CN114080567A

CN114080567A - Composition containing colorant

Info

Publication number: CN114080567A
Application number: CN202080049401.XA
Authority: CN
Inventors: 朴昭妍
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2019-07-10
Filing date: 2020-06-18
Publication date: 2022-02-22
Also published as: WO2021005997A1; JP2021014568A; KR20220034155A; TW202111012A

Abstract

The thickening of a colored curable composition can be suppressed by preparing in advance a composition containing a compound represented by the following formula (1a) or the like as a colorant (A) and a resin (B1) containing a constituent unit (B1-1) represented by the following formula (1B) as a resin (B) and having a content of the colorant (A) of 35 to 70 wt% relative to the total amount of solid components of the composition, and then producing the colored curable composition using the composition (the definition of the symbol in the following formula is described in the specification).

Description

Composition containing colorant

Technical Field

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

Background

The colored curable composition is used for producing a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, or a plasma display, and various compositions have been developed. For example, patent document 1 describes a resin composition for a color filter, which contains a solvent, a reactive diluent, a photopolymerization initiator, a colorant, and a copolymer containing a constituent unit represented by formula (1).

The symbol in formula (1) is defined as described in patent document 1. ]

Documents of the prior art

Patent document

Patent document 1: WO2018/110097A1

Disclosure of Invention

The present inventors have found that a colored curable composition comprising a colorant (a), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) has the following problems: depending on the kind of the colorant (A) used, the viscosity thereof increases during storage. The present invention has been made in view of such circumstances, and an object thereof is to suppress thickening of a colored curable composition containing a specific colorant.

The present invention which can achieve the above object is as follows.

[1] A composition comprising a colorant (A), a resin (B) and a solvent (E),

the colorant (A) contains at least one selected from the group consisting of a compound represented by formula (1a), a compound represented by formula (2a), and a compound represented by formula (3a),

[ in the formula (1a), R^41aAnd R^42aEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^41aAnd R^42aBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^43aand R^44aEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^43aAnd R^44aBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^47a～R^54aeach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or-SO₃ ^－、－SO₂－N^－－SO₂－R^fOr an alkyl group having 1 to 8 carbon atoms which may have a substituent,

R^frepresents a fluoroalkyl group having 1 to 12 carbon atoms,

ring T^1aRepresents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted five-to ten-membered aromatic heterocycle,

the saturated hydrocarbon group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group,

the C6-14 aromatic hydrocarbon group can have substituents selected from halogen atoms, nitro, hydroxyl, formyl and-SO₃ ^－、－SO₂－N^－－SO₂－R^fAnd optionally a substituted alkyl group having 1 to 8 carbon atoms,

the aralkyl group having 7 to 30 carbon atoms may have a substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and a-SO group₃ ^－、－SO₂－N^－－SO₂－R^fAnd optionally a substituted alkyl group having 1 to 8 carbon atoms,

the above-mentioned C6-14 aromatic hydrocarbon ring may have a substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a formyl group and a-SO group₃ ^－、－SO₂－N^－－SO₂－R^fAnd optionally substituted alkyl group having 1 to 8 carbon atomsAt least one of the first and second electrodes is,

the five-to ten-membered aromatic heterocyclic ring may have a substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and a-SO group₃ ^－、－SO₂－N^－－SO₂－R^fAnd optionally a substituted alkyl group having 1 to 8 carbon atoms,

the alkyl group having 1 to 8 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl 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, the saturated hydrocarbon group contains-CH₂-may be substituted by-O-or-CO-,

when the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, the alkyl group contains-CH₂-may be substituted by-O-or-CO-,

r represents an integer of 1 or more,

M^r+represents hydrogen ion, a metal ion of valence r or N⁺(R^55a)₄Four R^55aWhich may be the same or different from each other,

R^55arepresents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms,

k represents-SO that the anion represented by the formula (1 a-A) has₃ ^－and-SO₂－N^－－SO₂－R^fIs an integer of 2 or more,

[ in the formula (1 a-A), ring T^1a、R^41a～R^44aAnd R^47a～R^54aRespectively, the same as above.]

When r is an integer of 2 or more, the plural anions represented by the formula (1 a-A) may be the same or different, and

k-1 is an integer of 2 or moreSeveral times, a plurality of M^r+May be the same or different.]

[ in the formula (2a), R^41bAnd R^42bEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^41bAnd R^42bBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^43band R^44bEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^43bAnd R^44bBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^47b～R^54beach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms which may have a substituent,

ring T^1bRepresents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted five-to ten-membered aromatic heterocycle,

the C6-14 aromatic hydrocarbon group may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an optionally substituted C1-8 alkyl group,

the aralkyl group having 7 to 30 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent,

the C6-14 aromatic hydrocarbon ring may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an optionally substituted C1-8 alkyl group,

the five-to ten-membered aromatic heterocyclic ring may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and an optionally substituted alkyl group having 1 to 8 carbon atoms,

m represents an integer of 1 or more,

[Y]^m－an anion representing a valence of m, and

when m is an integer of 2 or more, the plural cations represented by the formula (2 a-C) may be the same or different,

[ formula (2 a-C) wherein the ring T^1b、R^41b～R^44bAnd R^47b～R^54bRespectively, the same as above.]]

[ in the formula (3a), R¹And R²Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 6 to 10 carbon atoms which may have a substituentAromatic hydrocarbon radical or-R¹²－Si(R¹³)₃Or R is¹And R²Bonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R³and R⁴Each independently represents 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 10 carbon atoms which may have a substituent, or-R¹²－Si(R¹³)₃A group represented by, or R³And R⁴Bonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R⁵represents-OH or-SO₃ ^－、－SO₃ ^－Z⁺、－SO₃R⁸、－CO₂ ^－Z⁺、－CO₂R⁸or-SO₂NR⁹R¹⁰，

R⁶And R⁷Each independently represents 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 R⁵Which may be the same or different from each other,

q represents a number of 0 or 1,

x represents a halogen atom, and X represents a halogen atom,

Z⁺represents N⁺(R¹¹)₄、Na⁺Or K⁺Four R¹¹Which may be the same or different from each other,

R⁸represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms and optionally having a halogen atom,

R⁹and R¹⁰Each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or R⁹And R¹⁰Bonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R¹¹represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms,

R¹²represents a carbon number of 1 to 1An alkanediyl group of 0 (c),

R¹³represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and three R¹³Each of which may be the same or different,

R¹～R⁴the saturated hydrocarbon group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, a formyl group and a carboxyl group,

R¹～R⁴the above-mentioned C6-10 aromatic hydrocarbon group may have a substituent selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group, a C1-20 saturated hydrocarbon group which may have a halogen atom, -OR⁸、－SO₃ ^－、－SO₃ ^－Z⁺、－SO₃R⁸、－CO₂ ^－Z⁺、－CO₂R⁸and-SO₂NR⁹R¹⁰At least one of the above-mentioned (B),

R¹～R⁴when the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, the saturated hydrocarbon group contains-CH₂May be substituted by-O-, -CO-or-NR¹¹－，

R⁹And R¹⁰The saturated hydrocarbon group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of a hydroxyl group, a formyl group and a halogen atom,

R⁹and R¹⁰When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, the saturated hydrocarbon group contains-CH₂May be substituted by-O-, -CO-or-NR⁸－，

R¹²When the alkanediyl group having 1 to 10 carbon atoms is an alkanediyl group having 2 to 20 carbon atoms, the alkanediyl group may contain-CH₂May be substituted by-O-, -CO-or-NR⁸-, and

-SO in the form of an ion present in the compound represented by formula (3a)₃ ^－In this case, the number of the cells is 1.]

The resin (B) comprises a resin (B1) containing a constituent unit (B1-1) represented by the formula (1B),

[ in the formula (1b), R^1BRepresents a hydrogen atom or a methyl group,

R^2B～R^4Beach independently represents 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 of 1 to 10, and

indicates the number of the bonding sites,

wherein R is^2B～R^4BAt least one of the above groups is an alkoxy group having 1 to 6 carbon atoms.]

And the content of the colorant (A) is 35-70 wt% relative to 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]According to the above [1]Or [2]]The composition, wherein, the ring T in the formula (1a)^1aIs a ring represented by the formula (1 t).

[ in the formula (1t), R^45aAnd R^46aEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^45aAnd R^46aBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^56arepresents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom which may have a substituentAn aromatic hydrocarbon group having 6 to 14 or an aralkyl group having 7 to 30 carbon atoms which may have a substituent,

L^1arepresents a sulfur atom, an oxygen atom or-NR^57a－，

R^57aRepresents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R^frepresents a fluoroalkyl group having 1 to 12 carbon atoms, and

denotes the bonding site to the carbenium ion. ]

[4]According to the above [1]～[3]The composition as described in any one of the above, wherein in the formula (1a), r is 2, and M^r+Is a 2-valent metal ion.

[5]According to the above [1]Or [2]]The composition, wherein, in the formula (1a), R^41aAnd R^43aEach independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R^42aand R^44aEach independently an alkyl group which may have 1 to 8 carbon atoms and-SO₃ ^－A phenyl group as at least one substituent in (1),

R^47a～R^54aeach independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or-SO₃ ^－，

Ring T^1aIs a ring represented by the formula (1t),

[ in the formula (1t), R^45aIs a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R^46amay have an alkyl group selected from the group consisting of 1 to 8 carbon atoms and-SO₃ ^－A phenyl group as at least one substituent in (1),

R^56amay have a halogen atom, an alkyl group having 1 to 8 carbon atoms and-SO₃ ^－A phenyl group as at least one substituent in (1),

L^1ais a sulfur atom, and

denotes the bonding site to the carbenium ion. ]

The number r is 2, and the number r,

k represents-SO that the anion represented by the formula (1 a-A) has₃ ^－The sum of the number of (a) and (b) is 2,

the two anions represented by the formula (1 a-A) are the same, and

M^r+is barium ion.

[6]According to the above [1]～[5]The composition as described in any one of the above, wherein the ring T in the formula (2a)^1bIs a ring represented by the formula (2t),

[ in the formula (2t), R^45bAnd R^46bEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^45bAnd R^46bBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^56brepresents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent,

L^1brepresents a sulfur atom, an oxygen atom or-NR^57b－，

R^57bRepresents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

the above-mentioned C6-14 aromatic hydrocarbon group may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and an optionally substituted C1-8 alkyl group,

The aralkyl group having 7 to 30 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and an alkyl group having 1 to 8 carbon atoms which may have a substituent,

the alkyl group having 1 to 8 carbon atoms may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group and an amino group, and

denotes the bonding site to the carbenium ion. ]

[7]According to the above [1]～[6]The composition as described in any one of the above, wherein [ Y ] in the formula (2a)]^m－Is a polyacid anion containing tungsten atoms.

[8]According to the above [1]～[6]The composition as described in any one of the above, wherein [ Y ] in the formula (2a)]^m－Is [ PW ]₁₂O₄₀]^3－、[P₂W₁₈O₆₂]^6－、[P₂W₁₈O₆₂]^6－、[SiW₁₂O₄₀]^4－、[SiW₁₂O₄₀]^4－、[SiW₁₂O₄₀]^4－、[P₂W₁₇O₆₁]^10－、[P₂W₁₅O₅₆]^12－、[H₂P₂W₁₂O₄₈]^12－、[NaP₅W₃₀O₁₁₀]^14－、[SiW₉O₃₄]^10－、[SiW₁₀O₃₆]^8－、[SiW₁₁O₃₉]^8－、[SiW₁₁O₃₉]^8－、[W₆O₁₉]^2－、[W₁₀O₃₂]^4－Or [ WO)₄]^2－。

[9]According to the above [1]～[5]The composition as described in any one of the above (2a), wherein R is represented by the formula^41b、R^43bAnd R^47b～R^54bEach independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R^42band R^44bEach independently a phenyl group which may have an alkyl group having 1 to 8 carbon atoms,

ring T^1bIs a ring represented by the formula (2t),

[ in the formula (2t), R^45bIs a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R^46ba phenyl group which may have an alkyl group having 1 to 8 carbon atoms,

R^56ba 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^1bis a sulfur atom, and

denotes the bonding site to the carbenium ion. ]

m is the number of 3,

the three cations represented by the formula (2 a-C) are the same, and

[Y]^m－is [ PW ]₁₂O₄₀]^3－。

[10]According to the above [1]～[9]Any one ofThe composition, wherein, in the formula (3a), R¹And R³Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a carboxyl group, an alkyl group having 1 to 8 carbon atoms which may have a group selected from the group consisting of₂NR⁹R¹⁰Phenyl of at least one substituent of (a), or-R¹²－Si(R¹³)₃，

R²And R⁴Each independently an alkyl group having 1 to 8 carbon atoms which may have a carboxyl group, and-SO₂NR⁹R¹⁰Phenyl of at least one substituent of (a), or-R¹²－Si(R¹³)₃，

R⁵is-SO₃ ^－，

R⁶And R⁷Are all hydrogen atoms, and are,

R⁹and R¹⁰Each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R¹²an alkanediyl group having 1 to 6 carbon atoms,

three R¹³All of which are C1-C4 alkoxy groups,

p is 1, and

q is 0.

[11] The composition according to any one of the above [1] to [10], wherein 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).

[12] The composition according to any one of the above [1] to [5], wherein 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), and 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).

[13] The composition according to any one of the above [1], [2] and [6] to [9], wherein 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), 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).

[14] The composition according to any one of the above [1] to [13], wherein the resin (B1) is a copolymer comprising a constituent unit (B1-1), a constituent unit (B1-2) derived from a polymerizable unsaturated compound having an acidic group, and another constituent unit (B1-3), and the amount of the constituent unit (B1-1) is 1 to 50 mol% based on 100 mol% of the total of all the constituent units in the copolymer.

[15] The composition according to any one of the above [1] to [14], wherein the weight average molecular weight of the resin (B1) is 1000 to 50000.

[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 based on 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 based on 100 parts by weight of the colorant (A).

First, by preparing the composition of the present invention in advance and then preparing the colored curable composition using the composition of the present invention, the thickening of the colored curable composition can be suppressed.

Detailed Description

The composition of the present invention comprises a colorant (A), a resin (B) and a solvent (E). The composition of the present invention is characterized in that the colorant (A) comprises at least one selected from the group consisting of a compound represented by formula (1a), a compound represented by formula (2a), and a compound represented by formula (3a), the resin (B) comprises a resin (B1) containing a constituent unit (B1-1) represented by formula (1B), and the content of the colorant (A) is 35 to 70% by weight relative to the total amount of the solid components of the composition. Here, the "total amount of solid components of the composition" means an amount obtained by subtracting the content of the solvent (H) from the total amount of the composition. The total amount of solid components 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, the "compound represented by the formula (1 a)" may be simply referred to as "compound (1 a)". In addition, compounds represented by other structural formulae, anions, and cations may be also abbreviated in some cases. The components of the composition of the present invention, the components of the colored curable composition, the raw materials for producing the components, and the like may be used in 1 type or 2 or more types in combination unless otherwise specified.

The invention is characterized in that: a specific colorant (i.e., at least one selected from the group consisting of the compound (1a), the compound (2a) and the compound (3 a)) is used. The present inventors found that the following problems exist: the viscosity of a colored curable composition containing a specific colorant increases upon storage. In order to solve the problem, the present inventors have conducted extensive studies and, as a result, have found that: the thickening of the colored curable composition can be suppressed by first mixing a colorant (a) containing a specific colorant, a resin (B) containing a resin (B1) containing a constituent unit (B1-1) represented by formula (1B), and a solvent (E) to produce a composition, and mixing the obtained composition, a polymerizable compound (C), a polymerization initiator (D), and other components as necessary to produce the colored curable composition. The present invention will be described below in order.

< definition >

First, the definitions of the groups used in the present specification will be described. Unless otherwise specified, the 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 any of linear, branched, and cyclic. Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms such as 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, a hexadecyl group, an eicosyl group, an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; and (c) 3-20 alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and the like.

In the present specification, the alkyl group may be either linear or branched. Examples of the alkyl group having 1 to 10 carbon atoms include the alkyl groups having 1 to 10 carbon atoms exemplified above as the alkyl group having 1 to 20 carbon atoms. Examples of other alkyl groups having different carbon atoms are also the same. Examples of groups other than alkyl groups having different carbon atoms are also the same. For example, the saturated hydrocarbon group having 2 to 20 carbon atoms includes the saturated hydrocarbon group having 2 to 20 carbon atoms exemplified above with respect to the saturated hydrocarbon group having 1 to 20 carbon atoms.

In the present specification, the alkanediyl group may be either linear or branched. Examples of the alkanediyl 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, an isopentylene group, an isohexylene group, an isooctylene group, and a 2-ethylhexyl 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, a perfluoroethyl group, a monofluoropropyl group, a difluoropropyl group, a trifluoropropyl group, a tetrafluoropropyl group, a pentafluoropropyl group, a perfluoropropyl group, a monofluorobutyl group, a difluorobutyl group, a trifluorobutyl group, a tetrafluorobutyl 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.

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

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 fused ring. Examples of the three-to ten-membered nitrogen-containing heterocyclic ring 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 single ring or a fused 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 heterocyclic ring may be any of a monocyclic ring and a fused ring. Examples of the five-to ten-membered aromatic heterocycle include a pyrrole ring,

An azole 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, an indole ring, a benzimidazole ring, a benzothiazole ring, a quinoline ring, a benzofuran ring and the like.

< colorant (A) >)

The colorant (a) contains at least one selected from the group consisting of the compound (1a), the compound (2a), and the compound (3 a).

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

R in the formula (1a)^41aAnd R^42aEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^41aAnd R^42aBonded and taken together with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring.

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

The saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (1a) is a saturated hydrocarbon having 2 to 20 carbon atomsWhen it is substituted, the group-CH contained in the above-mentioned saturated hydrocarbon group₂-may be substituted by-O-or-CO-. Here, the above-mentioned-CH₂Does not contain-CH bonded to a nitrogen atom₂and-CH in the methyl group as the terminal of the above-mentioned saturated hydrocarbon group₂-. Further, the saturated hydrocarbon group contains-CH₂－CH₂-is not substituted by-O-O-or-CO-CO-.

The substituent that the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (1a) may have is selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and a-SO₃ ^－、－SO₂－N^－－SO₂－R^fAnd an alkyl group having 1 to 8 carbon atoms which may have a substituent.

The aralkyl group having 7 to 30 carbon atoms in the formula (1a) may have a substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and a-SO₃ ^－、－SO₂－N^－－SO₂－R^fAnd an alkyl group having 1 to 8 carbon atoms which may have a substituent.

R in the formula (1a)^fRepresents a fluoroalkyl group having 1 to 12 carbon atoms.

The alkyl group having 1 to 8 carbon atoms in the formula (1a) may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl 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, the alkyl group contains-CH₂-may be substituted by-O-or-CO-. Here, the above-mentioned-CH₂-CH in a methyl group not included in the above-mentioned alkyl group as a terminal₂-. Further, the group-CH contained in the above alkyl group₂－CH₂-is not substituted by-O-O-or-CO-CO-.

R^41aPreferably 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 still more preferably an alkyl group having 1 to 4 carbon atoms.

R^42aPreferably an alkyl group having 1 to 8 carbon atoms and-SO₃ ^－The phenyl group as at least one substituent in (1) is more preferably an alkyl group having 1 or 2 carbon atoms of 1 to 8 and may have-SO₃ ^－The phenyl group of (1) is more preferably an alkyl group having 1 or 2 carbon atoms of 1 to 4 as a substituent and may have-SO₃ ^－A phenyl group of (a).

R in the formula (1a)^43aAnd R^44aEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^43aAnd R^44aBonded and taken together with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring.

R^43aPreferably 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 still more preferably an alkyl group having 1 to 4 carbon atoms.

R^44aPreferably, the alkyl group may have 1 to 8 carbon atoms and-SO₃ ^－The phenyl group as at least one substituent in (1) is more preferably an alkyl group having 1 or 2 carbon atoms of 1 to 8 and may have-SO₃ ^－The phenyl group of (1) is more preferably an alkyl group having 1 or 2 carbon atoms of 1 to 4 as a substituent and may have-SO₃ ^－A phenyl group of (a).

R in the formula (1a)^47a～R^54aEach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or-SO₃ ^－、－SO₂－N^－－SO₂－R^fOr an alkyl group having 1 to 8 carbon atoms which may have a substituent. R^47a～R^54aEach independently preferably represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or-SO₃ ^－More preferably a hydrogen atom or-SO₃ ^－。

Ring T in formula (1a)^1aRepresents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted penta ℃ -A ten-membered aromatic heterocycle.

The substituent that the aromatic hydrocarbon ring having 6 to 14 carbon atoms in the formula (1a) may have is selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and a-SO₃ ^－、－SO₂－N^－－SO₂－R^fAnd an alkyl group having 1 to 8 carbon atoms which may have a substituent.

The five-to ten-membered aromatic heterocycle in the formula (1a) may have a substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and a-SO₃ ^－、－SO₂－N^－－SO₂－R^fAnd an alkyl group having 1 to 8 carbon atoms which may have a substituent.

Ring T^1aPreferred is a ring represented by the formula (1 t).

R in the formula (1t)^45aAnd R^46aEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^45aAnd R^46aBonded and taken together with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring.

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

The substituent that the aromatic hydrocarbon group having 6 to 14 carbon atoms in the formula (1t) may have is selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and a-SO₃ ^－、－SO₂－N^－－SO₂－R^fAnd an alkyl group having 1 to 8 carbon atoms which may have a substituent.

The aralkyl group having 7 to 30 carbon atoms in the formula (1t) may have a substituent selected from a halogen atom, a nitro group, and a hydroxyl groupFormyl, -SO₃ ^－、－SO₂－N^－－SO₂－R^fAnd an alkyl group having 1 to 8 carbon atoms which may have a substituent.

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

R^45aPreferably 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 still more preferably an alkyl group having 1 to 4 carbon atoms.

R^46aPreferably, the alkyl group may have 1 to 8 carbon atoms and-SO₃ ^－The phenyl group as at least one substituent in (1) is more preferably an alkyl group having 1 or 2 carbon atoms of 1 to 8 and may have-SO₃ ^－The phenyl group of (1) is more preferably an alkyl group having 1 or 2 carbon atoms of 1 to 4 as a substituent and may have-SO₃ ^－A phenyl group of (a).

R in the formula (1t)^56aRepresents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

R^56aPreferably, the halogen atom-containing group may have a group selected from a halogen atom, an alkyl group having 1 to 8 carbon atoms and-SO₃ ^－The phenyl group having at least one substituent in (1) or (2) halogen atoms as a substituent and may have-SO₃ ^－Further preferably a phenyl group having 1 or 2 fluorine atoms as a substituent and may have-SO₃ ^－A phenyl group of (a).

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

In formula (1t), an x represents a bonding site to a carbenium ion. In other words, -, in formula (1t) represents a bond. And in other structural formulas, the-star also represents a bond.

R in formula (1a) represents an integer of 1 or more. r is preferably 2. When r is an integer of 2 or more, the plurality of anions represented by the formula (1 a-A) may be the same or different. The plurality of anions (1 a-A) are preferably the same.

In the formula (1a), k represents-SO that the anion (1 a-A) has₃ ^－and-SO₂－N^－－SO₂－R^fThe total number of (b) is an integer of 2 or more. k is preferably 2.

M in the formula (1a)^r+Represents hydrogen ion, a metal ion of valence r or N⁺(R^55a)₄Four R^55aMay be the same or different. R^55aRepresents 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, a plurality of M^r+May be the same or different.

M^r+Preferably an r-valent metal ion. Examples of the metal ion having a valence of r 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, barium ion, etc.; transition metal ions such as titanium ions, zirconium 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, bismuth ions, and the like.

M^r+More preferably a metal ion having a valence of 2, still more preferably an alkaline earth metal ion, and particularly preferably a barium ion (Ba)² ⁺)。

As the compound (1a), the following compounds (hereinafter, sometimes referred to as "compound (1 a')") are preferred:

R^41aand R^43aEach independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

Ring T^1aIs a ring represented by the formula (1t) [ formula (1t) wherein R^45aIs a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

L^1ais a sulfur atom, and

denotes the bonding site to the carbenium ion. ],

the number r is 2, and the number r,

k represents-SO that the anion (1 a-A) has₃ ^－And 2 in total, the two anions (1 a-A) being identical, and

M^r+is Ba²⁺。

In the compound (1 a'), R^41aAnd R^43aMore 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, R^42aAnd R^44aEach independently more preferably an alkyl group having 1 or 2 carbon atoms of 1 to 8 and may have-SO₃ ^－The phenyl group of (1) is more preferably an alkyl group having 1 or 2 carbon atoms of 1 to 4 as a substituent and may have-SO₃ ^－Phenyl of (A), R^47a～R^54aMore preferably a hydrogen atom or-SO₃ ^－，R^45aMore preferably a hydrogen atom or a carbon atomAlkyl group having 1 to 4 subgroups, more preferably alkyl group having 1 to 4 carbon atoms, R^46aMore preferably an alkyl group having 1 or 2 carbon atoms of 1 to 8 and optionally having-SO₃ ^－The phenyl group of (1) is more preferably an alkyl group having 1 or 2 carbon atoms of 1 to 4 as a substituent and may have-SO₃ ^－And R is^56aMore preferably having 1 or 2 halogen atoms as substituents and may have-SO₃ ^－Further preferably a phenyl group having 1 or 2 fluorine atoms as a substituent and may have-SO₃ ^－A phenyl group of (a).

Among the compounds (1a), the compounds represented by the following formula (1 a-1) are particularly preferable. Note that, in the following formula (1 a-1), two-SO₃ ^－The statement "means that each anion has-SO₃ ^－As substituents, and-SO in each anion₃ ^－The sum of the number of (a) is 2 (i.e., -SO in both anions)₃ ^－The total of the number of (2) is 4).

The compound (1a) can be produced by a known method (for example, the method described in Journal of Organic Chemistry (1994), vol.59, #11, pp.3232-3236, the method described in Japanese patent laid-open publication No. 2018-127596).

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

R in the formula (2a)^41bAnd R^42bEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^41bAnd R^42bBonded and taken together with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring.

The saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (2a) may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl 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, the saturated hydrocarbon group contains-CH₂-may be substituted by-O-or-CO-. Here, the above-mentioned-CH₂Does not contain-CH bonded to a nitrogen atom₂and-CH in the methyl group as the terminal of the above-mentioned saturated hydrocarbon group₂-. Further, the saturated hydrocarbon group contains-CH₂－CH₂-is not substituted by-O-O-or-CO-CO-.

The C6-14 aromatic hydrocarbon group in the formula (2a) may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an optionally substituted C1-8 alkyl group.

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

The alkyl group having 1 to 8 carbon atoms in the formula (2a) may have at least one substituent selected from the group consisting of a halogen atom, a hydroxyl 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, the alkyl group contains-CH₂-may be substituted by-O-or-CO-. Here, the above-mentioned-CH₂-CH in a methyl group not included in the above-mentioned alkyl group as a terminal₂-. Further, the group-CH contained in the above alkyl group₂－CH₂-is not substituted by-O-O-or-CO-CO-.

R^41bPreferably 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 still more preferably an alkyl group having 1 to 4 carbon atoms.

R^42bThe phenyl group may have an alkyl group having 1 to 8 carbon atoms is preferable, the phenyl group may have an alkyl group having 1 to 4 carbon atoms is more preferable, and the phenyl group is further preferable.

R in the formula (2a)^43bAnd R^44bEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^43bAnd R^44bBonded and taken together with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring.

R^43bPreferably 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 still more preferably an alkyl group having 1 to 4 carbon atoms.

R^44bThe phenyl group may have an alkyl group having 1 to 8 carbon atoms is preferable, the phenyl group may have an alkyl group having 1 to 4 carbon atoms is more preferable, and the phenyl group is further preferable.

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

R^47b～R^54bEach independently 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 still more preferably a hydrogen atom.

Ring T in formula (2a)^1bRepresents an optionally substituted aromatic hydrocarbon ring having 6 to 14 carbon atoms or an optionally substituted five-to ten-membered aromatic heterocycle.

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

The five-to ten-membered aromatic heterocyclic ring in the formula (2a) may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group, and an alkyl group having 1 to 8 carbon atoms which may have a substituent.

Ring T^1bPreferred is a ring represented by the formula (2 t).

R in the formula (2t)^45bAnd R^46bEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^45bAnd R^46bBonded and taken together with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring.

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

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

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

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

R^45bPreferably 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 still more preferably an alkyl group having 1 to 4 carbon atoms.

R^46bThe phenyl group may preferably 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 still more preferably a phenyl group having 1 or 2 alkyl groups having 1 to 4 carbon atoms as a substituent.

Formula (2t)R in (1)^56bRepresents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

R^56bThe phenyl group 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, is preferable, the phenyl group having 1 or 2 halogen atoms as a substituent is more preferable, and the phenyl group having 1 or 2 fluorine atoms as a substituent is even more preferable.

L in the formula (2t)^1bRepresents a sulfur atom, an oxygen atom or-NR^57b－。R^57bRepresents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L is^1bPreferably a sulfur atom.

In formula (2t), an x represents a bonding site to a carbenium ion.

M in the formula (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, further preferably an integer of 2 to 8, and particularly preferably 3. When m is an integer of 2 or more, the plural cations represented by the formula (2 a-C) may be the same or different. The multiple cations (2 a-C) are preferably the same.

[ formula (2 a-C) wherein the ring T^1b、R^41b～R^44bAnd R^47b～R^54bRespectively, the same as above.]

[ Y ] in the formula (2a)]^m－Represents an m-valent anion. [ Y ]]^m－Preferably a polyacid anion containing tungsten atoms, more preferably [ PW₁₂O₄₀]^3－、[P₂W₁₈O₆₂]^6－、[P₂W₁₈O₆₂]^6－、[SiW₁₂O₄₀]^4－、[SiW₁₂O₄₀]^4－、[SiW₁₂O₄₀]^4－、[P₂W₁₇O₆₁]^10－、[P₂W₁₅O₅₆]^12－、[H₂P₂W₁₂O₄₈]^12－、[NaP₅W₃₀O₁₁₀]^14－、[SiW₉O₃₄]^10－、[SiW₁₀O₃₆]^8－、[SiW₁₁O₃₉]^8－、[SiW₁₁O₃₉]^8－、[W₆O₁₉]^2－、[W₁₀O₃₂]^4－Or [ WO)₄]^2－More preferably [ PW₁₂O₄₀]^3－。

As the compound (2a), the following compounds (hereinafter, sometimes referred to as "compound (2 a')") are preferred:

R^41b、R^43band R^47b～R^54bEach independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R^42bAnd R^44bEach independently a phenyl group which may have an alkyl group having 1 to 8 carbon atoms,

ring T^1bIs a ring represented by the formula (2t) [ formula (2t), R^45bIs a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R^46ba phenyl group which may have an alkyl group having 1 to 8 carbon atoms,

L^1bis a sulfur atom, and

denotes a bonding site with a carbenium ion ],

m is the number of 3,

the three cations (2 a-C) being identical, and

[Y]^m－is [ PW ]₁₂O₄₀]^3－。

In the compound (2 a'), R^41bAnd R^43bEach independently 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, still more preferably an alkyl group having 1 to 4 carbon atoms, R^42bAnd R^44bEach independently of the other, more preferably a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, still more preferably a phenyl group, R^47b～R^54bEach independently of the other, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, further preferably a hydrogen atom, R^45bMore 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, R^46bMore preferably a phenyl group having 1 or 2 alkyl groups having 1 to 8 carbon atoms as a substituent, still more preferably a phenyl group having 1 or 2 alkyl groups having 1 to 4 carbon atoms as a substituent, and R^56bMore preferred is a phenyl group having 1 or 2 halogen atoms as a substituent, and still more preferred is a phenyl group having 1 or 2 fluorine atoms as a substituent.

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

The compound (2a) can be produced by a known method (for example, the methods described in japanese patent application laid-open nos. 2015-28121 and 2015-38201).

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

In the formula (3a), R¹And R²Each independently represents 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 10 carbon atoms which may have a substituent, or-R¹²－Si(R¹³)₃Or R is¹And R²Bonded and taken together with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring.

In the formula (3a), R³And R⁴Each independently represents a hydrogen atom, an optionally substituted saturated hydrocarbon having 1 to 20 carbon atomsA group which may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms or-R¹²－Si(R¹³)₃A group represented by, or R³And R⁴Bonded and taken together with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring.

R¹～R⁴The saturated hydrocarbon group having 1 to 20 carbon atoms may have at least one substituent selected from the group consisting of an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group, a formyl group and a carboxyl group.

R¹～R⁴The above-mentioned C6-10 aromatic hydrocarbon group may have a substituent selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group, a C1-20 saturated hydrocarbon group which may have a halogen atom, -OR⁸、－SO₃ ^－、－SO₃ ^－Z⁺、－SO₃R⁸、－CO₂ ^－Z⁺、－CO₂R⁸and-SO₂NR⁹R¹⁰At least one of (a).

Note that-SO in the form of an ion is present in the compound (3a)₃ ^－In this case, the number of the cells is 1.

R¹～R⁴When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, the saturated hydrocarbon group contains-CH₂May be substituted by-O-, -CO-or-NR¹¹-. Here, the above-mentioned-CH₂Does not contain-CH bonded to a nitrogen atom₂and-CH in the methyl group as the terminal of the above-mentioned saturated hydrocarbon group₂-. Further, the saturated hydrocarbon group contains-CH₂－CH₂Unsubstituted by-O-, -CO-or-NR¹¹－NR¹¹－。

R¹And R³Each independently is preferably a hydrogen atom; an alkyl group having 1 to 8 carbon atoms which may have a carboxyl group; may have an alkyl group selected from the group consisting of C1-8 alkyl groups and-SO₂NR⁹R¹⁰Phenyl of at least one substituent of (1); or-R¹²－Si(R¹³)₃More preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a carboxyl group.

R²And R⁴Each independently preferably an alkyl group having 1 to 8 carbon atoms which may have a carboxyl group; may have an alkyl group selected from the group consisting of C1-8 alkyl groups and-SO₂NR⁹R¹⁰Phenyl of at least one substituent of (1); or-R¹²－Si(R¹³)₃More preferably an alkyl group having 1 to 4 carbon atoms; may have an alkyl group selected from the group consisting of C1-4 alkyl groups and-SO₂NR⁹R¹⁰Phenyl of at least one substituent of (1); or-R¹²－Si(R¹³)₃。

In the formula (3a), p represents an integer of 0 to 5. When p is an integer of 2 or more, plural R⁵May be the same or different. p is preferably 1.

In the formula (3a), R⁵represents-OH or-SO₃ ^－、－SO₃ ^－Z⁺、－SO₃R⁸、－CO₂ ^－Z⁺、－CO₂R⁸or-SO₂NR⁹R¹⁰。Z⁺Represents N⁺(R¹¹)₄、Na⁺Or K⁺. Four R¹¹May be the same or different. R⁵Is preferably-SO₃ ^－。

In the formula (3a), R⁶And R⁷Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R⁶And R⁷Preferably both are hydrogen atoms.

In the formula (3a), R⁸Represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms and optionally having a halogen atom.

In the formula (3a), R⁹And R¹⁰Each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or R⁹And R¹⁰Bonded and taken together with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring.

R⁹And R¹⁰The above-mentioned C1-20 saturated hydrocarbonAnd the substituent which the hydrocarbon group may have is at least one selected from the group consisting of a hydroxyl group, a formyl group and a halogen atom.

R⁹And R¹⁰When the saturated hydrocarbon group having 1 to 20 carbon atoms is a saturated hydrocarbon group having 2 to 20 carbon atoms, the saturated hydrocarbon group contains-CH₂May be substituted by-O-, -CO-or-NR⁸-. Here, the above-mentioned-CH₂Does not contain-CH bonded to a nitrogen atom₂and-CH in the methyl group as the terminal of the above-mentioned saturated hydrocarbon group₂-. Further, the saturated hydrocarbon group contains-CH₂－CH₂Unsubstituted by-O-, -CO-or-NR⁸－NR⁸－。

R⁹And R¹⁰Each independently preferably represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In the formula (3a), R¹¹Represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

In the formula (3a), R¹²Represents an alkanediyl group having 1 to 10 carbon atoms. R¹²When the alkanediyl group having 1 to 10 carbon atoms is an alkanediyl group having 2 to 20 carbon atoms, the alkanediyl group may contain-CH₂May be substituted by-O-, -CO-or-NR⁸-. Here, the above-mentioned-CH₂Does not contain-CH bonded to a nitrogen atom₂and-CH bonded to the silicon atom₂-. Further, a-CH contained in the above-mentioned alkanediyl group₂－CH₂Unsubstituted by-O-, -CO-or-NR⁸－NR⁸－。

R¹²Preferably an alkanediyl group having 1 to 6 carbon atoms.

In the formula (3a), R¹³Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. And three R¹³Each of which may be the same or different. Three R¹³Preferably, the alkoxy group has 1 to 4 carbon atoms.

In the formula (3a), X represents a halogen atom.

In formula (3a), q is shown in the tableRepresents 0 or 1. Here, q is 0 means that it is absent (X)^－)_q. q is preferably 0.

As the compound (3a), the following compounds (hereinafter, sometimes referred to as "compound (3 a')") are preferable:

R¹and R³Each independently is a hydrogen atom; an alkyl group having 1 to 8 carbon atoms which may have a carboxyl group; may have an alkyl group selected from the group consisting of C1-8 alkyl groups and-SO₂NR⁹R¹⁰Phenyl of at least one substituent of (1); or-R¹²－Si(R¹³)₃，

R²And R⁴Each independently is an alkyl group having 1 to 8 carbon atoms which may have a carboxyl group; may have an alkyl group selected from the group consisting of C1-8 alkyl groups and-SO₂NR⁹R¹⁰Phenyl of at least one substituent of (1); or-R¹²－Si(R¹³)₃，

R⁵is-SO₃ ^－，

R⁶And R⁷Are all hydrogen atoms, and are,

R¹²an alkanediyl group having 1 to 6 carbon atoms,

three R¹³All of which are C1-C4 alkoxy groups,

p is 1, and

q is 0.

In the compound (3 a'), R¹And R³Each independently more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a carboxyl group, and R²And R⁴More preferably an alkyl group having 1 to 4 carbon atoms, which may have a structure selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and-SO₂NR⁹R¹⁰Phenyl of at least one substituent of (a), or-R¹²－Si(R¹³)₃。

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

In the formulae (3 a-2) and (3 a-3), R¹⁴represents-SO₂－NH(CH₂)－CH(CH₂CH₃)－CH₂CH₂CH₂CH₃。

The compound (3a) can be produced by a known method (for example, the method described in Japanese patent application laid-open No. 2010-32999).

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

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

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

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

As other colorants, xanthene dyes may be used. Examples of the xanthene dye include c.i. acid red 51 (hereinafter, the description of c.i. acid red is omitted, and only the number is described, and the same applies to the others), 52, 87, 92, 94, 289, 388, c.i. acid violet 9, 30, 102, c.i. basic red 1 (rhodamine 6G), 2,3,4, 8, c.i. basic red 10, 11, c.i. basic violet 10 (rhodamine B), 11, c.i. solvent red 218, c.i. mordant red 27, c.i. reactive red 36 (banglas rose red B), and sulforhodamine G.

As other colorants, coumarin dyes may be used. Examples of the coumarin dye include c.i. acid yellow 227, 250; c.i. disperse yellow 82, 184; c.i. solvent orange 112; c.i. solvent yellow 160, 172; coumarin dyes described in japanese patent No. 1299948, and the like.

Examples of The dyes other than The above-mentioned dyes include dyes described in The color index (published by The Society of Dyers and Colourists) and dyes described in The dyeing guide (chromo). Examples of the dye include azo dyes, cyanine dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, quinoline dyes, nitro dyes, and the like.

Specific examples of the dye include the following.

(1) C.I. solvent dyes

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, 59:1, 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; and the like.

(2) C.I. acid dyes

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; and the like.

(3) C.I. basic dyes

C.i. alkaline green 1; and the like.

(4) C.I. reactive dyes

C.i. reactive yellow 2, 76, 116;

c.i. reactive orange 16; and the like.

(5) C.I. direct dyes

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; and the like.

(6) C.I. disperse dyes

C.i. disperse yellow 51, 54, 76;

c.i. disperse violet 26, 27;

c.i. disperse blue 1, 14, 56, 60; and the like.

(7) C.I. mordant dyeing dye

C.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. mordant oranges 3,4,5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; and the like.

(8) C.I. vat dyes

C.i. vat green 1, etc.

In addition, as other colorants, for example, pigments described in The color index (The Society of Dyers and Colourists publication) may be used.

Specific examples of the pigment include the following.

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, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and the like;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as 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;

c.i. pigment blue 15, 15:3, 15:4, 15:6, 60, etc.;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

green pigments such as c.i. pigment green 7, 36, 58;

c.i. brown pigments such as pigment brown 23, 25;

and black pigments such as c.i. 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, and still more preferably 45 to 60% by weight, based on the total amount of solid components in the composition of the present invention.

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

In the embodiment where at least one selected from the compound (1a), the compound (2a) and the compound (3a) is the compound (1a), the content of the compound (1a) is preferably 50 to 100% by weight, more preferably 55 to 100% by weight, further preferably 60 to 100% by weight, particularly preferably 65 to 100% by weight, and most preferably 80 to 100% by weight, based on the total amount of the colorant (a).

In the embodiment where at least one selected from the compound (1a), the compound (2a) and the compound (3a) is the compound (2a), the content of the compound (2a) is preferably 50 to 100% by weight, more preferably 55 to 100% by weight, further preferably 60 to 100% by weight, particularly preferably 65 to 100% by weight, and most preferably 80 to 100% by weight, based on the total amount of the colorant (a).

< resin (B) >

The resin (B) includes a resin (B1) containing a constituent unit (B1-1) represented by formula (1B) (hereinafter, sometimes referred to as "constituent unit (B1-1)"). In the resin (B1), the constituent unit (B1-1) may include only 1 species, or may include 2 or more species.

[ in the formula (1b), R^1BRepresents a hydrogen atom or a methyl group,

n represents an integer of 1 to 10, and

indicates the number of the bonding sites,

wherein R is^2B～R^4BAt least one ofThe alkoxy group has 1 to 6 carbon atoms.]

R^2B～R^4BEach independently is preferably methoxy, ethoxy or propoxy, more preferably methoxy or ethoxy.

n is preferably an integer of 1 to 6, more preferably an integer of 1 to 3.

The resin (B1) is preferably a copolymer comprising a constituent unit (B1-1), a constituent unit (B1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter sometimes referred to as "constituent unit (B1-2)"), and another constituent unit (B1-3) (hereinafter sometimes referred to as "constituent unit (B1-3)"). Here, the other constituent unit (b 1-3) is a constituent unit different from the constituent unit (b 1-1) and the constituent unit (b 1-2). In the copolymer resin (B1), each of the constituent unit (B1-1), the constituent unit (B1-2) and the constituent unit (B1-3) may be contained in 1 species or 2 or more species.

Examples of the acidic group of the constituent unit (b 1-2) include a carboxyl group and a phosphate group (-O-P (═ O) (OH)₂) Sulfo (-O)₂OH). Among them, a carboxyl group is preferable.

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

From the viewpoint of developability of the colored curable composition, the amount of the constituent unit (b 1-2) is preferably 10 to 50 mol%, more preferably 15 to 45 mol%, and still more preferably 20 to 40 mol%, based on 100 mol% of the total of all constituent units in the copolymer.

The amount of the constituent unit (b 1-3) is preferably 1 to 89 mol%, more preferably 15 to 80 mol%, and still more preferably 30 to 70 mol% when the total of all constituent units in the copolymer is 100 mol%, from the viewpoints of developability of the colored curable composition and solvent resistance of a color filter or the like obtained from the colored curable composition.

The weight average molecular weight (Mw) of the resin (B1) is 1000 to 50000, preferably 2000 to 40000, more preferably 3000 to 30000, from the viewpoint of developability of the colored curable composition. The weight average molecular weight (Mw) is calculated from polystyrene conversion using Gel Permeation Chromatography (GPC).

The silyl equivalent weight of the resin (B1) is preferably 400 to 4000, more preferably 450 to 3000, from the viewpoints of thermal decomposition resistance, thermal yellowing resistance, and solvent resistance of a color filter or the like obtained from the colored curable composition. When the silyl equivalent weight of the resin (B1) is 400 or more, it is effective for further improving the thermal decomposition resistance and thermal yellowing resistance of the colored pattern or colored coating film. The silyl equivalent weight of the resin (B1) was calculated from the following formula.

Silyl equivalent weight (weight average molecular weight of resin (B1)/average number of silyl groups per 1 molecule)

The silyl equivalent weight can be calculated from the charged amount of the monomer used for producing the resin (B1).

When the resin (B1) is a copolymer containing the constituent unit (B1-2), the acid value of the resin (B1) is preferably 20 to 300mgKOH/g, more preferably 30 to 200mgKOH/g, from the viewpoint of developability of the colored curable composition. The acid value of the resin (B1) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K69015.3, and is a value calculated as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B1), and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin (B1) is preferably 10 to 100 parts by weight, more preferably 10 to 60 parts by weight, even 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, based on 100 parts by weight of the colorant (a), from the viewpoint of suppressing the thickening of the colored curable composition.

The resin (B1) can be produced by copolymerizing only the compound (m 1-1) (hereinafter, sometimes referred to as "compound (m 1-1)") represented by the following formula (2B) or a monomer mixture containing the compound (m 1-1) and another compound in the presence of a solvent according to a known radical polymerization method.

[ the symbols in the formula (2b) have the same meanings as described above ]

The resin (B1) as a copolymer can be produced, for example, by dissolving the compound (m 1-1) and, if necessary, other compounds in a solvent to prepare a solution, adding a polymerization initiator to the solution, and reacting the mixture at 50 to 130 ℃ for 1 to 20 hours.

The resin (B1) which is a copolymer comprising the constituent unit (B1-1), the constituent unit (B1-2) and the constituent unit (B1-3) can be produced by copolymerizing a monomer mixture comprising the compound (m 1-1), the polymerizable unsaturated compound having an acidic group (m 1-2) (hereinafter, sometimes referred to as "compound (m 1-2)") and the other polymerizable unsaturated compound (m 1-3) (hereinafter, sometimes referred to as "compound (m 1-3)") in the presence of a solvent according to a known radical polymerization method. Here, the other polymerizable unsaturated compound (m 1-3) is a polymerizable unsaturated compound different from the compound (m 1-1) and the compound (m 1-2). Further, the constituent unit (b 1-1) was derived from the compound (m 1-1), the constituent unit (b 1-2) was derived from the compound (m 1-2), and the constituent unit (b 1-3) was derived from the compound (m 1-3).

The resin (B1) as a copolymer can be produced, for example, by dissolving the compound (m 1-1), the compound (m 1-2) and the compound (m 1-3) in a solvent to prepare a solution, adding a polymerization initiator to the solution, and reacting at 50 to 130 ℃ for 1 to 20 hours.

Examples of the compound (m 1-1) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and the like. Among them, 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane are preferable from the viewpoint of ease of obtaining and reactivity. Here, "3- (meth) acryloyloxypropylmethyldimethoxysilane" means at least one selected from the group consisting of 3-acryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropylmethyldimethoxysilane. The same description applies to the other elements.

Examples of the acidic group of the compound (m 1-2) include a carboxyl group and a phosphate group (-O-P (═ O) (OH)₂) Sulfo (-O)₂OH). Among them, a carboxyl group is preferable.

Examples of the compound (m 1-2) include (meth) acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and 2- (meth) acryloyloxyethylacid phosphate. Among them, (meth) acrylic acid is preferable from the viewpoint of ease of obtaining and reactivity.

Examples of the compound (m 1-3) include the following:

butadiene;

methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 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 (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, rosin (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 1, cyclohexyl (meth) acrylate, methyl) acrylate, cyclohexyl (meth) acrylate, 1, cyclohexyl (meth) acrylate, methyl) acrylate, 1, methyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate, methyl (acrylate, methyl) acrylate, methyl (meth) acrylate, methyl (acrylate, methyl) acrylate, methyl (acrylate, methyl) acrylate, methyl (acrylate, methyl 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, perfluoropropyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, glycerol mono (meth) acrylate, butanetriol mono (meth) acrylate, pentanetriol mono (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl acrylate, and allyl acrylate, and allyl acrylate, and allyl acrylate, wherein, Naphthyl (meth) acrylate, anthracenyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3-ethyloxetan-3-yl) meth (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, and (meth) acrylate having a blocked isocyanate group obtained by blocking the isocyanate group of the above-mentioned (meth) acrylate having an isocyanate group (for example, 2-isocyanatoethyl (meth) acrylate) with a blocking agent Acrylic ester, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, tetramethylpiperidine (meth) acrylate, hexamethylpiperidine (meth) acrylate;

(meth) acrylamide, N-dimethylamide (meth) acrylate, N-diethylamide (meth) acrylate, N-dipropylamide (meth) acrylate, N-diisopropylamide (meth) acrylate, anthracylamide (meth) acrylate, N-isopropyl (meth) acrylamide, (meth) acryloylmorpholine, 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]Dodec-3-ene, 8-methyltetracyclo [4.4.0.1^2,5.1⁷ ^,10]Dodec-3-ene, 8-ethyltetracyclo [4.4.0.1^2,5.1^7,10]Dodec-3-ene, dicyclopentadiene, tricyclo [5.2.1.0^2,6]Dec-8-ene, tricyclo [5.2.1.0^2,6]Dec-3-ene, 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]Undec-4-ene, tetracyclo [4.4.0.1^2,5.1^7, ¹⁰.0^1,6]Dodec-3-ene, 8-methyltetracyclo [4.4.0.1^2,5.1^7,10.0^1,6]Dodec-3-ene, 8-ethylidene tetracyclo [4.4.0.1^2,5.1^7,12]Dodec-3-ene, 8-ethylidene tetracyclo [4.4.0.1^2,5.1^7,10.0^1,6]Dodec-3-ene, pentacyclic [6.5.1.1 ]^3,6.0^2,7.0^9,13]Pentadec-4-ene, pentacyclic [7.4.0.1 ]^2,5.1^9,12.0^8,13]Pentadecan-3-ene, 5-norbornene-2, 3-dicarboxylic anhydride, aniline (meth) acrylate, (meth) acrylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinylpyridine, vinyl acetate, vinyltoluene;

styrene and its derivatives;

citraconic acid diethyl ester, maleic acid diethyl ester, fumaric acid diethyl ester, itaconic acid diethyl ester;

maleic anhydride, itaconic anhydride, citraconic anhydride.

From the viewpoint of ease of obtaining and reactivity, as the compound (m 1-3), methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, N-dimethylamide (meth) acrylate, morpholine (meth) acrylate, styrene, vinyltoluene and norbornene are preferable, more preferred are methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, styrene and vinyltoluene.

From the viewpoint of thermal decomposition resistance and thermal yellowing resistance, the compound (m 1-3) is preferably an alkyl (meth) acrylate, and more preferably methyl (meth) acrylate, benzyl (meth) acrylate, or dicyclopentanyl (meth) acrylate.

From the viewpoint of solvent resistance of a color filter or the like obtained from the colored curable composition, the compound (m 1-3) is preferably a polymerizable compound having a functional group reactive with an acidic group (for example, a glycidyl group, an oxetanyl group, an isocyanate group, or a blocked isocyanate group), and more preferably glycidyl (meth) acrylate or (3-ethyloxetan-3-yl) methyl methacrylate.

Examples of the blocking agent used for blocking the isocyanate group include the following:

lactam-based blocking agents such as epsilon-caprolactam, delta-valerolactam, gamma-butyrolactam, beta-propiolactam, and the like;

alcohol-based capping agents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol;

phenol-based end-capping agents such as butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoates, thymol, p-naphthol, p-nitrophenol and p-chlorophenol;

active methylene-based blocking agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone;

mercaptan-based blocking agents such as butyl mercaptan, thiophenol and tert-dodecyl mercaptan;

amine-based blocking agents such as diphenylamine, phenylnaphthylamine, aniline, and carbazole;

amide-based blocking agents such as acetanilide, methoxyacetanilide, acetamide, and benzamide;

imide-based capping agents such as succinimide and maleimide;

imidazole-based capping agents such as imidazole, 2-methylimidazole and 2-ethylimidazole;

urea-based blocking agents such as urea, thiourea and ethylene urea;

phenyl N-phenylcarbamate, 2-

Carbamate-based capping agents such as oxazolidinones;

imine-based blocking agents such as ethyleneimine and polyethyleneimine;

oxime blocking agents such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, methylisobutylketone oxime, and cyclohexanone oxime;

bisulfite blocking agents such as sodium bisulfite and potassium bisulfite.

The solvent used for the polymerization preferably contains a hydroxyl group-containing solvent having 3 to 10 carbon atoms in order to control the weight molecular weight (Mw) and polydispersity (Mw/Mn) of the resin (B1) within desirable ranges and to suppress gelation during polymerization. Examples of the hydroxyl group-containing solvent having 3 to 10 carbon atoms include monohydric alcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and benzyl alcohol; (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, 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 monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and the like.

The solvent used for the polymerization may contain a solvent other than the hydroxyl 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; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; and carboxylic acid amides such as N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide. Among them, (poly) alkylene glycol monoalkyl ether acetates are preferable from the viewpoint of reactivity.

From the viewpoint of controlling the weight molecular weight and polydispersity (Mw/Mn) of the resin (B1), the content of the hydroxyl group-containing solvent having 3 to 10 carbon atoms relative to the total amount of the solvent used in the polymerization is preferably 10 to 100% by weight, 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 1000 parts by weight, more preferably 50 to 800 parts by weight, based on 100 parts by weight of the total amount of the compound (m 1-1), the compound (m 1-2) and the compound (m 1-3).

The polymerization initiator usable in the above polymerization is not particularly limited, and examples thereof include 2,2 ' -azobis (isobutyronitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), dimethyl 2,2 ' -azobis (isobutyrate), benzoyl peroxide, tert-butyl peroxy (2-ethylhexanoate), and the like. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.5 to 20 parts by weight, more preferably 1.0 to 10 parts by weight, based on 100 parts by weight of the total amount of the compound (m 1-1), the compound (m 1-2) and the compound (m 1-3).

The resin (B) may contain a resin (B2) different from the resin (B1). The resin (B2) is preferably an alkali-soluble resin, and is preferably a polymer containing a constituent unit derived from at least one monomer (hereinafter, sometimes referred to as "monomer (m 2-1)") selected from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. In the polymer, the constituent unit may include only 1 kind, or may include 2 or more kinds.

The resin (B2) is more preferably a copolymer comprising a constituent unit derived from the monomer (m 2-1) and a constituent unit derived from a monomer having a cyclic ether structure of 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (m 2-2)"). The above copolymer may also contain other constituent units. Examples of the other constituent units include a constituent unit derived from a monomer different from the monomer (m 2-1) and the monomer (m 2-2) (hereinafter, sometimes referred to as "monomer (m 2-3)"), a constituent unit having an ethylenically unsaturated bond, and the like. In the copolymer, the constituent units may be contained in 1 kind alone, or may be contained in 2 or more kinds.

Examples of the monomer (m 2-1) include the following:

unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and o-, m-and p-vinylbenzoic acid;

unsaturated dicarboxylic acids such as 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, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexene dicarboxylic acid;

carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxymethylbicyclo [2.2.1] hept-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;

carboxylic acid anhydrides such as anhydrides of the above unsaturated dicarboxylic acids except fumaric acid and mesaconic acid;

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [ 2- (meth) acryloyloxyethyl ] ester;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylate.

As the monomer (m 2-1), acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoints of reactivity and solubility of the obtained resin in an aqueous alkali solution.

The monomer (m 2-2) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. The monomer (m 2-2) 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 oxirane ring, an oxetane ring and a tetrahydrofuran ring.

Examples of the monomer (m 2-2) include a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (m 2-2-1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (m 2-2-2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (m 2-2-3)"), and the like.

Examples of the monomer (m 2-2-1) include a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "monomer (m 2-2-1 a)") and a monomer having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "monomer m 2-2-1 b)").

As the monomer (m 2-2-1 a), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Examples of the monomer (m 2-2-1 a) include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, α -methylvinylbenzyl 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 (glycidoxymethyl) styrene, and the like.

Examples of the monomer (M2-2-1 b) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel), a compound represented by the formula (BI), and a compound represented by the formula (BII).

[ formula (BI) and formula (BII) wherein R^aAnd R^bEach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group,

X^aand X^bEach independently represents a single bond, [ R ]^c－、*－R^c－O－、*－R^c-S-or R^c－NH－，

R^cAn alkanediyl group having 1 to 6 carbon atoms, and

denotes the bonding site to O. ]

Examples of the compound represented by formula (BI) include compounds represented by any one of formulae (I-1) to (I-15). Among them, preferred are compounds represented by any of the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) and the formulae (I-11) to (I-15), and more preferred are compounds represented by any of the formula (I-1), the formula (I-7), the formula (I-9) and the formula (I-15).

Examples of the compound represented by formula (BII) include compounds represented by any of formulae (II-1) to (II-15). Among them, preferred are compounds represented by any one of the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) and the formulae (II-11) to (II-15), and more preferred are compounds represented by any one of the formula (II-1), the formula (II-7), the formula (II-9) and the formula (II-15).

In addition, the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone, or the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used in combination. When they are used in combination, the molar ratio of the compound represented by the formula (BI) to the compound represented by the formula (BII) (compound represented by the formula (BI): compound represented by the formula (BII)) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and further preferably 20:80 to 80: 20.

Examples of the monomer (m 2-3) 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 (meth) acrylate^2,6]Decan-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2；6]Decen-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decen-9-yl ester, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate(meth) acrylic acid esters such as esters, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

hydroxyl 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 itaconate;

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-bis (2.1) hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxyhept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-2.1 ] hept-2-ene, 5-hydroxy-2-hydroxy-2-hydroxy-1-2-hydroxy-2-1-hydroxy-2-hydroxy-2-1-2-ethyl-2-ene, 5-hydroxy-2-hydroxy-2, 5, 6-2-hydroxy-2-one, 5-2-one, 5, 6-one, 2-one, 2-one, 5, Bicyclic unsaturated compounds such as 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [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 (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate 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, styrene, vinyltoluene, and tricyclo [5.2.1.0 ] meth (acrylic acid) are preferable as the monomer (m 2-3)^2,6]Decan-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decen-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decen-9-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1]Hept-2-ene and benzyl (meth) acrylate.

The constituent unit having an ethylenically unsaturated bond is preferably a constituent unit having a (meth) acryloyl group. The resin (B2) having such a constituent unit can be obtained by adding a monomer having a group reactive with the group of the above-mentioned constituent unit and an ethylenically unsaturated bond to a polymer containing a constituent unit derived from the monomer (m 2-1) and a constituent unit derived from the monomer (m 2-2).

Examples of the constituent unit having an ethylenically unsaturated bond include a constituent unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit, a constituent unit obtained by adding 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit, a constituent unit obtained by adding (meth) acrylic acid to a glycidyl (meth) acrylate unit, and a constituent unit obtained by adding a carboxylic anhydride to a constituent unit having a hydroxyl group.

The polymer containing a constituent unit derived from the monomer (m 2-1) can be produced, for example, by polymerizing a monomer constituting a constituent unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator and the solvent are not particularly limited, and polymerization initiators and solvents generally used in this field can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide). The solvent is not particularly limited as long as it dissolves each monomer, and examples thereof include a solvent (H) described later. The polymer obtained may be used as it is, as a solution after the reaction, as a concentrated or diluted solution, or as a solid (powder) taken out by a method such as reprecipitation.

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

Examples of the resin (B2) include a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and a 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, and 3, 4-epoxy tricyclo [5.2.1.0 ] of (meth) acrylic acid^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] of (meth) acrylic acid^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] of (meth) acrylic acid^2,6]Decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid tricyclo [5.2.1.0^2,6]Decenyl ester/(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 resins described in Japanese patent application laid-open Nos. 9-106071, 2004-29518 and 2004-361455.

When a combination of 2 or more resins (B2) is used, the combination preferably contains a compound selected from the group consisting of (meth) acrylic acid 3, 4-epoxytricyclo [ 5.2.1.0%^2,6]Decyl ester/(meth) acrylic acid copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, and 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid^2,6]At least one decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer.

The weight average molecular weight (Mw) of the resin (B2) is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. The polydispersity (Mw/Mn) (i.e., the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) of the resin (B2) is preferably 1.1 to 6, more preferably 1.2 to 4. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (B2) were calculated from polystyrene conversion using Gel Permeation Chromatography (GPC).

The acid value (solid content equivalent value) of the resin (B2) is preferably 10 to 300mgKOH/g, more preferably 20 to 250mgKOH/g, still more preferably 20 to 200mgKOH/g, yet more preferably 20 to 170mgKOH/g, yet more preferably 30 to 170mgKOH/g, particularly preferably 50 to 150mgKOH/g, particularly preferably 60 to 140mgKOH/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 for neutralizing 1g of the resin (B2), and can be determined by titration with an aqueous solution of potassium hydroxide, for example.

When the resin (B2) is used, the content thereof is preferably 10 to 40 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the colorant (a), from the viewpoints of the storage stability of the colored curable composition and the heat resistance of a color filter or the like obtained from the colored curable composition.

< solvent (E) >

The solvent (E) is not particularly limited, and a solvent known in the field of a colored curable composition can be used. Examples of the solvent (E) include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule), an ether solvent (a solvent containing-O-and not containing-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and not containing-COO-in the molecule), a ketone solvent (a solvent containing-CO-and not containing-COO-in the molecule), an alcohol solvent (a solvent containing OH and not containing-O-, -CO-, and-COO-, a solvent), an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide. The concept of "-O-" does not include "-O-" in "-COO-" and the concept of "-CO-" does not include "-CO-" in "-COO-".

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

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, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-di-n

Alkane, diethyl etherGlycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, 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, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, and the like, Diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, diacetone alcohol, cyclopentanone, 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, mesitylene, and the like.

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

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

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, and still more preferably 80 to 90% by weight, based on the total amount of the composition of the present invention.

< other ingredients of the composition >

The composition of the present invention may contain other components different from the above-described components within a range not to inhibit the effect of the present invention. Examples of the other components include additives known in the field of colored curable compositions.

As other ingredients, a dispersant may be used. Examples of the dispersant include a surfactant. The surfactant may be any one of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Examples of the surfactant include a polyester surfactant, a polyamine surfactant, and an acrylic surfactant. Commercially available products of the dispersant include KP (manufactured by shin-Etsu chemical industries), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (manufactured by BASF Co., Ltd.), AJISPER (registered trademark) (manufactured by Naoriko Fine chemical Co., Ltd.), DISPERBYK (registered trademark) (manufactured by BYK-Chemie Japan Co., Ltd.), BYKLPN (manufactured by BYK-Chemie Japan Co., Ltd.), and the like.

When the dispersant is used, the content thereof 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, and particularly preferably 40 to 60 parts by weight, based on 100 parts by weight of the colorant (a).

< method for producing composition >

The composition of the present invention can be produced, for example, by mixing a colorant (a) containing at least one selected from the group consisting of the compound (1a), the compound (2a) and the compound (3a), a resin (B) containing the resin (B1), a solvent (E), and other components (for example, a dispersant) as needed.

The apparatus for mixing the components is not particularly limited, and apparatuses known in the field of coloring curable compositions can be used. When a component (for example, a pigment) insoluble in the solvent (E) is used, the mixture of the components is preferably sufficiently stirred using a bead mill, Paint Conditioner, or the like.

< colored curable composition >

The colored 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 colored curable composition, components different from the composition of the present invention, the polymerizable compound (C) and the polymerization initiator (D) may be used. For example, the solvent (E) may be further added. Examples of the solvent (E) usable for producing the colored curable composition include the solvents described for 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, and still more preferably 80 to 90% by weight, based on the total amount of the colored curable composition.

The viscosity (initial viscosity) of the colored curable composition immediately after production is preferably 3 to 15mPa · s, more preferably 3 to 13mPa · s, and still more preferably 3 to 10mPa · s. The initial viscosity was measured by using a cone-plate type (E-type) viscometer at a rotation speed of 100rpm and a measurement temperature of 23 ℃.

< polymerizable Compound (C) >)

The polymerizable compound (C) is a compound that can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D). The polymerizable compound (C) is preferably a radical polymerizable compound. Examples of the radical polymerizable compound include compounds having a polymerizable ethylenically unsaturated bond. The radical polymerizable compound is preferably a (meth) acrylate.

Examples of the polymerizable compound (C) include the following:

compounds having 1 ethylenically unsaturated bond such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone;

compounds having 2 ethylenically unsaturated bonds such as 1, 6-cyclohexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate;

compounds having 3 ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and the like;

compounds having 4 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 having 5 ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate;

compounds having 6 ethylenically unsaturated bonds 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;

and compounds having 7 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. Examples of commercially available products of the polymerizable compound (C) include KAYARAD (registered trademark) DPHA (Nippon chemical Co., Ltd.), A-TMM-3 LM-N (Nongmura chemical Industrial Co., Ltd.), and A9550 (Nongmura chemical Industrial Co., Ltd.).

The molecular weight of the polymerizable compound (C) is preferably 150 to 2900, more preferably 250 to 1500. The molecular weight of the polymerizable compound (C) of 1000 or more is the weight average molecular weight (Mw) calculated from polystyrene conversion 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, and still more preferably 17 to 55% by weight, based on the total solid content of the colored curable composition. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

< polymerization initiator (D) >)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat to initiate polymerization of the polymerizable compound (C), and a known polymerization initiator can be used. The polymerization initiator (D) is preferably a photo radical polymerization initiator. More preferably, the polymerizable compound (C) is a radical polymerizable compound, and the polymerization initiator (D) is a photo radical polymerization initiator (that is, the curable composition is a photocurable composition).

The photo radical 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 bisimidazole compound, and more preferably an O-acyloxime compound.

The O-acyloxime compound is a compound having a partial structure represented by formula (d1) (in the following formulae, a represents a bonding site).

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylthiophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1- [ 4- (2-hydroxyethyloxy) phenylsulfanylphenyl ] propane-1-one-2-imine and the like. Commercially available products such as TR-PBG 327 (manufactured by Changzhou powerful electronic new material Co., Ltd.), Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) OXE03, Irgacure (registered trademark) OXE04 (manufactured by BASF Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.) and the like may be used.

The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3) (in the following formulae, a represents a bonding site). 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-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholino) phenyl ] butan-1-one. Commercially available products such as Irgacure (registered trademark) 369, Irgacure (registered trademark) 907, and Irgacure (registered trademark) 379 (both manufactured by BASF) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d 2).

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1, 3, 5-triazine and the like.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. 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, 2' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (alkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (dialkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (trialkoxyphenyl) biimidazole (see, for example, japanese unexamined patent publication No. 48-38403, japanese unexamined patent publication No. 62-174204, etc.), 4', and biimidazole compounds in which the phenyl group at the 5, 5' -position is substituted with a carbonylalkoxy group (see, for example, Japanese patent laid-open No. 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 compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like.

Examples of the acid generator include onium salts such as 4-hydroxyphenyl dimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl/methyl/benzyl sulfonium hexafluoroantimonate, triphenyl sulfonium p-toluenesulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonate and benzoin toluenesulfonate.

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).

< other component of colored curable composition >

The colored curable composition may contain other components different from the above components. Examples of the other components include additives known in the field of colored curable compositions.

As other components, leveling agents may be used. Examples of the leveling agent include silicone surfactants and fluorine surfactants.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Examples of commercially available products include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning, Inc.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), Toray 400, TSF401, TSF410, F4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by JAMENTIVE PERFURANIACES MATERIALIAL, LS).

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

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Examples of commercially available products include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Material electronics), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Nitrosun corporation), and E5844 (manufactured by Seiki chemical research).

When the leveling agent is used, the content thereof is preferably 0.001 to 0.2% by weight, more preferably 0.002 to 0.1% by weight, and still more preferably 0.01 to 0.05% by weight, based on the total amount of the colored curable composition. When the content of the leveling agent is within the above range, the color filter obtained from the colored curable composition can have good flatness.

Examples

The present invention will be described in more detail with reference to examples and the like below, but the present invention is not limited to the examples and the like below, and can be carried out with appropriate modifications within a range that can meet the gist described above and below, and these are included in the technical scope of the present invention. In the following examples and the like, "part" means "part by weight", and "%" other than the thickening ratio (%) described later means "% by weight".

Production example 1: production of resin (B1-1)

750.0 parts of 3-methoxybutanol was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an air-guide tube, and the flask was stirred while being purged with nitrogen, and the temperature was raised to 80 ℃. Next, a mixture obtained by adding 28.8 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile) (polymerization initiator) to a monomer mixture comprising 25.6 parts of methacrylic acid, 146.4 parts of 3-methacryloxypropyltrimethoxysilane and 49.2 parts of methyl methacrylate was added dropwise from a dropping funnel to the flask. After completion of the dropwise addition, the mixture was stirred at 80 ℃ for 5 hours to effect copolymerization reaction, thereby obtaining a copolymer (hereinafter referred to as "resin (B1-1)") solution (solid content: 20%). The acid value (solid content equivalent) of the resin (B1-1) was 82mgKOH/g, the weight-average molecular weight (Mw) was 5500, and the silyl equivalent weight was 500.

Production example 2: production of resin (B2-1)

A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 80 ℃ with stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were dissolved in 125 parts of propylene glycol monomethyl ether acetate by using a dropping pump^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0^2,6]289 parts of a mixture of decan-9-yl esters (containing the ratio 50:50 in terms of molar ratio) was added dropwise to the flask over about 5 hours. On the other hand, a solution prepared by dissolving 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator in 235 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask using another dropping pump over about 6 hours. After the dropping of the polymerization initiator is completed, the mixture is mixedThe resulting mixture was kept at 80 ℃ for about 4 hours, and then cooled to room temperature to obtain a copolymer (hereinafter referred to as "resin (B2-1)") solution (solid content: 35.1%). The acid value (solid content equivalent) of the resin (B2-1) was 77mgKOH/g, the weight-average molecular weight (Mw) was 9200, and the polydispersity (Mw/Mn) was 2.08.

Production example 3: production of resin (B2-2)

A1L flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen atmosphere, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was heated to 85 ℃ with stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 5 hours^2,6]Decan-8-yl ester with acrylic acid 3, 4-epoxytricyclo [5.2.1.0^2,6]A mixed solution of 25 parts of a mixture of decane-9-yl ester, 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution in which 5 parts of 2, 2-azobisisobutyronitrile was dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was held at 85 ℃ 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 ℃ measured with a B-type viscometer was 23 mPas. The resin (B2-2) had an acid value (solid content conversion) of 111mgKOH/g, a weight-average molecular weight (Mw) of 8000 and a polydispersity (Mw/Mn) of 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.

The device comprises the following steps: k2479 (Shimadzu corporation)

Column: shimadzu Shim GPC-80M

Column temperature: 40 deg.C

Solvent: THF (tetrahydrofuran)

And (3) detecting the concentration of the solution: 25mg/mL (solvent; THF)

Flow rate: 1.0mL/min

A detector: RI (Ri)

Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh corporation)

Production example 4: production of Compound represented by formula (1 a-1)

A compound represented by the following formula (1 a-1) is produced as a colorant (A) in the same manner as in example 7 of Japanese patent application laid-open No. 2018-127596.

Production example 5: production of Compound represented by formula (2 a-1)

A compound represented by the following formula (2 a-1) is produced as a colorant (A) in the same manner as in synthetic example 19 of Japanese patent application laid-open No. 2015-38201.

Example 1: production of composition (1)

7 parts of the compound (1 a-1), 3 parts of a dispersant (DISPERBYK (registered trademark) -2050 (BYK-Chemie Japan Co., Ltd.)), 3 parts of a resin (B1-1) (in terms of solid content), 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol and 300 parts of 0.2mm zirconia beads were mixed, and the resulting mixture was shaken for 3 hours using a Paint Conditioner (LAU Co., Ltd.). Thereafter, the zirconia beads were removed by filtration to obtain composition (1).

The content of the colorant (a) (compound (1 a-1)) in the composition (1) was 53.8% based on the total amount of the solid components.

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 the compound (1 a-1), 3 parts of a dispersant (DISPERBYK (registered trademark) -2050 (BYK-Chemie Japan Co., Ltd.)), 1 part of a resin (B1-1) (in terms of solid content), 2 parts of a resin (B2-1) (in terms of solid content), 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol and 300 parts of 0.2mm zirconia beads were mixed, and the resulting mixture was shaken for 3 hours using a Paint Conditioner (LAU Co., Ltd.). Thereafter, the zirconia beads were removed by filtration to obtain composition (2).

The content of the colorant (a) (compound (1 a-1)) in the composition (2) was 53.8% based on the total amount of the solid components.

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 the compound (1 a-1), 3 parts of a dispersant (DISPERBYK (registered trademark) -2050 (BYK-Chemie Japan Co., Ltd.)), 3 parts of a resin (B2-1) (in terms of solid content), 81 parts of propylene glycol monomethyl ether acetate, 6 parts of diacetone alcohol and 300 parts of 0.2mm zirconia beads were mixed and shaken for 3 hours using a Paint Conditioner (LAU Co., Ltd.). Thereafter, the zirconia beads were removed by filtration to obtain composition (3).

The content of the colorant (a) (compound (1 a-1)) in the solid content of the composition (3) was 53.8% based on 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)

The resulting mixture was shaken for 3 hours using a Paint Conditioner (manufactured by LAU) comprising 5 parts of the compound (2 a-1), 4 parts of a dispersant (BYKLPN-21324 (manufactured by BYK-Chemie Japan)), 4 parts of a resin (B1-1) (in terms of solid content), 87 parts of propylene glycol monomethyl ether acetate and 300 parts of 0.2mm zirconia beads. Thereafter, the zirconia beads were removed by filtration to obtain composition (4).

The content of the colorant (a) (compound (2 a-1)) in the composition (4) was 38.5% based on the total amount of the solid components.

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 the compound (2 a-1), 4 parts of a dispersant (BYKLPN-21324 (BYK-Chemie Japan Co., Ltd.)), 4 parts of a resin (B2-1) (solid content conversion), 87 parts of propylene glycol monomethyl ether acetate and 300 parts of 0.2mm zirconia beads were mixed and shaken for 3 hours using a Paint Conditioner (Paint Conditioner, LAU Co., Ltd.). Thereafter, the zirconia beads were removed by filtration to obtain composition (5).

The content of the colorant (a) (compound (2 a-1)) in the composition (5) was 38.5% based on the total amount of the solid components.

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) >

Colored 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 follows, and the thickening ratio of the obtained colored curable compositions was measured.

(1-1) production of colored curable compositions (1) to (3)

281 parts of any one of the compositions (1) to (3), 50 parts of a resin (B2-2) (in terms of solid content), 50 parts of dipentaerythritol hexaacrylate (polymerizable compound (C) manufactured by Nippon chemical Co., Ltd.), 3 parts of N-benzoyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine ("Irgacure (registered trademark) OXE 01" manufactured by BASF Co., Ltd., polymerization initiator (D)) 500 parts of propylene glycol monomethyl ether acetate (solvent (E)) and 0.1 part of a polyether-modified organic Silicone oil ("Toray Silicone SH 8400" manufactured by Dow Corning Toray Co., Ltd., leveling agent) were mixed to obtain colored curable compositions (1) to (3).

(1-2) production of colored curable compositions (4) and (5)

424 parts of either of the compositions (4) and (5), 50 parts of a resin (B2-2) (in terms of solid content), 50 parts of dipentaerythritol hexaacrylate (manufactured by Nippon chemical Co., Ltd., polymerizable compound (C)), 3 parts of N-benzoyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01, manufactured by BASF Co., Ltd., polymerization initiator (D)), 430 parts of propylene glycol monomethyl ether acetate (solvent (E)), and 0.1 part of a polyether-modified organic Silicone oil (Toray Silicone SH8400, manufactured by Dow Corning ay Totorro., Ltd., leveling agent) were mixed to obtain colored curable compositions (4) and (5).

(1-3) production of colored curable composition (6)

The composition (5)424 parts, the resin (B2-2) (in terms of solid content), dipentaerythritol hexaacrylate (polymerizable compound (C) manufactured by Nippon chemical Co., Ltd.), 50 parts, N-benzoyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01 manufactured by BASF Co., Ltd., polymerization initiator (D))3 parts, propylene glycol monomethyl ether acetate (solvent (E))360 parts, 3-methoxybutanol (solvent (E))70 parts, and polyether modified organic Silicone oil (Toray Silicone SH8400 manufactured by Dow Corning Toray corporation, leveling agent) 0.1 part were mixed to obtain a colored curable composition (6).

(2) Measurement of thickening ratio

The viscosities (═ initial viscosities) of the colored curable compositions (1) to (6) immediately after production were measured using a cone-plate (E) Viscometer ("Viscometer TV-25" manufactured by eastern mechanical industries) at a rotation speed of 100rpm and a measurement temperature of 23 ℃. The results are shown in Table 1.

The viscosities (i.e., viscosities after storage) of the colored curable compositions (1) to (6) after storage at 40 ℃ for 7 days were measured in the same manner as described above, and the thickening ratio was calculated from the following formula. The results are shown in Table 1.

The thickening ratio (%). 100X viscosity after storage (mPas)/initial viscosity (mPas)

[ Table 1]

From table 1, it can be seen that: the thickening ratios (101% and 102%) of the colored curable compositions (1) and (2) obtained from the compositions (1) and (2) containing the resin (B-1) (examples 1 and 2) were further suppressed in the colored curable compositions (1) to (3) obtained from the composition (3) not containing the resin (B-1) (comparative example 1) using the compound (1 a-1) as the colorant (a).

In addition, as can be seen from table 1: in the case of the colored curable compositions (4) to (6) obtained using the compound (2 a-1) as the colorant (a), the thickening ratio (100%) of the colored curable composition (4) obtained from the composition (4) containing the resin (B-1) (example 3) was further suppressed from the thickening ratios (104% and 103%) of the colored curable compositions (5) and (6) obtained from the composition (5) not containing the resin (B-1) (comparative example 2).

Industrial applicability

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

Claims

1. A composition comprising a colorant (A), a resin (B) and a solvent (E),

the resin (B) comprises a resin (B1) containing a constituent unit (B1-1) represented by the formula (1B), and

the content of the colorant (A) is 35-70 wt% relative to the total solid content of the composition;

in the formula (1a), R^41aAnd R^42aEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^41aAnd R^42aBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^43aand R^44aEach independently represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atomsAn optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, an optionally substituted aralkyl group having 7 to 30 carbon atoms, or R^43aAnd R^44aBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^frepresents a fluoroalkyl group having 1 to 12 carbon atoms,

the substituent that the aromatic hydrocarbon group having 6 to 14 carbon atoms may have is selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and a-SO group₃ ^－、－SO₂－N^－－SO₂－R^fAnd optionally a substituted alkyl group having 1 to 8 carbon atoms,

the substituent that the aromatic hydrocarbon ring having 6 to 14 carbon atoms may have is selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and a-SO group₃ ^－、－SO₂－N^－－SO₂－R^fAnd optionally a substituted alkyl group having 1 to 8 carbon atoms,

a substituent which the five-to ten-membered aromatic heterocycle may haveIs selected from halogen atom, nitro group, hydroxy group, formyl group, -SO₃ ^－、－SO₂－N^－－SO₂－R^fAnd optionally a substituted alkyl group having 1 to 8 carbon atoms,

when the alkyl group having 1 to 8 carbon atoms is an alkyl group having 2 to 8 carbon atoms, -CH contained in the alkyl group₂-may be substituted by-O-or-CO-,

r represents an integer of 1 or more,

k represents-SO of the anion represented by the formula (1 a-A)₃ ^－and-SO₂－N^－－SO₂－R^fIs an integer of 2 or more,

in the formula (1 a-A), ring T^1a、R^41a～R^44aAnd R^47a～R^54aEach of which has the same meaning as described above,

when k-1 is an integer of 2 or more, a plurality of M^r+May be the same or different;

in the formula (2a), R^41bAnd R^42bEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^41bAnd R^42bBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

the five-to ten-membered aromatic heterocyclic ring may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, a hydroxyl group, a formyl group and an alkyl group having 1 to 8 carbon atoms which may have a substituent,

m represents an integer of 1 or more,

[Y]^m－an anion representing a valence of m, and

in the formula (2 a-C), ring T^1b、R^41b～R^44bAnd R^47b～R^54bEach having the same meaning as described above;

in the formula (3a), R¹And R²Each independently represents 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 10 carbon atoms which may have a substituent, or-R¹²－Si(R¹³)₃Or R is¹And R²Bond mergingTogether with the nitrogen atom to which they are bonded form a three-to ten-membered nitrogen-containing heterocyclic ring,

q represents a number of 0 or 1,

x represents a halogen atom, and X represents a halogen atom,

R¹²an alkanediyl group having 1 to 10 carbon atoms,

R¹³represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or a C1 to C4 alkoxy, and three R¹³Each of which may be the same or different,

R¹～R⁴the C6-10 aromatic hydrocarbon group may have a substituent selected from the group consisting of a halogen atom, a hydroxyl group, a formyl group, a C1-20 saturated hydrocarbon group which may have a halogen atom, -OR⁸、－SO₃ ^－、－SO₃ ^－Z⁺、－SO₃R⁸、－CO₂ ^－Z⁺、－CO₂R⁸and-SO₂NR⁹R¹⁰At least one of the above-mentioned (B),

-SO in the form of an ion present in the compound represented by formula (3a)₃ ^－When the number is 1;

in the formula (1b), R^1BRepresents a hydrogen atom or a methyl group,

n represents an integer of 1 to 10, and

indicates the number of the bonding sites,

wherein R is^2B～R^4BAt least one of the above groups is an alkoxy group having 1 to 6 carbon atoms.

2. The composition according to claim 1, wherein the content of the colorant (A) is 40 to 70% by weight with respect to the total amount of solid components of the composition.

3. The composition according to claim 1 or 2, wherein the ring T in formula (1a)^1aIs a ring represented by the formula (1t),

in the formula (1t), R^45aAnd R^46aEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^45aAnd R^46aBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^56arepresents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent,

L^1arepresents a sulfur atom, an oxygen atom or-NR^57a－，

R^57aRepresents a hydrogen atom or a carbon atom number of 1 to 1An alkyl group of 0 (a) or (b),

R^frepresents a fluoroalkyl group having 1 to 12 carbon atoms, and

denotes the bonding site to the carbenium ion.

4. The composition according to any one of claims 1 to 3, wherein in formula (1a), r is 2, and M^r+Is a 2-valent metal ion.

5. The composition according to claim 1 or 2, wherein in formula (1a), R^41aAnd R^43aEach independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

Ring T^1aIs a ring represented by the formula (1t),

the number r is 2, and the number r,

k represents-SO that the anion represented by the formula (1 a-A) has₃ ^－And is 2, the two anions represented by formula (1 a-A) are the same, and

M^r+is a barium ion, and the barium ion is a barium ion,

in the formula (1t), R^45aIs a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

L^1ais a sulfur atom, and

denotes the bonding site to the carbenium ion.

6. The composition according to any one of claims 1 to 5, wherein the ring T in formula (2a)^1bIs a ring represented by the formula (2t),

in the formula (2t), R^45bAnd R^46bEach independently represents 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or R^45bAnd R^46bBonded and form a three-to ten-membered nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded,

R^56brepresenting a hydrogen atom which may have a substituentA saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent,

L^1brepresents a sulfur atom, an oxygen atom or-NR^57b－，

R^57bRepresents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

denotes the bonding site to the carbenium ion.

7. The composition according to any one of claims 1 to 6, wherein [ Y ] in the formula (2a)]^m－Is a polyacid anion containing tungsten atoms.

8. The composition according to any one of claims 1 to 6, wherein [ Y ] in the formula (2a)]^m－Is [ PW ]₁₂O₄₀]^3－、[P₂W₁₈O₆₂]^6－、[P₂W₁₈O₆₂]^6－、[SiW₁₂O₄₀]^4－、[SiW₁₂O₄₀]^4－、[SiW₁₂O₄₀]^4－、[P₂W₁₇O₆₁]^10－、[P₂W₁₅O₅₆]^12－、[H₂P₂W₁₂O₄₈]^12－、[NaP₅W₃₀O₁₁₀]^14－、[SiW₉O₃₄]^10－、[SiW₁₀O₃₆]^8－、[SiW₁₁O₃₉]^8－、[SiW₁₁O₃₉]^8－、[W₆O₁₉]^2－、[W₁₀O₃₂]^4－Or [ WO)₄]^2－。

9. The composition according to any one of claims 1 to 5, wherein R in the formula (2a)^41b、R^43bAnd R^47b～R^54bEach independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

ring T^1bIs a ring represented by the formula (2t),

m is the number of 3,

the three cations represented by the formula (2 a-C) are the same, and

[Y]^m－is [ PW ]₁₂O₄₀]^3－，

In the formula (2t), R^45bIs a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R^46ba phenyl group which may have an alkyl group having 1 to 8 carbon atoms,

L^1bis a sulfur atom, and

denotes the bonding site to the carbenium ion.

10. Any of claims 1 to 9The composition, wherein in the formula (3a), R¹And R³Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a carboxyl group, an alkyl group having 1 to 8 carbon atoms which may have a group selected from the group consisting of₂NR⁹R¹⁰Phenyl of at least one substituent of (a), or-R¹²－Si(R¹³)₃，

R⁵is-SO₃ ^－，

R⁶And R⁷Are all hydrogen atoms, and are,

R¹²an alkanediyl group having 1 to 6 carbon atoms,

three R¹³All of which are C1-C4 alkoxy groups,

p is 1, and

q is 0.

11. The composition according to any one of claims 1 to 10, wherein the total content of the compound represented by formula (1a), the compound represented by formula (2a) and the compound represented by formula (3a) is 50 to 100% by weight based on the total amount of the colorant (A).

12. The composition according to any one of claims 1 to 5, wherein at least one selected from the group consisting of the compound represented by formula (1a), the compound represented by formula (2a) and the compound represented by formula (3a) is the compound represented by formula (1a), and the content of the compound represented by formula (1a) is 50 to 100% by weight based on the total amount of the colorant (A).

13. The composition according to any one of claims 1,2 and 6 to 9, wherein at least one selected from the group consisting of the compound represented by formula (1a), the compound represented by formula (2a) and the compound represented by formula (3a) is the compound represented by formula (2a), and the content of the compound represented by formula (2a) is 50 to 100% by weight with respect to the total amount of the colorant (a).

14. The composition according to any one of claims 1 to 13, wherein the resin (B1) is a copolymer comprising the constituent unit (B1-1), the constituent unit (B1-2) derived from a polymerizable unsaturated compound having an acidic group, and the other constituent unit (B1-3), and the amount of the constituent unit (B1-1) is 1 to 50 mol% when the total of all the constituent units in the copolymer is 100 mol%.

15. The composition according to any one of claims 1 to 14, wherein the weight average molecular weight of the resin (B1) is 1000 to 50000.

16. The composition according to any one of claims 1 to 15, wherein the resin (B1) is contained in an amount of 10 to 100 parts by weight based on 100 parts by weight of the colorant (a).

17. The composition according to any one of claims 1 to 15, wherein the resin (B1) is contained in an amount of 10 to 60 parts by weight based on 100 parts by weight of the colorant (a).