Next, the groups and the like in the following formula (2a) will be described in order.

R ^41b and R ^42b in the formula (2a) may independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^41b and R ^42b are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with a nitrogen atom.

The substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (2a) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

When the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (2a) is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH _2- contained in the saturated hydrocarbon group is -O- or-. It may be replaced with CO-. Here, -CH _2- does not include -CH ₂ -bonded to a nitrogen atom and -CH _2- in the methyl group at the end of the saturated hydrocarbon group. Further, -CH _2- CH _2- contained in the saturated hydrocarbon group is not replaced with -O-O- or -CO-CO-.

The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (2a) may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent. It is at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms.

The substituent which may have an aralkyl group having 7 to 30 carbon atoms in the formula (2a) may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 carbon number. At least one selected from the group consisting of up to 8 alkyl groups.

The substituent which the alkyl group having 1 to 8 carbon atoms in the formula (2a) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

When the alkyl group having 1 to 8 carbon atoms in the formula (2a) is an alkyl group having 2 to 8 carbon atoms, -CH _2- contained in the alkyl group is replaced with -O- or -CO-. May be good. Wherein the -CH 2 _- The, -CH 2 in a methyl group is the terminal of the alkyl group _- is not included. Further, -CH _2- CH _2- contained in the alkyl group is not replaced with -OO- or -CO-CO-.

R ^41b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
R ^42b preferably has a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, and further preferably a phenyl group. Is.

R ^43b and R ^44b in the formula (2a) may independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or nitrogen in which R ^43b and R ^44b are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with the atoms.

R ^43b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.
R ^44b preferably has a phenyl group having 1 to 8 carbon atoms, more preferably a phenyl group having 1 to 4 carbon atoms, and even more preferably a phenyl group. Is.

R ^47b to R ^54b in the formula (2a) each independently represent an alkyl group having 1 to 8 carbon atoms which may have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a substituent. ..

Each of R ^47b to R ^54b is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom.

The ring T ^1b in the formula (2a) is an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10-membered aromatic heterocycle which may have a substituent. Represents.

The substituent which the aromatic hydrocarbon ring having 6 to 14 carbon atoms in the formula (2a) may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent. It is at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms.

The substituent which the 5- to 10-membered aromatic heterocycle in the formula (2a) may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a number of carbon atoms which may have a substituent. At least one selected from the group consisting of 1 to 8 alkyl groups.

Ring T ^1b is preferably of formula (2t):

It is a ring represented by.
R ^45b and R ^46b in the formula (2t) may independently have a hydrogen atom and a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R ^45b and R ^46b are bonded to each other. It forms a 3- to 10-membered nitrogen-containing heterocycle with a nitrogen atom.

The substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (2t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

The substituent which the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (2t) may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group and a carbon which may have a substituent. It is at least one selected from the group consisting of alkyl groups of numbers 1-8.

The substituent which may have an aralkyl group having 7 to 30 carbon atoms in the formula (2t) may have a halogen atom, a nitro group, a hydroxy group, a formyl group and a substituent having 1 to 1 carbon atoms. At least one selected from the group consisting of 8 alkyl groups.

The substituent that the alkyl group having 1 to 8 carbon atoms in the formula (2t) may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.

R ^45b is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms.

R ^46b is preferably a phenyl group which may have an alkyl group having 1 to 8 carbon atoms, more preferably a phenyl group having 1 or 2 alkyl groups having 1 to 8 carbon atoms as a substituent, and further. It is preferably a phenyl group having one or two alkyl groups having 1 to 4 carbon atoms as a substituent.

R ^56b in the formula (2t) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic having 6 to 14 carbon atoms which may have a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have a hydrocarbon group or a substituent.

R ^56b is preferably a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms, and more preferably one or two substituents. A phenyl group having a halogen atom, more preferably a phenyl group having one or two fluorine atoms as a substituent.

L ^1b in the formula (2t) represents a sulfur atom, an oxygen atom or -NR ^57b- . R ^57b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L ^1b is preferably a sulfur atom.
* In the formula (2t) represents the bond position with the carbocation.

M in equation (2a) represents an integer of 1 or more. m is preferably an integer of 1 to 20, more preferably an integer of 2 to 14, still more preferably an integer of 2 to 8, and particularly preferably 3. When m is an integer of 2 or more, the equation (2a-C):

[In the formula (2a-C), rings T ^1b , R ^41b to R ^44b and R ^47b to R ^54b are synonymous with the above, respectively. ]
The plurality of cations represented by may be the same or different. The plurality of cations (2a-C) are preferably the same.

[Y] ^m− in the formula (2a) represents an m-valent anion. [Y] ^m- is preferably a polyacid anion containing a tungsten atom, more preferably [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [P ₂ W ₁₈ O _62]. ] ^6- , [SiW ₁₂ O ₄₀ ] ^4- , [SiW ₁₂ O ₄₀ ] ^4- , [SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , [SiW ₉ O ₃₄ ] ^10- , [SiW ₁₀ O ₃₆ ] ^8- , [SiW ₁₁ O _39] ] ^8- , [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- or [WO ₄ ] ^2- , more preferably [PW ₁₂ O ₄₀ ] ^{3 -} .

As compound (2a),
R ^41b , R ^43b and R ^47b to R ^54b are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R ^42b and R ^44b are phenyl groups which may independently have an alkyl group having 1 to 8 carbon atoms.
Ring T ^1b is a ring represented by the formula (2t) [in formula (2t), R ^45b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^46b is a phenyl group which may have an alkyl group having 1 to 8 carbon atoms.
R ^56b is a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms.
L ^1b is a sulfur atom, and * represents a bond position with a carbocation. ],
m is 3,
A compound in which the three cations (2a-C) are the same and [Y] ^m- is [PW ₁₂ O ₄₀ ] ^3- (hereinafter sometimes referred to as "compound (2a')") preferable.

In the compound (2a'), R ^41b and R ^43b are independent of each other, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having a hydrogen atom or 1 to 4 carbon atoms, and more preferably. Is an alkyl group having 1 to 4 carbon atoms, and R ^42b and R ^44b are phenyl groups which may independently have an alkyl group having 1 to 4 carbon atoms, and more preferably a phenyl group. R ^47b to R ^54b are each independently, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom, and R ^45b is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. An alkyl group having 1 to 4, more preferably an alkyl group having 1 to 4 carbon atoms, and R ^46b more preferably a phenyl group having 1 or 2 alkyl groups having 1 to 8 carbon atoms as a substituent. More preferably, it is a phenyl group having one or two alkyl groups having 1 to 4 carbon atoms as a substituent, and R ^56b is more preferably a phenyl group having one or two halogen atoms as a substituent. More preferably, it is a phenyl group having one or two fluorine atoms as a substituent.

Among the compounds (2a), the compound represented by the following formula (2a-1) is particularly preferable.

Compound (2a) can be produced according to a known method (for example, the methods described in JP-A-2015-28121, JP-A-2015-38201, etc.).

Next, the groups and the like in the following formula (3a) will be described in order.

In the formula (3a), R ¹ and R ² may independently have a hydrogen atom and a substituent, and may have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group with 6 to 10 carbon atoms or -R ^12- Si (R ¹³ ) ₃ , or R ¹ and R ² are bonded and 3 to 10 members together with the nitrogen atom to which they are bonded. Form a nitrogen-containing heterocycle.

In the formula (3a), R ³ and R ⁴ may independently have a hydrogen atom and a substituent, and may have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or a group represented by -R ^12- Si (R ¹³ ) ₃ , or R ³ and R ⁴ are bonded together with a nitrogen atom to which they are bonded. It forms a 3- to 10-membered nitrogen-containing heterocycle.

The substituents that the saturated hydrocarbon groups having 1 to 20 carbon atoms of R ¹ to R ⁴ may have are aromatic hydrocarbon groups having 6 to 10 carbon atoms, halogen atoms, hydroxy groups, formyl groups and carboxy groups. At least one selected from the group consisting of groups.

The substituents that may have the aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ may have a halogen atom, a hydroxy group, a formyl group, and a halogen atom. saturated hydrocarbon group of ^{_{^{_{~ 20, -OR 8, -SO 3}}}} -, -SO 3 - Z +, -SO 3 R 8, -CO 2 - Z +, -CO 2 R 8 and _-SO 2 ^NR 9 ^{R 10} At least one selected from the group consisting of.
The compound (3a) of the ions form in the -SO ₃ ^- if there is, the number is one.

When the saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH _2- contained in the saturated hydrocarbon group is -O-, -CO- or ^{-NR 11} - it may be replaced to. Here, -CH _2- does not include -CH ₂ -bonded to a nitrogen atom and -CH _2- in the methyl group at the end of the saturated hydrocarbon group. Furthermore, the _-CH 2 -CH ₂ contained in a saturated hydrocarbon group - is, -O-O -, - CO -CO- or ^-NR 11 ^{-NR 11} - does not replace.

R ¹ and R ³ are independent and preferably hydrogen atoms; alkyl groups having 1 to 8 carbon atoms which may have a carboxy group; alkyl groups having 1 to 8 carbon atoms and -SO ₂ NR ⁹ R. ^A phenyl group which may have at least one substituent selected from the group consisting of ¹⁰ ; or a carbon which may have a -R ^12- Si (R ¹³ ) ₃ , more preferably a hydrogen atom or a carboxy group. It is an alkyl group of numbers 1 to 4.

R ² and R ⁴ are each independently composed of an alkyl group having 1 to 8 carbon atoms, preferably having a carboxy group; an alkyl group having 1 to 8 carbon atoms and -SO ₂ NR ⁹ R ^10. A phenyl group which may have at least one substituent selected from the group; or an alkyl group having -R ^12- Si (R ¹³ ) ₃ , more preferably an alkyl group having 1 to 4 carbon atoms; an alkyl having 1 to 4 carbon atoms. A phenyl group which may have at least one substituent selected from the group consisting of groups and -SO ₂ NR ⁹ R ¹⁰ ; or -R ^12- Si (R ¹³ ) ₃ .

In the formula (3a), p represents an integer of 0 to 5. When p is an integer of 2 or more, the plurality of R ^5s may be the same or different. p is preferably 1.

Wherein ^(3a), R 5 _{^{_{^{^{is, -OH, -SO 3 -, -SO}}}}} 3 - Z +, -SO 3 R 8, -CO 2 - Z +, -CO 2 R 8 or _-SO 2 NR ^9, Represents R ¹⁰ . Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ . Four R ¹¹ may be the same or different. R ⁵ is preferably -SO ₃ ^- is.

In formula (3a), R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁶ and R ⁷ are preferably both hydrogen atoms.

In formula (3a), R ⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a halogen atom.

In formula (3a), R ⁹ and R ¹⁰ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, or R ⁹ and R ^{10 respectively.} To form a 3- to 10-membered nitrogen-containing heterocycle with the nitrogen atoms they bind to.

The substituents that the saturated hydrocarbon groups having 1 to 20 carbon atoms of R ⁹ and R ¹⁰ may have are at least one selected from the group consisting of a hydroxy group, a formyl group and a halogen atom.

When the saturated hydrocarbon group having 1 to 20 carbon atoms of R ⁹ and R ¹⁰ is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH _2- contained in the saturated hydrocarbon group is -O-, -CO- or -NR ⁸ - may be replaced to. Here, -CH _2- does not include -CH ₂ -bonded to a nitrogen atom and -CH _2- in the methyl group at the end of the saturated hydrocarbon group. Furthermore, the _-CH 2 -CH ₂ contained in a saturated hydrocarbon group - is, -O-O -, - CO -CO- or ^-NR 8 -NR ⁸ - never replace.

R ⁹ and R ¹⁰ are each independently, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In formula (3a), R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

In formula (3a), R ¹² represents an alkanediyl group having 1 to 10 carbon atoms. When the alkanediyl group having 1 to 10 carbon atoms of R ^{12 is} an alkanediyl group having 2 to 20 carbon atoms, -CH _2- contained in the alkanediyl group is -O-, -CO- or -NR. ^It may be replaced with 8-. Here, -CH _2- does not include -CH _2- bonded to a nitrogen atom and -CH _2- bonded to a silicon atom. Furthermore, the _-CH 2 -CH ₂ contained in the alkanediyl group - is, -O-O -, - CO -CO- or ^-NR 8 -NR ⁸ - never replace.
R ¹² is preferably an alkanediyl group having 1 to 6 carbon atoms.

In formula (3a), R ¹³ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. And three R ¹³ may be each the same or may be different. Three ^{R 13} is preferably both an alkoxy group having 1 to 4 carbon atoms.

In formula (3a), X represents a halogen atom.
In formula (3a), q represents 0 or 1. Here, when q is 0, it means that (X ⁻ ) _q does not exist. q is preferably 0.

As compound (3a),
R ¹ and R ³ are independently hydrogen atoms; alkyl groups having 1 to 8 carbon atoms which may have a carboxy group; alkyl groups having 1 to 8 carbon atoms and -SO ₂ NR ⁹ R ¹⁰ A phenyl group which may have at least one substituent selected from the group; or -R ^12- Si (R ¹³ ) ₃ .
R ² and R ⁴ each independently consist of an alkyl group having 1 to 8 carbon atoms which may have a carboxy group; an alkyl group having 1 to 8 carbon atoms and -SO ₂ NR ⁹ R ^10. A phenyl group which may have at least one substituent of choice; or -R ^12- Si (R ¹³ ) ₃
R ⁵ is, -SO ₃ ^- and is,
R ⁶ and R ⁷ are both hydrogen atoms,
R ⁹ and R ¹⁰ are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R ¹² is an alkanediyl group having 1 to 6 carbon atoms.
All three R ^13s are alkoxy groups having 1 to 4 carbon atoms.
A compound in which p is 1 and q is 0 (hereinafter, may be referred to as “compound (3a')”) is preferable.

In the compound (3a'), R ¹ and R ³ are independently alkyl groups having 1 to 4 carbon atoms, which may have a hydrogen atom or a carboxy group, respectively, and R ² and R. ⁴ may more preferably have an alkyl group having 1 to 4 carbon atoms; an alkyl group having 1 to 4 carbon atoms and at least one substituent selected from the group consisting of −SO ₂ NR ⁹ R ^10. Group; or -R ^12- Si (R ¹³ ) ₃ .

The compound (3a) is particularly preferably a compound represented by the following formula (3a-1), a compound represented by the following formula (3a-2), a compound represented by the following formula (3a-3), and the following. A compound represented by the formula (3a-4), a compound represented by the following formula (3a-5), a compound represented by the following formula (3a-6), and a compound represented by the following formula (3a-7). At least one selected from the group consisting of.

In formulas (3a-2) and (3a-3), R ¹⁴ represents -SO _2- NH (CH ₂ ) -CH (CH ₂ CH ₃ ) -CH ₂ CH ₂ CH ₂ CH ₃ .

Compound (3a) can be produced according to a known method (for example, the method described in JP-A-2010-32999).

In one aspect of the invention, at least one selected from the group consisting of compound (1a), compound (2a) and compound (3a) is preferably at least selected from the group consisting of compound (1a) and compound (2a). It is one, more preferably compound (1a) or compound (2a), and even more preferably compound (1a).

In another aspect of the invention, at least one selected from the group consisting of compound (1a), compound (2a) and compound (3a) is preferably compound (1a'), compound (2a') and compound ( At least one selected from the group consisting of 3a'), more preferably at least one selected from the group consisting of compound (1a') and compound (2a'), and even more preferably compound (1a') or It is compound (2a'), and particularly preferably compound (1a').

In another aspect of the invention, at least one selected from the group consisting of compound (1a), compound (2a) and compound (3a) is preferably compound (1a-1), compound (2a-1), Consists of compound (3a-1), compound (3a-2), compound (3a-3), compound (3a-4), compound (3a-5), compound (3a-6) and compound (3a-7). At least one selected from the group, more preferably at least one selected from the group consisting of compound (1a-1) and compound (2a-1), and even more preferably compound (1a-1) or compound ( It is 2a-1), and particularly preferably compound (1a-1).

The colorant (A) may contain a compound (1a), a compound (2a), and another colorant different from the compound (3a).

Xanthene dye can be used as another colorant. Examples of the xanthene dye include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. The same applies to the others), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10, 11, C.I. I. Basic Violet 10 (Rhodamine B), 11, C.I. I. Solvent Red 218, C.I. I. Modant Red 27, C.I. I. Examples thereof include Reactive Red 36 (Rose Bengal B) and Sulforhodamine G.

Coumarin dye can be used as another colorant. Examples of the coumarin dye include C.I. I. Acid Yellow 227, 250; C.I. I. Disperse Yellow 82, 184; C.I. I. Solvent Orange 112; C.I. I. Solvent Yellow 160, 172; coumarin dyes and the like described in Japanese Patent No. 12999948.

Examples of dyes other than the above include dyes listed in the Color Index (published by The Society of Dyers and Colorists) and dyes listed in the dyeing notebook (Color Dyeing Co., Ltd.). Examples of the dye include azo dye, cyanine dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acrydin dye, styryl dye, quinoline dye and nitro dye. ..

Specific examples of the dye include the following.
(1) C.I. I. Solvent dye C. I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;
C. I. Solvent Orange 2,7,11,15,26,41,54,56,99;
C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247;
C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 5, 28, 29, 32, 33; etc.

(2) C.I. I. Acid dye C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,149,162,169,173;
C. I. Acid Red 73, 80, 91, 97, 138, 151, 211,274;
C. I. Acid Green 3, 5, 9, 25, 27, 28, 41;
C. I. Acid Violet 34, 120;
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112; etc.

(3) C.I. I. Basic dye C. I. Basic Green 1; etc.

(4) C.I. I. Reactive dye C. I. Reactive Yellow 2,76,116;
C. I. Reactive orange 16; etc.

(5) C.I. I. Direct dye C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct blue 40; etc.

(6) C.I. I. Disperse dye C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60; etc.

(7) C.I. I. Mordant dye C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; etc.

(8) C.I. I. Vat dye C. I. Bat green 1st prize.

Further, as another colorant, for example, a pigment described in the Color Index (published by The Society of Dyers and Colorists) can be used.

Specific examples of pigments include:
C. I. Pigment Yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,129,137,138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Black pigments such as Pigment Black 1 and 7.

The content of the colorant (A) is 35 to 70% by weight, preferably 40 to 70% by weight, more preferably 40 to 65% by weight, still more preferably, based on the total solid content of the composition of the present invention. It is 45 to 60% by weight.

The total content of compound (1a), compound (2a) and compound (3a) is preferably 50-100% by weight, more preferably 55-100% by weight, based on the total amount of colorant (A). It is preferably 60 to 100% by weight, particularly preferably 65 to 100% by weight, and most preferably 80 to 100% by weight.

In an embodiment in which at least one selected from the group consisting of compound (1a), compound (2a) and compound (3a) is compound (1a), the content of compound (1a) is relative to the total amount of colorant (A). It is preferably 50 to 100% by weight, more preferably 55 to 100% by weight, still more preferably 60 to 100% by weight, particularly preferably 65 to 100% by weight, and most preferably 80 to 100% by weight.

In an embodiment in which at least one selected from the group consisting of compound (1a), compound (2a) and compound (3a) is compound (2a), the content of compound (2a) is relative to the total amount of colorant (A). It is preferably 50 to 100% by weight, more preferably 55 to 100% by weight, still more preferably 60 to 100% by weight, particularly preferably 65 to 100% by weight, and most preferably 80 to 100% by weight.

<Resin (B)>
This resin (B) is based on the formula (1b):

[In formula (1b), R ^1B represents a hydrogen atom or a methyl group.
R ^2B to R ^4B independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
n represents an integer from 1 to 10, and * represents the bond position.
However, at least one of R ^2B to R ^4B is an alkoxy group having 1 to 6 carbon atoms. ]
Includes a resin (B1) containing a structural unit (b1-1) represented by (hereinafter, may be referred to as “constituent unit (b1-1)”). In the resin (B1), the constituent unit (b1-1) may contain only one type, or may contain two or more types.

R ^2B to R ^4B are independently, preferably a methoxy group, an ethoxy group or a propoxy group, and more preferably a methoxy group or an ethoxy group.
n is preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.

The resin (B1) is preferably described as a structural unit (b1-1), a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter, “constituent unit (b1-2)”). (There is) and other structural units (b1-3) (hereinafter sometimes referred to as “constituent unit (b1-3)”). Here, the other structural unit (b1-3) means a structural unit different from the structural unit (b1-1) and the structural unit (b1-2). In the resin (B1) which is a copolymer, only one kind of the structural unit (b1-1), the structural unit (b1-2) and the structural unit (b1-3) may be contained. Two or more kinds may be included.

Examples of the acidic group contained in the structural unit (b1-2) include a carboxy group, a phosphoric acid group (-OP (= O) (OH) ₂ ), and a sulfo group (-S (= O) ₂ OH). Can be mentioned. Of these, a carboxy group is preferred.

The amount of the structural units (b1-1) when the total of all the structural units in the copolymer is 100 mol% is preferably from the viewpoint of solvent resistance of a color filter or the like obtained from the color curable composition. It is 1 to 50 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 30 mol%.

The amount of the structural unit (b1-2) when the total of all the structural units in the copolymer is 100 mol% is preferably 10 to 50 mol% from the viewpoint of the developability of the color curable composition. It is preferably 15 to 45 mol%, more preferably 20 to 40 mol%.

The amount of the structural units (b1-3) when the total of all the structural units in the copolymer is 100 mol% is determined by the developability of the color curable composition and the color filter obtained from the color curable composition. From the viewpoint of solvent resistance, it is preferably 1 to 89 mol%, more preferably 15 to 80 mol%, still more preferably 30 to 70 mol%.

The weight average molecular weight (Mw) of the resin (B1) is 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 3, from the viewpoint of developability of the color-curable composition. It is 000 to 30,000. The weight average molecular weight (Mw) is a value calculated in terms of polystyrene using gel permeation chromatography (GPC).

The silyl group equivalent of the resin (B1) is preferably 400 to 4,000, more preferably 450 to, from the viewpoint of solvent resistance of a color filter or the like obtained from a heat-decomposable, heat-yellowing and color-curable composition. It is 3,000. When the silyl group equivalent of the resin (B1) is 400 or more, it is effective in further enhancing the heat-resistant decomposition property and heat-resistant yellowing of the colored pattern or the colored coating film. The silyl group equivalent of the resin (B1) is calculated by the following formula:
Cyril group equivalent = a value calculated from the weight average molecular weight of the resin (B1) / the average number of silyl groups per molecule. The silyl group equivalent can be calculated from the amount of the monomer charged in the production of the resin (B1).

When the resin (B1) is a copolymer containing a constituent unit (b1-2), the acid value of the resin (B1) is preferably 20 to 300 mgKOH / g from the viewpoint of the developability of the color curable composition. More preferably, it is 30 to 200 mgKOH / g. The acid value of the resin (B1) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3, and is necessary for neutralizing 1 g of the resin (B1). It is a value calculated as the amount of potassium hydroxide (mg), and can be obtained, for example, by titrating with an aqueous solution of potassium hydroxide.

From the viewpoint of suppressing thickening of the color curable composition, the content of the resin (B1) is preferably 10 to 100 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the colorant (A). It is more preferably 10 to 55 parts by weight, particularly preferably 25 to 55 parts by weight, and most preferably 30 to 55 parts by weight.

The resin (B1) is prepared by the following formula (2b) in the presence of a solvent.

[The meanings of the symbols in equation (2b) are as described above]
Only the compound represented by (m1-1) (hereinafter sometimes referred to as "compound (m1-1)") or a monomer mixture containing the compound (m1-1) and other compounds is subjected to known radical polymerization. It can be produced by copolymerizing according to the method.

For the resin (B1) which is a copolymer, for example, a compound (m1-1) and, if necessary, another compound are dissolved in a solvent to prepare a solution, and then a polymerization initiator is added to the solution. It can be produced by reacting at 50 to 130 ° C. for 1 to 20 hours.

The resin (B1), which is a copolymer containing the structural unit (b1-1), the structural unit (b1-2) and the structural unit (b1-3), is a compound (m1-1) and an acidic group in the presence of a solvent. Polymerizable unsaturated compound (m1-2) (hereinafter sometimes referred to as "compound (m1-2)"), and other polymerizable unsaturated compounds (m1-3) (hereinafter "compound (m1-m1-)"). It can be produced by copolymerizing a monomer mixture consisting of (which may be described as "3)" according to a known radical polymerization method. Here, the other polymerizable unsaturated compound (m1-3) means a polymerizable unsaturated compound different from the compound (m1-1) and the compound (m1-2). Further, the structural unit (b1-1) is derived from the compound (m1-1), the structural unit (b1-2) is derived from the compound (m1-2), and the structural unit (b1-3) is derived from the compound (m1-m1-). Derived from 3).

The resin (B1), which is a copolymer, is obtained by dissolving, for example, compound (m1-1), compound (m1-2) and compound (m1-3) in a solvent to prepare a solution, and then polymerizing the solution. It can be produced by adding an initiator and reacting at 50 to 130 ° C. for 1 to 20 hours.

Examples of the compound (m1-1) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- Examples thereof include (meth) acryloyloxypropyl ethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3- (meth) acryloyloxypropyltriethoxysilane. Among these, 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane are preferable from the viewpoint of availability and reactivity. Here, "3- (meth) acryloyloxypropylmethyldimethoxysilane" means at least one selected from 3-acryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane. Other similar statements have the same meaning.

Examples of the acidic group contained in the compound (m1-2) include a carboxy group, a phosphoric acid group (-OP (= O) (OH) ₂ ), and a sulfo group (-S (= O) ₂ OH). Be done. Of these, a carboxy group is preferred.

Examples of the compound (m1-2) include (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl sulfonic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2- (meth). ) Acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl acid phosphate and the like. Among these, (meth) acrylic acid is preferable from the viewpoint of availability and reactivity.

Examples of the compound (m1-3) include the following:
butadiene;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylic rate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) ) Acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl ( Meta) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, rosin (Meta) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (meth) acrylate, 5-ethylnorbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1 , 1-Trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate , 3- (N, N-dimethylamino) propyl (meth) acrylate, glycerylol mono (meth) acrylate, butanetriol mono (meth) acrylate, pentatriol mono (meth) acrylate, dicyclopentenyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) ) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate , 3-Isocyanatopropyl (meth) acrylate, 2-Isocyanato-1 -Methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate, the above-mentioned (meth) acrylate having an isocyanato group (for example, 2-isocyanato). Ethyl (meth) acrylate) (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino having a blocked isocyanato group obtained by blocking the isocyanato group with a blocking agent. Ethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, hexamethylpiperidyl (meth) acrylate;
(Meta) Acrylic Acid Amide, (Meta) Acrylic Acid N, N-Dimethylamide, (Meta) Acrylic Acid N, N-Diethylamide, (Meta) Acrylic Acid N, N-Dipropylamide, (Meta) Acrylic Acid N, N-diisopropylamide, (meth) acrylic acid anthracenylamide, N-isopropyl (meth) acrylamide, (meth) acrylic morpholine, diacetone (meth) acrylamide;
Norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene , Tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] Dodeca-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] deca-8-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3 -En, tricyclo [4.4.0.1 ^2,5 ] undec-3-ene, tricyclo [6.2.1.0 ^1,8 ] undec-9-ene, tricyclo [6.2.1.0] ^1,8 ] Undeca-4-ene, tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} . 0 ^1,6 ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} . 0 ^1,6 ] Dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 17 and ¹² ] Dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} . 0 ^1,6 ] Dodeca-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, pentacyclo [7.4.0.1 ^2,5. ^{19 and 12} . 0 ^8,13] pentadeca-3-ene, 5-norbornene-2,3-dicarboxylic acid anhydride, (meth) anilide acrylic acid, (meth) acryloyl nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, Vinylidene chloride, vinylpyridine, vinyl acetate, vinyltoluene;
Styrene and its derivatives;
Diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid;
Maleic anhydride, itaconic anhydride, citraconic anhydride.

From the viewpoint of availability and reactivity, the compound (m1-3) includes methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. Glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (meth) acrylate N, N-dimethylamide, (meth) acrylic morpho Phosphorus, styrene, vinyltoluene and norbornene are preferred, methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (3-ethyloxetane-3-yl) methyl ( Meta) Acrylate, styrene and vinyl toluene are more preferred.

From the viewpoint of heat decomposition and heat yellowing, the compound (m1-3) is preferably an alkyl (meth) acrylate, more preferably a methyl (meth) acrylate, a benzyl (meth) acrylate, or a dicyclopentanyl (meth) acrylate. preferable.

From the viewpoint of solvent resistance of a color filter or the like obtained from a color curable composition, the compound (m1-3) includes a functional group that reacts with an acidic group (for example, a glycidyl group, an oxetanyl group, an isocyanato group, a block isocyanato). A polymerizable compound having a group) is preferable, and glycidyl (meth) acrylate and (3-ethyloxetane-3-yl) methyl methacrylate are more preferable.

Examples of the blocking agent used for blocking the above-mentioned isocyanato group include the following:
Lactam-based blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam;
Alcohol-based blocking agents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol;
Butylphenol such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid ester, timole, p-naphthol, p. -Phenol-based blocking agents such as nitrophenol and p-chlorophenol;
Active methylene block agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone;
Mercaptan-based blocking agents such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan;
Amine-based blocking agents such as diphenylamine, phenylnaphthylamine, aniline, and carbazole;
Acid amide blocking agents such as acetanilide, acetanilide, acetate amide, benzamide;
Acid-imide-based blocking agents such as succinate imide and maleate imide;
Imidazole-based blocking agents such as imidazole, 2-methylimidazole, and 2-ethylimidazole;
Urea-based blocking agents such as urea, thiourea, and ethylene urea;
Carbamide-based blocking agents such as phenyl N-phenylcarbamate and 2-oxazolidone;
Imine-based blocking agents such as ethyleneimine and polyethyleneimine;
Oxime-based blocking agents such as formaldehyde, acetoaldoxime, acetooxime, methylethylketooxime, methylisobutylketooxime, cyclohexanoneoxime;
Sodium bisulfite, potassium bisulfite and other bisulfite-based blocking agents.

In order to control the weight molecular weight (Mw) and polydispersity (Mw / Mn) of the resin (B1) within a preferable range and to suppress gelation during polymerization, the solvent used for the polymerization has 3 carbon atoms. It is preferable to contain a hydroxy group-containing solvent of ~ 10. Examples of the hydroxy group-containing solvent having 3 to 10 carbon atoms include monoalcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and benzyl alcohol; ethylene glycol monomethyl ether and ethylene. Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol Examples thereof include (poly) alkylene glycol monoalkyl ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether and tripropylene glycol monomethyl ether.

The solvent used for the polymerization may contain a solvent other than the hydroxy group-containing solvent having 3 to 10 carbon atoms. Examples of the solvent include (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether and diethylene glycol methyl. Ethers such as ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, acetate Butyl, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxo Examples include ethers such as ethyl butyrate; aromatic hydrocarbons such as toluene and xylene; and carboxylic acid amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. Among these, (poly) alkylene glycol monoalkyl ether acetates are preferable from the viewpoint of reactivity.

The content of the hydroxy group-containing solvent having 3 to 10 carbon atoms with respect to the total amount of the solvent used for the polymerization is 10 to 100% by weight from the viewpoint of controlling the weight molecular weight and the polydispersity (Mw / Mn) of the resin (B1). It is preferably, and more preferably 20 to 100% by weight.

The amount of the solvent used in the polymerization is not particularly limited, but is preferably 30 to 30 parts by weight based on 100 parts by weight of the total amount of the compound (m1-1), the compound (m1-2) and the compound (m1-3). It is 1,000 parts by weight, more preferably 50 to 800 parts by weight.

The polymerization initiator that can be used for the polymerization is not particularly limited, and is, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2, Examples thereof include 2'-azobis (isobutyric acid) dimethyl, benzoyl peroxide, and tert-butylperoxy-2-ethylhexanoate. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.5 with respect to 100 parts by weight of the total amount of the compound (m1-1), the compound (m1-2) and the compound (m1-3) used. It is ~ 20 parts by weight, more preferably 1.0 to 10 parts by weight.

The resin (B) may contain a resin (B2) different from the resin (B1). The resin (B2) is preferably an alkali-soluble resin, and at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, "monomer (m2-1)"). It is preferable that the polymer contains a structural unit derived from (may be described as). In the polymer, the structural unit may contain only one type, or may contain two or more types.

The resin (B2) is a monomer having a structural unit derived from the monomer (m2-1), a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond (hereinafter, “monomer (m2-)”. It is more preferable that the copolymer contains a structural unit derived from (2) ”. The copolymer may contain other structural units. As other structural units, for example, a monomer (m2-1) and a monomer different from the monomer (m2-2) (hereinafter, "monomer (m2-3)" may be described. ), A structural unit having an ethylenically unsaturated bond, and the like. In the copolymer, each of the constituent units may contain only one type, or may contain two or more types.

Examples of the monomer (m2-1) include the following:
Acrylic acid, methacrylic acid, crotonic acid and unsaturated monocarboxylic acids such as o-, m-, p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, Bicyclounsaturated compounds containing carboxy groups such as 5-carboxymethylbicyclo [2.2.1] hept-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;
Carboxylic anhydrides such as the above unsaturated dicarboxylic acid anhydrides excluding fumaric acid and mesaconic acid;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. Kind;
Unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

As the monomer (m2-1), acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of reactivity and the solubility of the obtained resin in an alkaline aqueous solution.

The monomer (m2-2) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. The monomer (m2-2) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group. Examples of the cyclic ether structure having 2 to 4 carbon atoms include an oxylan ring, an oxetane ring, and a tetrahydrofuran ring.

Examples of the monomer (m2-2) include a monomer having an oxylanyl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “monomer (m2-2-1)”), and oxetanyl. A monomer having a group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-2)") and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond. (Hereinafter, it may be described as "monomer (m2-2-3)") and the like.

As the monomer (m2-2-1), for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, “monomer (m2-2)”. -1a) ”) and a monomer having an alicyclic unsaturated hydrocarbon epoxidized structure (hereinafter, may be described as“ (monomer m2-2-1b) ”. ).

As the monomer (m2-2-1a), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Examples of the monomer (m2-2-1a) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, and α-methyl. 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-tris (glycidyloxymethyl) styrene and the like can be mentioned.

Examples of the monomer (m2-2-1b) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide® 2000; manufactured by Daicel), 3,4-epoxy. Cyclohexylmethyl (meth) acrylate (eg, Cyclomer® A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth) acrylate (eg, Cyclomer® M100; manufactured by Daicel), formula. Examples thereof include a compound represented by (BI) and a compound represented by the formula (BII).

[In formulas (BI) and (BII), ^Ra and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxy group.
X ^a and ^{X b} are each independently a single ^{^{bond, * - R c -, *}} - R c -O -, * - R c -S- or ^* -R c -NH- the stands,
R ^c represents an alkanediyl group having 1 to 6 carbon atoms, and * represents a bond position with O. ]

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

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

Further, the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used independently, respectively, and the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone. May be used in combination with. When these are used in combination, the molar ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) (the compound represented by the formula (BI): the compound represented by the formula (BII)) is used. , It is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.

Examples of the monomer (m2-3) include the following:
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, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] Decene-9-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate , (Meta) acrylates such as naphthyl (meth) acrylates and benzyl (meth) acrylates;
Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-Phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene;
Vinyl group-containing nitriles such as (meth) acrylonitrile;
Halogenated hydrocarbons such as vinyl chloride and vinylidene chloride;
Vinyl group-containing amides such as (meth) acrylamide;
Esters such as vinyl acetate;
Dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

From the viewpoint of reactivity and heat resistance, the monomers (m2-3) include styrene, vinyltoluene, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, and tricyclo [ 5.2.1.0 ^2,6 ] Decane-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] Decene-8-yl (meth) acrylate, tricyclo [5.2. 1.0 ^2,6 ] Decene-9-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and benzyl (meth) Acrylate is preferred.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group. The resin (B2) having such a structural unit is a polymer containing a structural unit derived from the monomer (m2-1) and a structural unit derived from the monomer (m2-2). It can be obtained by adding a group capable of reacting with the group having the group and a monomer having an ethylenically unsaturated bond.

As the structural unit having an ethylenically unsaturated bond, for example, a structural unit obtained by adding glycidyl (meth) acrylate to the (meth) acrylic acid unit, and 2-hydroxyethyl (meth) acrylate as the maleic anhydride unit. Constituent units obtained by addition, structural units obtained by adding (meth) acrylic acid to glycidyl (meth) acrylate units, and structural units obtained by adding carboxylic acid anhydride to structural units having a hydroxy group. Units and the like can be mentioned.

A polymer containing a structural unit derived from the monomer (m2-1) can be produced, for example, by polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, solvent and the like are not particularly limited, and those usually used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Can be mentioned. The solvent is not particularly limited as long as it dissolves each monomer, and examples thereof include the solvent (H) described later. As the obtained polymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the polymer is taken out as a solid (powder) by a method such as reprecipitation. May be used.

In the production of a polymer containing a structural unit derived from a monomer (m2-1), a carboxylic acid anhydride having an ethylenically unsaturated bond may be used as the monomer. Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic acid anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and the like. Examples thereof include 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.

Examples of the resin (B2) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl. (Meta) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid common weight Combined, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, 3,4-epoxytricyclo [5 2.1.0 ^2,6 ] Decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2] .1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (Meta) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / tricyclo [5.2.1 .0 ^2,6 ] Decenyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer , Benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer and JP-A-9-106071, JP-A-2004-29518 and JP-A-2004-361455. Examples of the resin described in 1.

When a combination of two or more resins (B2) is used, the combination is a combination of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid. Polymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer , 3,4-Epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyltoluene copolymer, and 3,4-epoxytricyclo [5.2] .1.0 ^2,6 ] It is preferable to contain at least one selected from the group consisting of decyl (meth) acrylate / (meth) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer.

The weight average molecular weight (Mw) of the resin (B2) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. .. The polydispersity (Mw / Mn) of the resin (B2) (that is, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) is preferably 1.1 to 6, more preferably 1.2. ~ 4. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (B2) are values calculated in terms of polystyrene using gel permeation chromatography (GPC).

The acid value (solid content conversion value) of the resin (B2) is preferably 10 to 300 mgKOH / g, more preferably 20 to 250 mgKOH / g, even more preferably 20 to 200 mgKOH / g, still more preferably 20 to 170 mgKOH / g. It is even more preferably 30 to 170 mgKOH / g, particularly preferably 50 to 150 mgKOH / g, even more preferably 60 to 140 mgKOH / g, and most preferably 60 to 135 mgKOH / g. The acid value of the resin (B2) is a value calculated as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B2), for example, by titrating with an aqueous potassium hydroxide solution. Can be sought.

When the resin (B2) is used, its content with respect to 100 parts by weight of the colorant (A) is from the viewpoint of storage stability of the color curable composition and heat resistance of a color filter or the like obtained from the color curable composition. Therefore, it is preferably 10 to 40 parts by weight, and more preferably 10 to 30 parts by weight.

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent known in the field of color curable composition can be used. Examples of the solvent (E) include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-) and an ether solvent (a solvent containing -O- in the molecule and not containing -COO-). , 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 (OH in the molecule) Included, -O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like. The concept of "-O-" does not include "-O-" in "-COO-", and the concept of "-CO-" includes "-CO-" in "-COO-". Is not included.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and the like. Examples thereof include butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol mono. Ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methyl anisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Methyl, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene Examples thereof include 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 the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, diacetone alcohol, and cyclo. Examples include pentanone, cyclohexanone and isophorone.

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

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

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

The solvent (E) is preferably 3-methoxybutanol, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diacetone. At least one selected from the group consisting of alcohol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide, more preferably 3-methoxybutanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether. , At least one selected from the group consisting of ethyl lactate, diacetone alcohol and ethyl 3-ethoxypropionate, and more preferably at least one selected from the group consisting of 3-methoxybutanol, propylene glycol monomethyl ether acetate and diacetone alcohol. It is one.

From the viewpoint of dispersibility, the content of the solvent (E) is preferably 70 to 95% by weight, more preferably 75 to 90% by weight, still more preferably 80 to 90% by weight, based on the total amount of the composition of the present invention. %.

<Other components of the composition>
The composition of the present invention may contain other components different from the above components as long as the effects of the present invention are not impaired. Other components include, for example, additives known in the field of color curable compositions.

A dispersant may be used as another component. Examples of the dispersant include surfactants. The surfactant may be any of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Examples of the surfactant include polyester-based surfactants, polyamine-based surfactants, acrylic-based surfactants, and the like. Commercially available dispersants include KP (Shin-Etsu Chemical Co., Ltd.), Floren (Kyoeisha Chemical Co., Ltd.), Solspers (registered trademark) (Zeneca), EFKA (BASF), Aziper (registered trademark) (Ajinomoto). (Fine Techno Co., Ltd.), DISPERBYK (registered trademark) (manufactured by Big Chemie Japan Co., Ltd.), BYKLPN (manufactured by Big Chemie Japan Co., Ltd.) and the like.

When a dispersant is used, its content is preferably 35 to 100 parts by weight, more preferably 35 to 65 parts by weight, still more preferably 40 to 65 parts by weight, based on 100 parts by weight of the colorant (A). Particularly preferably, it is 40 to 60 parts by weight.

<Manufacturing method of composition>
The composition of the present invention is, for example, a colorant (A) containing at least one selected from the group consisting of compound (1a), compound (2a) and compound (3a), and a resin (B) containing a resin (B1). , Solvent (E), and if necessary, other components (eg, dispersant) can be mixed.

The device for mixing each component is not particularly limited, and a device known in the field of color curable composition can be used. When a component (for example, a pigment) insoluble in the solvent (E) is used, it is preferable to sufficiently stir the mixture of each component using a bead mill, a paint conditioner, or the like.

<Color curable composition>
A color-curable composition can be produced by mixing the composition of the present invention obtained as described above, the polymerizable compound (C), and the polymerization initiator (D).

In the production of the color curable composition, components different from the composition, the polymerizable compound (C) and the polymerization initiator (D) of the present invention may be used. For example, the solvent (E) may be further added. Examples of the solvent (E) that can be used for producing the color-curable composition include those described in the solvent (E) of the composition of the present invention.

The content of the solvent (E) is preferably 70 to 90% by weight, more preferably 75 to 90% by weight, still more preferably 80 to 90% by weight, based on the total amount of the color curable composition.

The viscosity (= initial viscosity) of the color-curable composition immediately after production is preferably 3 to 15 mPa · s, more preferably 3 to 13 mPa · s, and further preferably 3 to 10 mPa · s. This initial viscosity is a value measured using a cone plate type (E type) viscometer under the conditions of a rotation speed of 100 rpm and a measurement temperature of 23 ° C.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D). The polymerizable compound (C) is preferably a radically polymerizable compound. Examples of the radically polymerizable compound include compounds having a polymerizable ethylenically unsaturated bond. The radically polymerizable compound is preferably (meth) acrylates.

Examples of the polymerizable compound (C) include the following:
Compounds having one ethylenically unsaturated bond such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone;
1,6-Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol A bis (acryloyloxyethyl) ether and Compounds with two ethylenically unsaturated bonds, such as 3-methylpentanediol di (meth) acrylate;
Compounds with three ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2- (meth) acryloyloxyethyl) isocyanurate;
Four ethylenically unsaturated bonds such as pentaerythritol tetra (meth) acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified pentaerythritol tetra (meth) acrylate. Compounds;
Compounds with 5 ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate;
Six ethylenic compounds such as dipentaerythritol hexa (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Compounds with unsaturated bonds;
A compound having seven or more ethylenically unsaturated bonds such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, and tetrapentaerythritol deca (meth) acrylate.

The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 or 6 ethylenically unsaturated bonds. Specifically, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable. Commercially available products of the polymerizable compound (C) include, for example, KAYARAD (registered trademark) DPHA (Nippon Kayaku Co., Ltd.), A-TMM-3LM-N (Shin-Nakamura Chemical Co., Ltd.) and A9550 (Shin-Nakamura Chemical Co., Ltd.). And so on.

The molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less. The molecular weight of the polymerizable compound (C) of 1,000 or more is a weight average molecular weight (Mw) calculated in terms of polystyrene using gel permeation chromatography (GPC).

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

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids and the like by the action of light or heat and initiating the polymerization of the polymerizable compound (C), and is known to initiate polymerization. Agents can be used. The polymerization initiator (D) is preferably a photoradical polymerization initiator. The polymerizable compound (C) is a radically polymerizable compound, and the polymerization initiator (D) is a photoradical polymerization initiator (that is, the curable composition is a photocurable composition). Is more preferable.

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

The O-acyloxime compound is a compound having a partial structure represented by the formula (d1) (in the following formula, * represents a binding position).

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. 1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-Il] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1 -On-2-imine, N-acetyloxy-1- [4- (2-hydroxyethyloxy) phenylsulfanylphenyl] propan-1-one-2-imine and the like can be mentioned. TR-PBG327 (manufactured by Joshu Powerful Electronics New Materials Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (above, manufactured by BASF), N- Commercially available products such as 1919 (manufactured by ADEKA) may be used.

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4). -Morphorinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one And so on. Commercially available products such as Irgacure (registered trademark) 369, Irgacure (registered trademark) 907, and Irgacure (registered trademark) 379 (all manufactured by BASF) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyl dimethyl ketal.

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

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naftyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) )-1,3,5-Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. Can be mentioned.

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

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4. , 4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373), 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 (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204), 4,4 Examples thereof include a biimidazole compound in which the phenyl group at the', 5, 5'-position is substituted with a carboalkoxy group (see, for example, JP-A-7-10913).

Examples of the other polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4 Benzoyl compounds such as -benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenance Kinone compounds such as lenquinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycioxylate, titanosen compounds and the like can be mentioned.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylate, benzoin Examples include tosilates.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the resin (B) and the polymerizable compound (C). It is a department.

<Other components of the color curable composition>
The color-curable composition may contain other components different from the above components. Other components include, for example, additives known in the field of color curable compositions.

A leveling agent may be used as another ingredient. Examples of the leveling agent include silicone-based surfactants and fluorine-based surfactants.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Examples of commercially available products include Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning), KP321, KP322, KP323, KP324, and KP326. , KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like.

The silicone-based surfactant may have a fluorine atom. Examples of the silicone-based surfactant having a fluorine atom include Megafuck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

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

When a leveling agent is used, its content is preferably 0.001 to 0.2% by weight, more preferably 0.002 to 0.1% by weight, still more preferably, based on the total amount of the color curable composition. Is 0.01 to 0.05% by weight. When the content of the leveling agent is within the above range, the flatness of the color filter obtained from the color curable composition can be improved.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited by the following Examples and the like, and appropriate modifications are made to the extent that the above and the following objectives can be met. It can also be carried out in addition, all of which are within the technical scope of the invention. Further, "part" described in the following examples and the like means "part by weight", and "%" other than the thickening ratio (%) described later means "% by weight".

Production Example 1: Production of resin (B1-1) Put 750.0 parts of 3-methoxybutanol in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and stir while replacing with nitrogen. The temperature was raised to 80 ° C. Next, 2,2'-azobis (2,4-dimethylvaleronitrile) was added to a monomer mixture consisting of 25.6 parts of methacrylic acid, 146.4 parts of 3-methacryloyloxypropyltrimethoxysilane and 49.2 parts of methyl methacrylate. A product to which 28.8 parts (polymerization initiator) was added was added dropwise to the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 80 ° C. for 5 hours to carry out a copolymerization reaction to obtain a copolymer (hereinafter referred to as “resin (B1-1)”) solution (solid content 20%). The acid value (solid content conversion value) of the resin (B1-1) was 82 mgKOH / g, its weight average molecular weight (Mw) was 5,500, and its silyl group equivalent was 500.

Production Example 2: Production of Resin (B2-1) A flask equipped with a reflux condenser, a dropping funnel and a stirrer was set to have a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, in the flask, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] A solution of 289 parts of a mixture of decan-9-ylacrylate (content ratio is 50:50 in molar ratio) in 125 parts of propylene glycol monomethyl ether acetate was dissolved in 125 parts of propylene glycol monomethyl ether acetate over about 5 hours using a dropping pump. And dropped. On the other hand, a solution prepared by dissolving 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate is added dropwise into the flask over about 6 hours using another dropping pump. did. After the dropping of the polymerization initiator is completed, the mixture is held at 80 ° C. for about 4 hours, cooled to room temperature, and the copolymer (hereinafter referred to as “resin (B2-1)”) solution (solid content 35). .1%) was obtained. The acid value (solid content conversion value) of the resin (B2-1) was 77 mgKOH / g, its weight average molecular weight (Mw) was 9,200, and its polydispersity (Mw / Mn) was 2.08.

Production Example 3: Production of resin (B2-2) The inside of a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer is replaced with a nitrogen atmosphere, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate are added and stirred. While heating to 85 ° C. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] ^{. 6} ] A mixed solution of 25 parts of a mixture of decane-9-ylacrylate, 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the mixture was held at 85 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (hereinafter referred to as "resin (B2-2)") solution (solid content 25.6%). .. The viscosity of the resin (B2-2) solution at 23 ° C. measured with a B-type viscometer was 23 mPa · s. The acid value (solid content conversion value) of the resin (B2-2) was 111 mgKOH / g, its weight average molecular weight (Mw) was 8,000, and its polydispersity (Mw / Mn) was 2.1. ..

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin were measured by GPC under the following conditions.
Equipment: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shima-pack GPC-80M
Column temperature; 40 ° C
Solvent; THF (tetrahydrofuran)
Test solution concentration; 25 mg / mL (solvent; THF)
Flow velocity; 1.0 mL / min
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

Production Example 4: Production of a compound represented by the formula (1a-1) A compound represented by the following formula (1a-1) is prepared in the same manner as in Example 7 of JP-A-2018-127596. Manufactured as a colorant (A).

Production Example 5: Production of a compound represented by the formula (2a-1) A compound represented by the following formula (2a-1) is prepared in the same manner as in the method described in Synthesis Example 19 of Japanese Patent Application Laid-Open No. 2015-38201. Manufactured as a colorant (A).

Example 1: Production of composition (1) 7 parts of compound (1a-1), 3 parts of dispersant (DISPERBYK (registered trademark) -2050 (manufactured by Big Chemie Japan)), resin (B1-1) (solid content) (Conversion) 3 parts, 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol and 300 parts of 0.2 mm zirconia beads are mixed, and the obtained mixture is mixed for 3 hours using a paint conditioner (manufactured by LAU). It was shaken. Then, the zirconia beads were removed by filtration to obtain the composition (1).
The content of the colorant (A) (compound (1a-1)) of the composition (1) was 53.8% with respect to the total amount of solids.
The content of the solvent (E) in the composition (1) was 87% with respect to the total amount of the composition.

Example 2: Production of composition (2) 7 parts of compound (1a-1), 3 parts of dispersant (DISPERBYK (registered trademark) -2050 (manufactured by Big Chemie Japan)), resin (B1-1) (solid content) 1 part of resin (B2-1) (solid content conversion), 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol and 300 parts of 0.2 mm zirconia beads are mixed and painted conditioner (LAU). The resulting mixture was shaken for 3 hours using. Then, the zirconia beads were removed by filtration to obtain the composition (2).
The content of the colorant (A) (compound (1a-1)) of the composition (2) was 53.8% with respect to the total amount of solids.
The content of the solvent (E) in the composition (2) was 87% with respect to the total amount of the composition.

Comparative Example 1: Production of composition (3) 7 parts of compound (1a-1), 3 parts of dispersant (DISPERBYK (registered trademark) -2050 (manufactured by Big Chemie Japan)), resin (B2-1) (solid content) (Conversion) 3 parts, 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol and 300 parts of 0.2 mm zirconia beads were mixed and shaken for 3 hours using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain the composition (3).
The content of the solid colorant (A) (compound (1a-1)) in the composition (3) was 53.8% of the total solid content.
The content of the solvent (E) in the composition (3) was 87% with respect to the total amount of the composition.

Example 3: Production of composition (4) 5 parts of compound (2a-1), 4 parts of dispersant (BYKLPN-21324 (manufactured by Big Chemie Japan)), 4 parts of resin (B1-1) (solid content conversion) , 87 parts of propylene glycol monomethyl ether acetate and 300 parts of 0.2 mm zirconia beads were mixed, and the obtained mixture was shaken for 3 hours using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain the composition (4).
The content of the colorant (A) (compound (2a-1)) of the composition (4) was 38.5% with respect to the total amount of solids.
The content of the solvent (E) in the composition (4) was 87% with respect to the total amount of the composition.

Comparative Example 2: Production of composition (5) 5 parts of compound (2a-1), 4 parts of dispersant (BYKLPN-21324 (manufactured by Big Chemie Japan)), 4 parts of resin (B2-1) (solid content conversion) , 87 parts of propylene glycol monomethyl ether acetate and 300 parts of 0.2 mm zirconia beads were mixed and shaken for 3 hours using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain the composition (5).
The content of the colorant (A) (compound (2a-1)) of the composition (5) was 38.5% with respect to the total amount of solids.
The content of the solvent (E) in the composition (5) was 87% with respect to the total amount of the composition.

<Evaluation of compositions (1) to (5)>
Color curable compositions (1) to (6) were produced using the compositions (1) to (5) obtained in Examples 1 to 3 and Comparative Examples 1 and 2 as described below. The thickening rate of the colored curable composition was measured.

(1-1) Production of Color Curable Compositions (1) to (3) 281 parts of any of the compositions (1) to (3), resin (B2-2) (solid content equivalent) 50 parts, dipenta 50 parts of erythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., polymerizable compound (C)), N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (manufactured by BASF, "Irgacure" Registered trademark) OXE01 ”, polymerization initiator (D) 3 parts, propylene glycol monomethyl ether acetate (solvent (E)) 500 parts, and polyether-modified silicone oil (Toray Dow Corning“ Torre Silicone SH8400 ”, leveling Agent) 0.1 part was mixed to obtain colored curable compositions (1) to (3).

(1-2) Production of Color Curable Compositions (4) and (5) 424 parts of any of the compositions (4) and (5), 50 parts of resin (B2-2) (solid content equivalent), dipenta 50 parts of erythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., polymerizable compound (C)), N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (manufactured by BASF, "Irgacure" Registered trademark) OXE01 ”, polymerization initiator (D) 3 parts, propylene glycol monomethyl ether acetate (solvent (E)) 430 parts, and polyether-modified silicone oil (Toray Dow Corning“ Torre Silicone SH8400 ”, leveling Agent) 0.1 parts were mixed to obtain color-curable compositions (4) and (5).

(1-3) Production of Color Curable Composition (6) Composition (5) 424 parts, resin (B2-2) (solid content equivalent) 50 parts, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., polymerization) 50 parts of sex compound (C)), N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-on-2-imine (BASF "Irgacure (registered trademark) OXE01", polymerization initiator (D) )) 3 parts, propylene glycol monomethyl ether acetate (solvent (E)) 360 parts, 3-methoxybutanol (solvent (E)) 70 parts, and polyether-modified silicone oil (Toray Dow Corning "Torre Silicone SH8400" , Leveling agent) 0.1 part was mixed to obtain a color curable composition (6).

(2) Measurement of thickening rate The viscosity (= initial viscosity) of the colored curable compositions (1) to (6) immediately after production is adjusted to a cone plate type (E type) under the conditions of a rotation speed of 100 rpm and a measurement temperature of 23 ° C. The measurement was performed using a viscometer (“Viscometer TV-25” manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 1.

The viscosity (= viscosity after storage) of the color-curable compositions (1) to (6) after being stored at 40 ° C. for 7 days was measured in the same manner as above, and the following formula:
Viscosity thickening rate (%) = 100 x viscosity after storage (mPa · s) / initial viscosity (mPa · s)
The thickening rate was calculated by. The results are shown in Table 1.

As shown in Table 1, the color-curable compositions (1) to (3) obtained by using the compound (1a-1) as the colorant (A) include the resin (B-1). The thickening rates (at 101% and 102%) of the color-curable compositions (1) and (2) obtained from (1) and (2) (Examples 1 and 2) are based on the resin (B-1). It was suppressed more than the thickening rate (111%) of the color-curable composition (3) obtained from the composition (3) (Comparative Example 1) containing no.

Further, as shown in Table 1, the color-curable compositions (4) to (6) obtained by using the compound (2a-1) as the colorant (A) contain the resin (B-1). The thickening rate (100%) of the color-curable composition (4) obtained from the composition (4) (Example 3) is the composition (5) containing no resin (B-1) (Comparative Example 2). The thickening rates (104% and 103%) of the color-curable compositions (5) and (6) obtained from) were suppressed.

By producing the composition of the present invention in advance and then producing a color-curable composition using the composition of the present invention, thickening of the color-curable composition can be suppressed. Such a color curable composition is useful for producing, for example, a color filter.

Claims

A composition containing a colorant (A), a resin (B) and a solvent (E).
The colorant (A) has the formula (1a) :.

[In the formula (1a), R 41a and R 42a may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents a good aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41a and R 42a are bonded to each other. Forming a 3 to 10-membered nitrogen-containing heterocycle with the nitrogen atom
R 43a and R 44a each independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 14 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R 43a and R 44a are bonded and bonded to each other. Forming a nitrogen-containing heterocycle,
R 47a ~ R 54a are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy group, -SO 3 -, -SO 2 -N - have -SO 2 -R f or a substituent, Represents a good alkyl group with 1 to 8 carbon atoms
R f represents a fluoroalkyl group having 1 to 12 carbon atoms.
Ring T 1a represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 - R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
Substituents which may be the aralkyl group have the carbon number of 7 to 30, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 -R f, And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
Aromatic hydrocarbon ring substituent that have the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 - R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
Wherein said 5 to 10-membered aromatic heterocyclic ring substituent which may have of a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 -R f , And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-. May be
When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH 2- contained in the alkyl group may be replaced with -O- or -CO-.
r represents an integer of 1 or more
Mr + represents a hydrogen ion, an r-valent metal ion or N + (R 55a ) 4 , and the four R 55a may be the same or different.
R 55a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
k is the formula (1a-A):

[In the formula (1a-A), the rings T 1a , R 41a to R 44a and R 47a to R 54a are synonymous with the above, respectively. ]
In -SO 3 anion has represented - and -SO 2 -N - represents the total number of -SO 2 -R f, a and an integer of 2 or more,
When r is an integer of 2 or more, the plurality of anions represented by the formula (1a-A) may be the same or different, and when k-1 is an integer of 2 or more, a plurality of M's may be present. r + may be the same or different. ]
Compound represented by,
Equation (2a):

[In the formula (2a), R 41b and R 42b may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents a good aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 41b and R 42b are bonded to each other. Forming a 3 to 10-membered nitrogen-containing heterocycle with the nitrogen atom
R 43b and R 44b independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 14 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or 3 to 10 members together with a nitrogen atom to which R 43b and R 44b are bonded and bonded to each other. Forming a nitrogen-containing heterocycle,
R 47b to R 54b each independently represent an alkyl group having 1 to 8 carbon atoms which may have a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or a substituent.
Ring T 1b represents an aromatic hydrocarbon ring having 6 to 14 carbon atoms which may have a substituent or a 5 to 10 member aromatic heterocycle which may have a substituent.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The substituents that the aromatic hydrocarbon group having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms. At least one selected from the group consisting of alkyl groups of
The substituents that the aralkyl group having 7 to 30 carbon atoms may have are a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl group having 1 to 8 carbon atoms that may have a substituent. At least one selected from the group consisting of
The substituents that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have may have a halogen atom, a nitro group, a hydroxy group, a formyl group, and a substituent having 1 to 8 carbon atoms. At least one selected from the group consisting of alkyl groups of
The substituents that the 5- to 10-membered aromatic heterocycle may have are a halogen atom, a nitro group, a hydroxy group, a formyl group, and an alkyl having 1 to 8 carbon atoms that may have a substituent. At least one selected from the group of groups,
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-. May be
When the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH 2- contained in the alkyl group may be replaced with -O- or -CO-.
m represents an integer of 1 or more
[Y] m- represents an m-valent anion, and when m is an integer of 2 or more, the formula (2a-C):

[In the formula (2a-C), rings T 1b , R 41b to R 44b and R 47b to R 54b are synonymous with the above, respectively. ]
The plurality of cations represented by may be the same or different. ]
The compound represented by, and formula (3a):

[In the formula (3a), R 1 and R 2 may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. A good aromatic hydrocarbon group with 6 to 10 carbon atoms or -R 12- Si (R 13 ) 3 is represented, or R 1 and R 2 are bonded and 3 to 10 members together with the nitrogen atom to which they are bonded. Forming a nitrogen-containing heterocycle,
R 3 and R 4 independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 10 carbon atoms which may have a substituent. It represents an aromatic hydrocarbon group or a group represented by -R 12- Si (R 13 ) 3 , or contains 3 to 10 members together with the nitrogen atom to which R 3 and R 4 are bonded. Forming a nitrogen heterocycle,
R 5 is, -OH, -SO 3 -, -SO 3 - Z +, -SO 3 R 8, -CO 2 - Z +, -CO 2 R 8, or represents -SO 2 NR 9 R 10,
R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
p represents an integer of 0 to 5, and when p is an integer of 2 or more, a plurality of R 5s may be the same or different.
q represents 0 or 1 and represents
X represents a halogen atom
Z + stands for N + (R 11 ) 4 , Na + or K + , and the four R 11s may be the same or different.
R 8 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a halogen atom.
R 9 and R 10 each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, or R 9 and R 10 are bonded to each other. Together with the nitrogen atoms they bind to, they form a 3-10 member nitrogen-containing heterocycle,
R 11 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
R 12 represents an alkanediyl group having 1 to 10 carbon atoms.
R 13 represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the three R 13s may be the same or different, respectively.
The substituents that the saturated hydrocarbon groups having 1 to 20 carbon atoms of R 1 to R 4 may have are aromatic hydrocarbon groups having 6 to 10 carbon atoms, halogen atoms, hydroxy groups, formyl groups and carboxy groups. At least one selected from the group of groups,
The substituents that may have the aromatic hydrocarbon group having 6 to 10 carbon atoms of R 1 to R 4 may have a halogen atom, a hydroxy group, a formyl group, and a halogen atom. saturated hydrocarbon group of ~ 20, -OR 8, -SO 3 -, -SO 3 - Z +, -SO 3 R 8, -CO 2 - Z +, -CO 2 R 8 and -SO 2 NR 9 R 10 At least one selected from the group consisting of
When the saturated hydrocarbon group having 1 to 20 carbon atoms in R 1 to R 4 is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is -O-, -CO- or -NR 11 - may be replaced to,
The substituents of the saturated hydrocarbon groups having 1 to 20 carbon atoms of R 9 and R 10 may have at least one selected from the group consisting of a hydroxy group, a formyl group and a halogen atom.
When the saturated hydrocarbon group having 1 to 20 carbon atoms of R 9 and R 10 is a saturated hydrocarbon group having 2 to 20 carbon atoms, -CH 2- contained in the saturated hydrocarbon group is -O-, -CO- or -NR 8 - may be replaced to,
When the alkanediyl group having 1 to 10 carbon atoms of R 12 is an alkanediyl group having 2 to 20 carbon atoms, -CH 2- contained in the alkanediyl group is -O-, -CO- or -NR. 8 - may be replaced in, and -SO 3 in the form of ions in the compound represented by formula (3a) - if there is, the number is one. ]
Containing at least one selected from the group consisting of compounds represented by
The resin (B) is the formula (1b):

[In formula (1b), R 1B represents a hydrogen atom or a methyl group.
R 2B to R 4B independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
n represents an integer from 1 to 10, and * represents the bond position.
However, at least one of R 2B to R 4B is an alkoxy group having 1 to 6 carbon atoms. ]
A composition containing a resin (B1) containing the structural unit (b1-1) represented by, and having a content of the colorant (A) of 35 to 70% by weight based on the total solid content of the composition. ..
The composition according to claim 1, wherein the content of the colorant (A) is 40 to 70% by weight based on the total solid content of the composition.
The ring T 1a in the formula (1a) is the formula (1t):

[In the formula (1t), R 45a and R 46a may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents a good aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 45a and R 46a are bonded to each other. Forming a 3 to 10-membered nitrogen-containing heterocycle with the nitrogen atom
R 56a is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have a group.
L 1a represents a sulfur atom, an oxygen atom or -NR 57a- .
R 57a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The aromatic hydrocarbon group substituents which may be possessed by the carbon number of 6 to 14, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 - R f , and at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
Substituents which may be the aralkyl group have the carbon number of 7 to 30, a halogen atom, a nitro group, hydroxy group, formyl group, -SO 3 -, -SO 2 -N - -SO 2 -R f, And at least one selected from the group consisting of alkyl groups having 1 to 8 carbon atoms which may have substituents.
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
R f represents a fluoroalkyl group having 1 to 12 carbon atoms, and * represents a bond position with a carbocation. ]
The composition according to claim 1 or 2, which is a ring represented by.
The composition according to any one of claims 1 to 3, wherein r is 2 and Mr + is a divalent metal ion in the formula (1a).
In formula (1a), R 41a and R 43a are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R 42a and R 44a are each independently an alkyl group and -SO 3 having 1 to 8 carbon atoms - at least one of which may have a substituent phenyl group selected from the group consisting of,
R 47a ~ R 54a are each independently a hydrogen atom, an alkyl group or -SO 3 having 1 to 8 carbon atoms - and ring T 1a has the formula (1t):

[In the formula (1t), R 45a is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R 46a is an alkyl group and -SO 3 having 1 to 8 carbon atoms - at least one of which may have a substituent phenyl group selected from the group consisting of,
R 56a is a halogen atom, an alkyl group and -SO 3 having 1 to 8 carbon atoms - at least one of which may have a substituent phenyl group selected from the group consisting of,
L 1a is a sulfur atom, and * represents a bond position with a carbocation. ]
It is a ring represented by
r is 2,
k is -SO 3 having the anion represented by the formula (1a-A) - represents the total number of, and 2, two anion represented by the formula (1a-A) is located in the same , And the composition according to claim 1 or 2, wherein Mr + is a barium ion.
The ring T 1b in the formula (2a) is the formula (2t):

[In the formula (2t), R 45b and R 46b may independently have a hydrogen atom and a substituent, even if they have a saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent. It represents a good aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R 45b and R 46b are bonded to each other. Forming a 3 to 10-membered nitrogen-containing heterocycle with the nitrogen atom
R 56b is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have a group.
L 1b represents a sulfur atom, an oxygen atom or -NR 57b-
R 57b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
The substituent which the saturated hydrocarbon group having 1 to 20 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group.
The substituent which may have the aromatic hydrocarbon group having 6 to 14 carbon atoms is a halogen atom, a nitro group, a hydroxy group, a formyl group and a substituent having 1 to 8 carbon atoms which may have a substituent. At least one selected from the group consisting of alkyl groups,
The substituent which the aralkyl group having 7 to 30 carbon atoms may have is from a halogen atom, a nitro group, a hydroxy group, a formyl group and an alkyl group having 1 to 8 carbon atoms which may have a substituent. At least one selected from the group
The substituent which the alkyl group having 1 to 8 carbon atoms may have is at least one selected from the group consisting of a halogen atom, a hydroxy group, a formyl group and an amino group, and * is a carbocation. Represents the connection position of. ]
The composition according to any one of claims 1 to 5, which is a ring represented by.
The composition according to any one of claims 1 to 6, wherein [Y] m− in the formula (2a) is a polyacid anion containing a tungsten atom.
[Y] m- in the formula (2a) is [PW 12 O 40 ] 3- , [P 2 W 18 O 62 ] 6- , [P 2 W 18 O 62 ] 6- , [SiW 12 O 40 ]. 4- , [SiW 12 O 40 ] 4- , [SiW 12 O 40 ] 4- , [P 2 W 17 O 61 ] 10- , [P 2 W 15 O 56 ] 12- , [H 2 P 2 W 12] O 48 ] 12- , [NaP 5 W 30 O 110 ] 14- , [SiW 9 O 34 ] 10- , [SiW 10 O 36 ] 8- , [SiW 11 O 39 ] 8- , [SiW 11 O 39 ] The composition according to any one of claims 1 to 6, which is 8- , [W 6 O 19 ] 2- , [W 10 O 32 ] 4- or [WO 4 ] 2- .
In formula (2a), R 41b , R 43b and R 47b to R 54b are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, respectively.
R 42b and R 44b are phenyl groups which may independently have an alkyl group having 1 to 8 carbon atoms.
Ring T 1b is the equation (2t):

[In formula (2t), R 45b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R 46b is a phenyl group which may have an alkyl group having 1 to 8 carbon atoms.
R 56b is a phenyl group which may have at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 8 carbon atoms.
L 1b is a sulfur atom, and * represents a bond position with a carbocation. ]
It is a ring represented by
m is 3,
The third aspect of any one of claims 1 to 5, wherein the three cations represented by the formula (2a-C) are the same, and [Y] m- is [PW 12 O 40 ] 3- . Composition.
In formula (3a), R 1 and R 3 are independently hydrogen atoms; alkyl groups having 1 to 8 carbon atoms which may have a carboxy group; alkyl groups having 1 to 8 carbon atoms and -SO. A phenyl group which may have at least one substituent selected from the group consisting of 2 NR 9 R 10 ; or -R 12- Si (R 13 ) 3 .
R 2 and R 4 each independently consist of an alkyl group having 1 to 8 carbon atoms which may have a carboxy group; an alkyl group having 1 to 8 carbon atoms and -SO 2 NR 9 R 10. A phenyl group which may have at least one substituent of choice; or -R 12- Si (R 13 ) 3
R 5 is, -SO 3 - and is,
R 6 and R 7 are both hydrogen atoms,
R 9 and R 10 are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.
R 12 is an alkanediyl group having 1 to 6 carbon atoms.
All three R 13s are alkoxy groups having 1 to 4 carbon atoms.
The composition according to any one of claims 1 to 9, wherein p is 1 and q is 0.
The total content of the compound represented by the formula (1a), the compound represented by the formula (2a) and the compound represented by the formula (3a) is 50 to 100% by weight based on the total amount of the colorant (A). The composition according to any one of claims 1 to 10, which is%.
At least one selected from the group consisting of the compound represented by the formula (1a), the compound represented by the formula (2a) and the compound represented by the formula (3a) is the compound represented by the formula (1a). The composition according to any one of claims 1 to 5, wherein the content of the compound represented by the formula (1a) is 50 to 100% by weight based on the total amount of the colorant (A).
At least one selected from the group consisting of the compound represented by the formula (1a), the compound represented by the formula (2a) and the compound represented by the formula (3a) is the compound represented by the formula (2a). The composition according to any one of claims 1, 2 and 6 to 9, wherein the content of the compound represented by the formula (2a) is 50 to 100% by weight based on the total amount of the colorant (A). Stuff.
The resin (B1) is a copolymer containing a structural unit (b1-1), a structural unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group, and other structural units (b1-3). The present invention according to any one of claims 1 to 13, wherein the amount of the structural unit (b1-1) is 1 to 50 mol% when the total of all the structural units in the copolymer is 100 mol%. Composition.
The composition according to any one of claims 1 to 14, wherein the resin (B1) has a weight average molecular weight of 1,000 to 50,000.
The composition according to any one of claims 1 to 15, wherein the content of the resin (B1) is 10 to 100 parts by weight with respect to 100 parts by weight of the colorant (A).
The composition according to any one of claims 1 to 15, wherein the content of the resin (B1) is 10 to 60 parts by weight with respect to 100 parts by weight of the colorant (A).