JP6463624B2 - Compound - Google Patents

Description

  The present invention relates to novel compounds.

  As a colored curable resin composition for forming a color filter contained in a liquid crystal display device or the like or a solid-state image sensor, a compound represented by the formula (A-III-1) in International Publication No. 2012/053211, A colored curable resin composition containing a binder resin, a solvent, a polymerization initiator, and a curing agent is described.

International Publication No. 2012/053211

  The above known compounds are not sufficiently satisfactory in heat resistance, and therefore the colored curable resin composition containing the compound is not sufficiently satisfactory in terms of heat resistance.

The present invention provides the following [1] to [11].
[1] A compound represented by formula (A-VI).

[In the formula (A-VI), the counter ion Y represents an m-valent anion.
R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aralkyl group.
R ^11A and R ^12A each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^11A and R ^12A is an alkyl group having 1 to 10 carbon atoms.
R ^13A and R ^14A each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^13A and R ^14A is an alkyl group having 1 to 10 carbon atoms.
R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
In R ^{1A to} R ^20A , an oxygen atom may be inserted between the methylene groups constituting the alkyl group.
A represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent.
m represents an integer of 1 to 14. ]

[2] A compound represented by the formula (AI).

[In the formula (AI), the counter ion Y represents an m-valent anion.
R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aralkyl group.
R ^11A and R ^12A each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^11A and R ^12A is an alkyl group having 1 to 10 carbon atoms.
R ^13A and R ^14A each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^13A and R ^14A is an alkyl group having 1 to 10 carbon atoms.
R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
In R ^{1A to} R ^20A , an oxygen atom may be inserted between the methylene groups constituting the alkyl group.
R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic hydrocarbon group.
R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic hydrocarbon group.
In R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the alkyl group may have an oxygen atom inserted between the methylene groups constituting the alkyl group.
m represents an integer of 1 to 14. ]

[3] The compound according to [1] or [2], wherein the counter ion is a fluorine-containing anion having a fluorine atom.
[4] The compound according to [1] or [2], wherein the counter ion is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements.
[5] A compound (A1) composed of an ion represented by the formula (A-VI) and a counter ion according to [1], a resin (B), a polymerizable compound (C), a polymerization initiator (D), and A colored curable resin composition containing a solvent (E).
[6] The colored curable resin composition according to [5], including at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye.
[7] The colored curable resin composition according to [5] or [6], including a colorless metal complex (F).
[8] The colored curable resin composition according to any one of [5] to [7], further including a blue pigment.
[9] A coating film formed from the colored curable resin composition according to [5] to [8].
[10] A color filter formed from the colored curable resin composition according to [5] to [8].
[11] A display device including the color filter according to [10].

  According to the present invention, a novel compound that can be preferably used for a color filter having good heat resistance can be obtained.

  The compound represented by the formula (A-VI) according to the present invention can be represented by the following formula.

[In the formula (A-VI), the counter ion Y represents an m-valent anion.
R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aralkyl group.
R ^11A and R ^12A each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^11A and R ^12A is an alkyl group having 1 to 10 carbon atoms.
R ^13A and R ^14A each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^13A and R ^14A is an alkyl group having 1 to 10 carbon atoms.
R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
In R ^{1A to} R ^20A , an oxygen atom may be inserted between the methylene groups constituting the alkyl group.
A represents an aromatic hydrocarbon group or a heteroaromatic group which may have a substituent.
m represents an integer of 1 to 14. ]

The alkyl group represented by R ^{1A to} R ^20A may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.
The cyclic alkyl group represented by R ^{1A to} R ^20A may be monocyclic or polycyclic. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic alkyl group preferably has 3 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.
Specific examples of the alkyl group represented by R ^{1A to} R ^20A include groups represented by the following formulas. In the following formula, * represents a bond.

Of the groups represented by R ^{1A to} R ^20A , examples of the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group include groups represented by the following formulae. In the following formula, * represents a bond.

  The group having an oxygen atom inserted between the methylene groups constituting the alkyl group is preferably a group having 1 to 10 carbon atoms, more preferably a group having 1 to 6 carbon atoms. The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group. Moreover, 1-4 are preferable and, as for carbon number between oxygen atoms, 2-3 are more preferable.

In R ^{9A to} R ^10A , examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

In R ^{9A to} R ^10A , examples of the aromatic hydrocarbon group in the aralkyl group include a phenyl group and a naphthyl group.

Among the groups represented by R ^{9A to} R ^10A , examples of the substituent in the aromatic hydrocarbon group and the aralkyl group include a halogen atom such as a fluorine atom, a chlorine atom and iodine; and a carbon number such as a methoxy group and an ethoxy group. An alkoxy group having 1 to 6 carbon atoms; a hydroxy group; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; a methoxycarbonyl group and an ethoxycarbonyl group Examples thereof include an alkoxycarbonyl group having 1 to 6 carbon atoms such as a group.

Specific examples of the aromatic hydrocarbon group which may be substituted include groups represented by the following formulae. In the following formula, * represents a bond.
Specific examples of the aralkyl group which may be substituted include groups in which a methylene group is bonded to the bond of each specific example of the following aromatic hydrocarbon group.

Among the groups represented by R ^{11A to} R ^14A , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

R ^{1A to} R ^8A are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group, from the viewpoint of ease of synthesis. .

R ^{9A to} R ^10A are each independently an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aralkyl group from the viewpoint of ease of synthesis. Each independently, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, a phenyl group having a methyl group, a naphthyl group having a methyl group; an unsubstituted or halogen atom, a methoxy group, an ethoxy group It is more preferably an aralkyl group substituted by one or more selected from a group, a sulfamoyl group, a methylsulfonyl group, a methoxycarbonyl group, and an ethoxycarbonyl group, and each independently has 1 to 4 carbon atoms. The linear alkyl group is more preferable.

From R ^{11A to} R ^12A , at least one of them is an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and preferably having 1 to 4 carbon atoms. An alkyl group is more preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable. When one of R ^{11A to} R ^12A is an alkyl group, the other may be a halogen atom, but is preferably an alkyl group having 1 to 10 carbon atoms, and preferably an alkyl group having 1 to 8 carbon atoms. Are more preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable.

R ^<13A > -R <^14A> is a C1-C10 alkyl group from a heat resistant point, It is more preferable that it is a C1-C8 alkyl group, and it is a C1-C4 alkyl group. Is more preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable. When one of R ^{13A to} R ^14A is an alkyl group, the other may be a halogen atom, but is preferably an alkyl group having 1 to 10 carbon atoms, and preferably an alkyl group having 1 to 8 carbon atoms. Are more preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable.

R ^{15A to} R ^20A are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, from the viewpoint of ease of synthesis. More preferably, it is more preferably a hydrogen atom or a methyl group.

In A, examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
Examples of the substituent in the aromatic hydrocarbon group represented by A include a halogen atom such as a fluorine atom, a chlorine atom and iodine, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. Alkyl group, hydroxy group, SO ₃ ^- group, methylsulfonyl group, dialkylamino group, phenylamino group, and the like. The phenylamino group is an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. It may be substituted with a group, a hydroxy group, a SO ₃ ^- group, a methylsulfonyl group, a dialkylamino group or the like.
In A, examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulae. * Represents a bond.

  Among these, groups represented by formula (A1-2) and formula (A1-7) are preferable.

In A, the heteroaromatic group includes an aromatic ring having a nitrogen atom, an oxygen atom, or a sulfur atom, such as a thiazolyl group, an imidazolyl group, or an oxazolyl group.
Examples of the substituent in the heteroaromatic group represented by A include a phenyl group and a phenylamino group, and the phenylamino group may be substituted with an alkyl group having 1 to 4 carbon atoms.

  In A, examples of the heteroaromatic group which may have a substituent include a group represented by the following formula (A-2). * Represents a bond.

[In the formula (A-2),
R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic hydrocarbon group.
R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic hydrocarbon group.
In R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the alkyl group may have an oxygen atom inserted between the methylene groups constituting the alkyl group. ]

^Examples of the alkyl group for R ⁴⁵ and R ⁴⁶ include C 1-10 alkyl groups for R ^{1A to} R ^20A , respectively.
In R ⁴⁵ and R ⁴⁶ , specific examples of the alkyl group having 1 to 10 carbon atoms include groups represented by the following formulae. In the following formula, * represents a bond. Among these, an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

In R ⁴⁵ and R ⁴⁶ , examples of the group in which an oxygen atom is inserted between methylene groups constituting the alkyl group include groups represented by the following formulae. In the following formula, * represents a bond.

  The group having an oxygen atom inserted between the methylene groups constituting the alkyl group is preferably a group having 1 to 10 carbon atoms, more preferably a group having 1 to 6 carbon atoms. The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group. Moreover, 1-4 are preferable and, as for carbon number between oxygen atoms, 2-3 are more preferable.

Examples of the aromatic hydrocarbon group for R ⁴⁵ and R ⁴⁶ include a phenyl group and a naphthyl group.
In R ⁴⁵ and R ⁴⁶ , the substituent in the aromatic hydrocarbon group includes a halogen atom such as a fluorine atom, a chlorine atom or iodine; a haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; Group, an alkoxy group having 1 to 6 carbon atoms such as ethoxy group; a hydroxy group; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; a sulfamoyl group; an alkylsulfonyl having 1 to 6 carbon atoms such as a methylsulfonyl group Group: C1-C6 alkoxycarbonyl groups, such as a methoxycarbonyl group, etc. are mentioned.

  Specific examples of the aromatic hydrocarbon group which may be substituted include groups represented by the following formulae. In the following formula, * represents a bond.

R ⁴⁵ and R ⁴⁶ are each independently preferably an alkyl group having 1 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group, from the viewpoint of ease of synthesis. An alkyl group having 8 carbon atoms, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or a methylsulfonyl group. It is more preferably an aromatic hydrocarbon group, and further preferably an alkyl group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bond.

The alkyl group in R ^55, include alkyl groups having 1 to 10 carbon atoms in R ^1A to R ^20A.
In R ^55, the alkyl group having 1 to 10 carbon atoms, a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl group, n- hexyl, n- octyl, n- nonyl Linear alkyl groups such as n-decyl group; branched alkyl groups such as isopropyl group, sec-butyl group, tert-butyl group, isopentyl group, 1-methylpentyl group, 1-propylbutyl group; cyclopropyl group A cyclic alkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc., and examples thereof include a group represented by the following formula. In the following formula, * represents a bond. Among these, an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

In R ⁵⁵ , examples of the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group include groups represented by the following formulae. In the following formula, * represents a bond.

Examples of the aromatic hydrocarbon group for R ⁵⁵ include a phenyl group and a naphthyl group, and a phenyl group is preferable.
In R ⁵⁵ , the substituent in the aromatic hydrocarbon group includes a halogen atom such as a fluorine atom, a chlorine atom or iodine; a haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; a methoxy group or an ethoxy group An alkoxy group having 1 to 6 carbon atoms such as a group; a hydroxy group; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; C1-C6 alkoxy carbonyl groups, such as a carbonyl group, etc. are mentioned. Specific examples of the aromatic hydrocarbon group which may be substituted include groups represented by the following formulae. In the following formula, * represents a bond.

R ⁵⁵ is preferably an alkyl group having 1 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group, more preferably an alkyl group having 1 to 8 carbon atoms or a halogen from the viewpoint of ease of synthesis. An aromatic hydrocarbon group which may be substituted with an atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or a methylsulfonyl group More preferably, it is an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bond.

The counter ion Y in the formula (A-VI) represents an m-valent anion. [Y] ^m- includes known anions, but from the viewpoint of heat resistance, boron-containing anions, aluminum-containing anions, fluorine-containing anions, and at least selected from the group consisting of tungsten, molybdenum, silicon and phosphorus An anion containing one element and oxygen as essential elements is preferred.

  Examples of the boron-containing anion and the aluminum-containing anion include anions represented by the following formula (4).

[In Formula (4), W ¹ and W ² each independently represent a group having two substituents formed by releasing a proton from a monovalent proton-donating substituent. M represents boron or aluminum. ]

  The group having two substituents formed by releasing protons from a monovalent proton-donating substituent is selected from compounds having at least two monovalent proton-donating substituents (for example, a hydroxy group, a carboxylic acid group, etc.). And groups in which protons are released from each of the two proton-donating substituents. As the compound, catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2′-biphenol which may have a substituent, a substituent 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent It may be an acid, an optionally substituted binaphthol, an optionally substituted salicylic acid, an optionally substituted benzylic acid or an optionally substituted mandelic acid. Is preferred.

  In the exemplified compounds, examples of the substituent include a saturated hydrocarbon group (for example, an alkyl group, a cycloalkyl group, etc.), a halogen atom, a haloalkyl group, a hydroxy group, an amino group, a nitro group, and an alkoxy group.

  Examples of the salicylic acid which may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di- monoaminosalicylic acid such as tert-butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2 , 4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), monohydroxysalicylic acid such as 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid); 4,5-dihydroxysalicylic acid, 4, 6-Dihydroxysalicyl Dihalosalicylic acid such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid and the like; And dihalosalicylic acid such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid and 3,5-diiodosalicylic acid; and trihalosalicylic acid such as 3,5,6-trichlorosalicylic acid.

  As benzylic acid which may have a substituent,

  As the mandelic acid which may have a substituent,

Etc.

  Among the anions represented by the formula (4), preferred anions are the anions represented by the following formulas, which have the substituents shown in Table 1 (BC-1) to anions (BC-24), In addition, anion (BC-25) to anion (BC-28) represented by formula (BC-25), formula (BC-26), formula (BC-27), and formula (BC-28), respectively, may be mentioned. .

  As an anion represented by Formula (4), an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), an anion (BC -27) is preferable, an anion (BC-1), an anion (BC-2), and an anion (BC-25) are more preferable, and an anion (BC-1) and an anion (BC-2) are still more preferable. A salt formed by any of these anions and an ion represented by the formula (A-VI) tends to be excellent in solubility in an organic solvent.

  Examples of the fluorine-containing anion include groups represented by the following formulas (6), (7), (8), and (9).

[In Formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ together represent 1 carbon atom. Represents a fluorinated alkanediyl group of ~ 4. ]

Wherein (7), the W ⁵ to ^W-7 each independently represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. ]

Wherein (8), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms. ]

Wherein (9), Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms. ]

In the formulas (6) and (7), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include —CF ₃ , —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —CF ₂ CF ₂ CF ₂ CF ₃ , —CF ₂ CF (CF ₃ ) ₂ , -C (CF ₃ ) _{3 and the} like.

In the formula (6), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and —CF ₂ —, —CF ₂ CF ₂ —, —CF ₂ CF ₂ CF ₂ —, — C (CF ₃ ) ₂ —, —CF ₂ CF ₂ CF ₂ CF ₂ — and the like can be mentioned.

In the formula (8), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group. The perfluoro alkanediyl _{group, -CF 2 -, - CF 2} CF 2 -, - CF 2 CF 2 CF 2 -, - C (CF 3) 2 -, - CF 2 CF 2 CF 2 CF 2 - and the like Can be mentioned.

In the formula (9), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. The perfluoroalkyl _{group, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3 ) ₂ , —C (CF ₃ ) _{3 and the} like.

  As the anion represented by the formula (6) (hereinafter sometimes referred to as “anion (6)”), the anion represented by the formula (6-1) to the formula (6-6) (hereinafter referred to as “anion (6)”). -1) "to" anion (6-6) ").

  Examples of the anion represented by the formula (7) (hereinafter sometimes referred to as “anion (7)”) include an anion (7-1) represented by the following formula.

  As the anion represented by the formula (8) (hereinafter sometimes referred to as “anion (8)”), the anions represented by the formula (8-1) to the formula (8-4) (hereinafter referred to as “anion (8— 1) "to" anion (8-4) ").

  As the anion represented by the formula (9) (hereinafter sometimes referred to as “anion (9)”), the anion represented by the formula (9-1) to the formula (9-4) (hereinafter referred to as “anion (9−)”). 1) "to" anion (9-4) ").

  At least one anion selected from the group consisting of anion (6), anion (7), anion (8) and anion (9) (that is, a fluorine-containing anion. Hereinafter, it may be referred to as “anions (6) to (9)”. ), The solubility of the salt represented by the ion represented by the formula (A-VI) and the anion in an organic solvent can be improved. Among these, anion (6-1), anion (6-2) and anion (7-1) are preferable, and anion (6-2) is particularly preferable.

  Examples of the anion that forms a salt with the ion represented by the formula (A-VI) include an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen as essential elements. An anion of heteropolyacid or isopolyacid containing tungsten as an essential element is preferable, and anions of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid are more preferable.

Examples of such anions of heteropolyacid or isopolyacid containing tungsten as an essential element include Keggin type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , β- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , Keggin type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ⁴⁻ , β- [SiW ₁₂ O ₄₀ ] ⁴⁻ , γ -[SiW ₁₂ O ₄₀ ] ⁴⁻ , and other examples include [P ₂ W ₁₇ O ₆₁ ] ¹⁰⁻ , [P ₂ W ₁₅ O ₅₆ ] ¹²⁻ , [H ₂ P ₂ W ₁₂ O ₄₈ ] ¹²⁻ , [NaP ₅ W ₃₀ O ₁₁₀ ] ¹⁴⁻ , α- [SiW ₉ O ₃₄ ] ¹⁰⁻ , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^{2- and the} like.

Of the anions other than the heteropolyacid or isopolyacid anion containing tungsten as an essential element, an anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus is preferred.
Examples of such an anion comprising at least one element selected from the group consisting of silicon and phosphorus and oxygen include SiO ₃ ²⁻ and PO ₄ ³⁻ .

In particular, because of the ease of synthesis and post-treatment, heteropolyacid anions such as Keggin-type phosphotungstate ion, Dawson-type phosphotungstate ion, Keggin-type silicate-tungstate ion, and isopolyacid anions such as [W ₁₀ O ₃₂ ] ^4- preferable.

  Examples of the cation moiety of the formula (A-VI) include cations 1 to 54 having the substituents represented by the formulas (A-VI-1) and (A-I-1) shown in the following table, respectively. .

  Among these, as the cation moiety represented by the formulas (A-VI-1) and (AI-1), a cation moiety represented by the formula (AI-1) is preferable, and the cation 25 to the cation 30; And cation 37 to cation 54 are more preferable, and cation 37 to cation 42 are particularly preferable.

Specific examples of the compound represented by the formula (A-VI) include any one of the cations 1 to 54, anions (BC-1) to (BC-28), anions (6-1). To (6-6), anion (7-1), anion (8-1) to (8-4), and a combination with any one anion among anions (9-1) to (9-4) A combination of any three cations out of the cations 1 to 54 and the anion α- [PW ₁₂ O ₄₀ ] ³⁻ ; any six cations out of the cations 1 to 54 and the anion α- [P ₂ W _18; the combination of O _62] ^6- and, any of the four cations and anions ^{_{α- [SiW 12 O 40] 4-}} , or [W ₁₀ O _32] ^4- combination of the like of the cationic 1-54 .

  The compound represented by formula (A-VI) is preferably a compound represented by formula (AI) (hereinafter sometimes referred to as compound (AI)). The compound represented by the formula (AI) includes tautomers thereof.

[In formula (AI), Y, m, R ^{1A to} R ^20A , R ⁴⁵ , R ⁴⁶ and R ⁵⁵ each have the same meaning as described above. ]

  Examples of the cation moiety of the formula (A-I) are each represented by the formula (A-I-I), and include the cation 19 to the cation 54 described above.

  Especially, as a cation part of a formula (AI), the cation 25-cation 30 and the cation 37-cation 54 are more preferable, and the cation 37-cation 42 is especially preferable.

[Y] ^m- includes the above-described various anions. From the viewpoint of heat resistance, preferred anions include a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, and an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements. It is.

Examples of the boron-containing anion and the aluminum-containing anion include the anion represented by the formula (4). [Y] Among the anions represented by ^m- , the anions represented by the formula (4) include anions (BC-1), anions (BC-2), anions (BC-3), and anions (BC). -25), anion (BC-26) and anion (BC-27) are preferred, anion (BC-1), anion (BC-2) and anion (BC-25) are more preferred, and anion (BC-1) And an anion (BC-2) is more preferable. When these anions are used, the compound (AI) of the present invention tends to be excellent in solubility in an organic solvent.

  Examples of the fluorine-containing anion include the anions represented by the above formula (6), formula (7), formula (8) and formula (9) (hereinafter, each anion is anion (6), anion (7), anion, respectively). (8), sometimes referred to as anion (9)).

  Containing at least one anion selected from the group consisting of anion (6), anion (7), anion (8) and anion (9) (hereinafter sometimes referred to as “anions (6) to (9)”) Thus, the solubility of the salt of the dye represented by the formula (AI) in an organic solvent can be improved. Among these, anion (6-1), anion (6-2) and anion (7-1) are preferable, and anion (6-2) is particularly preferable.

[Y] Among the anions represented by ^m- , an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements contains tungsten as an essential element Heteropolyacid or isopolyacid anions are preferred, in particular phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid anions.

Examples of such anions of heteropolyacid or isopolyacid containing tungsten as an essential element include Keggin type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , β- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , Keggin type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ⁴⁻ , β- [SiW ₁₂ O ₄₀ ] ⁴⁻ , γ -[SiW ₁₂ O ₄₀ ] ⁴⁻ , and other examples include [P ₂ W ₁₇ O ₆₁ ] ¹⁰⁻ , [P ₂ W ₁₅ O ₅₆ ] ¹²⁻ , [H ₂ P ₂ W ₁₂ O ₄₈ ] ¹²⁻ , [NaP ₅ W ₃₀ O ₁₁₀ ] ¹⁴⁻ , α- [SiW ₉ O ₃₄ ] ¹⁰⁻ , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^{2- and the} like.

Of the anions other than the heteropolyacid or isopolyacid anion containing tungsten as an essential element, an anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus is preferred.
Examples of such an anion comprising at least one element selected from the group consisting of silicon and phosphorus and oxygen include SiO ₃ ²⁻ and PO ₄ ³⁻ .

In particular, because of the ease of synthesis and post-treatment, heteropolyacid anions such as Keggin-type phosphotungstate ion, Dawson-type phosphotungstate ion, Keggin-type silicate-tungstate ion, and isopolyacid anions such as [W ₁₀ O ₃₂ ] ^4- preferable.

  m is usually 1-14, preferably 1-12, more preferably 1-10, still more preferably 1-6, and particularly preferably 1-4.

As the compound (AI), any one of the cations 19 to 54, anions (BC-1) to (BC-28), anions (6-1) to (6-6), anions (7-1), anions (8-1) to (8-4), and combinations with any one anion among anions (9-1) to (9-4), among the cations 19 to 54 A combination of any three cations and an anion α- [PW ₁₂ O ₄₀ ] ³⁻ , a combination of any six cations of the cations 19 to 54 and an anion α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ A combination of any four cations out of the cations 19 to 54 and the anion α- [SiW ₁₂ O ₄₀ ] ⁴⁻ or [W ₁₀ O ₃₂ ] ⁴⁻ is exemplified.

Compound (AI) includes a salt containing a cation moiety of (AI) (hereinafter sometimes referred to as compound (A-II)), an alkali metal salt of an anion [Y] ^m- or a protonic acid. It can be manufactured by mixing. Salts containing a cationic portion of (A-I), for example, hydrochloride, phosphate, sulfate, benzenesulfonate, naphthalenesulfonate, perchlorate, BF ₄ salt, PF ₆ salt and Can be mentioned. Examples of the alkali metal include lithium, sodium and potassium.

With respect to compound (A-II), the amount of an anion [Y] ^m− alkali metal salt or proton acid used is such that the charge of the anion [Y] ^m− is balanced with the cation of compound (A-II). Although it is good to add by stoichiometric ratio, it is preferably 0.5 mol or more and 8 mol or less, and more preferably 1 mol or more and 3 mol or less with respect to 1 mol of the compound (A-II).

Mixing of the compound (A-II) and the anion [Y] ^{m- with} an alkali metal salt or protonic acid may be carried out by dissolving both in the above solvent or not.

Solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, water and chloroform. Is mentioned.
Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol and water are preferable. When these solvents are used, the solubility of the alkali metal salt of the compound (A-II) and the anion [Y] ^m- tends to be high.
The amount of the solvent to be used is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 20 parts by mass or less with respect to 1 part by mass of the compound (A-II).
When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added.

The mixing temperature of the compound (A-II) and the anion [Y] ^m- alkali metal salt is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, and further preferably 20 ° C to 100 ° C. . The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, and further preferably 3 hours to 12 hours.

  When a solvent compatible with water is used, the solution is mixed and further stirred for 1 to 3 hours as necessary, and then the precipitate is obtained by filtration to obtain the compound (AI). Can be obtained. If necessary, the obtained compound (AI) may be washed with ion-exchanged water.

  When a solvent that is not compatible with water is used, the reaction mixture and ion-exchanged water are mixed, and further stirred for 1 to 3 hours as necessary. Thereafter, the organic layer is obtained by liquid separation, whereby the compound ( A solution containing AI) can be obtained. If necessary, the solution may be washed with ion exchange water. The compound (AI) can be obtained by removing the solvent from the solution containing the compound (AI).

  Compound (A-II) can be produced, for example, by reacting a compound represented by formula (BI) with a compound represented by formula (CI). Such a reaction may be performed in the presence of an organic solvent or may be performed without a solvent.

[In formula (BI) and formula (CI), R ^{1A to} R ^20A , R ⁴⁵ , R ⁴⁶ and R ⁵⁵ each have the same meaning as described above. ]

  Compound (A-II) is produced by reacting a compound represented by formula (B-II) with a compound represented by formula (C-II) and formula (C-III). Can do. Such a reaction may be performed in the presence of an organic solvent or may be performed without a solvent.

[In Formula (B-II), Formula (C-II), and Formula (C-III), R ^{1A to} R ^20A , R ⁴⁵ , R ^46, and R ⁵⁵ each have the same meaning as described above. ]

  The amount of the compound represented by the formula (CI) to be used is preferably 0.5 mol or more and 8 mol or less, more preferably 1 mol per 1 mol of the compound represented by the formula (BI). It is 1 mol or more and 3 mol or less.

  The total amount of the compound represented by the formula (C-II) and the compound represented by the formula (C-III) is preferably 0 with respect to 1 mol of the compound represented by the formula (B-II). .5 mol or more and 8 mol or less, more preferably 1 mol or more and 3 mol or less.

  The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

  Any reaction is preferably performed in an organic solvent from the viewpoint of yield. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl Ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like. The amount of the organic solvent to be used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass with respect to 1 part by mass of the compound represented by the formula (BI) or formula (B-II). Part to 10 parts by mass.

The above reaction is preferably carried out in the presence of a condensing agent from the viewpoint of yield. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, thionyl chloride and the like.
The amount of the condensing agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass with respect to 1 part by mass of the compound represented by the formula (BI) or formula (B-II). 0.2 parts by mass or more and 5 parts by mass or less.

  The method for obtaining compound (A-II) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with a solvent such as alcohol (for example, methanol) and the precipitated crystals can be collected by filtration. The reaction mixture is preferably added to a solvent such as the alcohol. The temperature at which the reaction mixture is added is preferably −100 ° C. or higher and 50 ° C. or lower, more preferably −80 ° C. or higher and 0 ° C. or lower. Thereafter, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystal collected by filtration is preferably washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  As a manufacturing method of a compound (BI) and a compound (B-II), the well-known various methods, for example, the method described in West Germany patent application P3928243.0 is mentioned.

  As a manufacturing method of compound (C-II) and (C-III), well-known various methods, such as the method described in the international publication 2012/053211, are mentioned.

When R ^9A and R ^10A are an alkyl group or an aralkyl group, the compound (CI) is a compound represented by the formula (C-IV) (hereinafter referred to as compound (C-IV)) as an alkylating agent or The compound (C-IV) can be produced by reacting with an aralkylating agent. The compound (C-IV) is represented by the compound represented by the formula (CV) (hereinafter referred to as the compound (CV)) and the formula (C-VI). It can manufacture by making the compound (henceforth a compound (C-VI)) made to react. Compound (CI) can also be produced directly from compound (CV) and compound (C-VI) regardless of the types of R ^9A and R ^10A .

(In the formula, R ^{1A to} R ^20A are the same as above. R ^1B is the same as R ^9A and R ^10A , R ^2B is the same as R ^11A and R ^13A , and R ^3B is R ^12A and R ^14A . R ^4B is the same as R ^15A and R ^18A , R ^5B is the same as R ^16A and R ^19A , R ^6B is the same as R ^17A and R ^20A, and R ^7B and R ^8B are halogen. Atom).

As the alkylating agent, known alkylating agents such as alkyl halides and sulfates can be used. In particular, alkyl halides are preferable because of their availability, and primary alkyl iodides are particularly preferable because of their ease of synthesis. . As the aralkylating agent, benzyl halide or the like can be used.
Specific examples of the alkylating agent include methyl iodide, ethyl iodide, normal butyl iodide, ethyl bromide, normal butyl bromide, dimethyl sulfate, diethyl sulfate and the like. Specific examples of the aralkylating agent include benzyl iodide, benzyl bromide and the like.
The amount of the alkylating agent or aralkylating agent to be used is preferably 2 to 6 mol, more preferably 2 to 4 mol, per 1 mol of the compound represented by the formula (C-IV). It is.
The reaction temperature is preferably 20 ° C to 180 ° C, more preferably 30 ° C to 50 ° C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 2 hours.

  Any reaction is preferably performed in an organic solvent from the viewpoint of yield. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl Ketone solvents such as ketones; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone; and the like. The amount of the organic solvent to be used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (C-IV). is there.

The above reaction is preferably carried out in the presence of a basic compound from the viewpoint of yield. Examples of the basic compound include sodium hydride, LDA, DIBAL, t-butoxypotassium and the like.
The amount of the basic compound used is preferably 2 mol or more and 6 mol or less, more preferably 2 mol or more and 4 mol or less, per 1 mol of the compound represented by the formula (C-IV).

  The method for obtaining the compound (C-IV) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with a solvent such as alcohol (for example, methanol) and the precipitated crystals can be collected by filtration. The reaction mixture is preferably added to a solvent such as the alcohol. The temperature at which the reaction mixture is added is preferably −100 ° C. or higher and 50 ° C. or lower, more preferably −80 ° C. or higher and 0 ° C. or lower. Thereafter, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystal collected by filtration is preferably washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  As described above, the compound (C-IV) can be produced by reacting the compound (CV) with the compound (C-VI). Moreover, the said compound (CI) can also be manufactured by making a compound (CV) and a compound (C-VI) react as mentioned above.

In the formula (C-VI), examples of the halogen atom represented by R ^7B and R ^8B include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. From the viewpoint of easy availability of raw materials, a fluorine atom and chlorine Atoms are preferred.

The amount of compound (CV) to be used is preferably 2 to 5 mol, more preferably 2 to 3 mol, per 1 mol of compound (C-VI).
The reaction temperature is preferably 20 ° C to 180 ° C, more preferably 30 ° C to 50 ° C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 2 hours.

  Any reaction is preferably carried out in an organic solvent from the viewpoint of yield. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl Ketone solvents such as ketones; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone; and the like. The amount of the organic solvent to be used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (C-VI). is there.

The above reaction is preferably carried out in the presence of a palladium compound, a phosphine compound and a basic compound from the viewpoint of yield.
Examples of the palladium compound include palladium acetate (II), palladium chloride (II), palladium bromide (II), bis (2,4-pentanedionato) palladium (II), bis (dibenzylideneacetone) palladium (0), And tris (dibenzylideneacetone) dipalladium (0).
The amount of the palladium compound to be used is preferably 0.0001 mol or more and 0.5 mol or less, more preferably 0.001 mol or more and 0.1 mol or less, per 1 mol of the compound (C-VI). .

Examples of the phosphine compound include dppf, Xantphos, BINAP, XPhos, SPhos, MePhos and the like.
The amount of the phosphine compound to be used is preferably 0.001 mol or more and 0.5 mol or less, and more preferably 0.003 mol or more and 0.1 mol or less, per 1 mol of the compound (C-VI). .

  Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, t-butoxy sodium, t-butoxy potassium and the like.

  The amount of the basic compound to be used is preferably 1 mol or more and 5 mol or less, more preferably 1 mol or more and 3 mol or less, per 1 mol of compound (C-VI).

  The method for obtaining the compound (C-IV) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with alcohol (for example, methanol etc.), and the precipitated crystals can be collected by filtration. The reaction mixture is preferably added to the alcohol. The temperature at which the reaction mixture is added is preferably −100 ° C. or higher and 50 ° C. or lower, more preferably −80 ° C. or higher and 0 ° C. or lower. Thereafter, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystal collected by filtration is preferably washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  As the alkali metal salt of the anion represented by the formula (4), a commercially available one may be used. For example, Japanese Patent No. 4097704, Japanese Patent No. 4341251 and Journal of The Electrochemical Society, Vol. 148 Phase 1, 2001. Can be produced by the method described in 1. above.

  As the alkali metal salt of the anion represented by the formula (6), the formula (7), the formula (8) or the formula (9), a commercially available one may be used, or International Application No. 2008/077562 and JP2010- It can be produced by the method described in Japanese Patent No. 280586.

  An alkali metal salt of an anion containing at least one element selected from the group consisting of tungsten, silicon, and phosphorus and oxygen as essential elements can be produced by a known and conventional method, but a commercially available product is used as it is. May be. Examples of such compounds include corresponding heteropoly acid salts, isopoly acid salts, silicates, and phosphates. As these various salts, monovalent metal salts such as sodium, lithium, and potassium are preferable because they are excellent in water solubility and can be easily synthesized and worked up.

  The colored curable resin composition of the present invention comprises, as a colorant (A), a compound (A1) composed of an ion represented by the formula (A-VI) and a counter ion, a resin (B), and a polymerizable compound (C ), A polymerization initiator (D) and a solvent (E).

  The colored curable resin composition of the present invention may further contain at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye as a colorant (A).

As a preferred composition of the colored curable resin composition of the present invention,
Colored curable resin composition 0 containing compound (A1), resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E);
A compound (A1), at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye, a resin (B), a polymerizable compound (C), and a polymerization initiator (D), Colored curable resin composition 1 containing a solvent (E);
Colored curable resin composition comprising compound (A1), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and colorless metal complex (F) 2;
Etc.

  The colored curable resin composition 1 includes, as the colorant (A), at least one dye (A2) selected from the group consisting of the compound (A1), an anthraquinone dye, and a tetraazaporphyrin dye (hereinafter referred to as the dye (A2)). And so on.)

As the anthraquinone dye, a known substance may be used. As an anthraquinone dye, for example,
C. I. Solvent Yellow 117 (hereinafter, CI Solvent Yellow is omitted, and only the number is described), 163, 167, 189,
C. I. Solvent orange 77, 86,
C. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Solvent Green 3, 28, 29, 32, 33,
C. I. Acid Red 80,
C. I. Acid Green 25, 27, 28, 41,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112
C. I. Disperse Yellow 51,
C. I. Disperse violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct Blue 40,
C. I. Modern Red 3, 11,
C. I. Modern Blue 8
Etc. The anthraquinone dye is preferably soluble in an organic solvent, and more preferably a blue, violet or red anthraquinone dye.

  Among these, as the anthraquinone dye, a compound represented by the formula (1b) (hereinafter sometimes referred to as “compound (1b)”) is preferable.

[In Formula (1b), R ⁹¹ and R ⁹² may each independently have a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a substituent. Good alicyclic hydrocarbon group having 3 to 10 carbon atoms, or
Formula (1b ′)

(In the formula (1b ′), R ⁹³ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, —SO ₃ H, —CO ₂ H, —CO ₂ R ⁹⁴ , —NHCOR ⁹⁴ , —SO ₃ R ⁹⁴ or It represents a -SO ₂ NR ⁹⁴ R ^95.
R ⁹⁴ represents an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxy group or an amino group, or a carbon number which may be substituted with a halogen atom, a hydroxy group or an amino group. 3-10 alicyclic hydrocarbon groups are represented.
R ⁹⁵ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.
r represents an integer of 0 to 5. When r is 2 or more, the plurality of R ⁹³ may be the same or different.
X ⁹¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. )
Represents a group represented by ]

When the compound (1b) has —SO ₃ H and / or —CO ₂ H, these may form a salt (for example, Na salt or K salt).

In R ⁹¹ and R ⁹² , examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Examples include decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and the like.
Examples of the substituent that these aliphatic hydrocarbon groups may have include a hydroxy group and a halogen atom.

Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ⁹¹ , R ⁹² and R ⁹⁴ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group. Is mentioned.
Examples of the substituent that these alicyclic hydrocarbon groups may have include a hydroxy group and a halogen atom.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁹³ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert- A butyl group, an isopentyl group, a neopentyl group, etc. are mentioned.

Examples of the aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ⁹⁴ and R ⁹⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and the like.

Examples of —CO ₂ R ⁹⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of —NHCOR ⁹⁴ include an N-acetylamino group, an N-propanoylamino group, an N-butyrylamino group, an N-isobutyrylamino group, and an N-pivaloylamino group.

Examples of —SO ₃ R ⁹⁴ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

-SO ₂ NR ⁹⁴ R ⁹⁵ includes N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- ( 1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2 -Methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group N-cyclohexylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5- N-1-substituted sulfamoyl groups such as (dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N- (5-aminopentyl) sulfamoyl group; N, N-dimethyl Sulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propiyl Methylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methyl) N, N-2 substituted sulfamoyl groups such as propyl) sulfamoyl group and N, N-heptylmethylsulfamoyl group.

In X ^91, as the alkanediyl group having 1 to 6 carbon atoms, a methylene group, an ethylene group, propane-1,3-diyl, propane-1,2-diyl group, butane-1,4-diyl group, pentane -1,5-diyl group, hexane-1,6-diyl group, ethane-1,1-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methyl Examples include a propane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like.

R ⁹³ is preferably an alkyl group having 1 to 5 carbon atoms that may have a hydroxyl group, —SO ₃ R ⁹⁴ , —SO ₂ NR ⁹⁴ R ^95, more preferably —SO ₂ NR ⁹⁴ R ⁹⁵ , and —SO _{2. 2} NHR ⁹⁴ is more preferred (wherein R ⁹⁴ and R ⁹⁵ are as defined above).

  Examples of compound (1b) include compounds represented by formula (3-1) to formula (3-11).

An anthraquinone dye is a compound represented by the formula (1b), wherein R ⁹¹ and R ⁹² are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group which may have a halogen atom, and a formula ( The compound which is group represented by 1b ') is preferable, and the compound represented by Formula (3-4) and Formula (3-11) is more preferable. When these anthraquinone dyes are used, a high-contrast coating film or pattern can be formed, and there is little generation of foreign matter, and a coating film or pattern with excellent light resistance can be formed.

  The tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in the molecule. Further, when the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.

  Among these, as the tetraazaporphyrin dye, a dye having a structure represented by the formula (1c) (hereinafter sometimes referred to as a compound (1c)) is preferable.

[In the formula (1c), R ^{71 to} R ⁷⁸ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted. An aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyloxy group, or a substituted or unsubstituted amino group, M represents two hydrogen atoms, two monovalent metal atoms, 2 A valent metal atom, a trivalent substituted metal atom, or a metal oxide atom is represented.

  In the formula (1c), the aryl group represents, for example, a carbocyclic aromatic group such as phenyl group or naphthyl group, for example, a heterocyclic aromatic group such as furyl group, thienyl group or pyridyl group, A carbocyclic aromatic group.

In the formula (1c), R ^{71 to} R ⁷⁸ are preferably each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, or 1 to 24 carbon atoms. Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms An oxy group and a substituted amino group having 1 to 30 carbon atoms.

R ^{71 to} R ⁷⁸ are more preferably each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, or a C 1 to 16 carbon atom. Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group having 6 to 24 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, substituted or unsubstituted aralkyloxy group having 7 to 24 carbon atoms Group, a substituted amino group having 1 to 16 carbon atoms.

R ^{71 to} R ⁷⁸ are more preferably each independently a hydrogen atom, a fluorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted group having 1 to 10 carbon atoms. Substituted alkoxy group, substituted or unsubstituted aryl group having 6 to 16 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 16 carbon atoms, substituted or unsubstituted aralkyloxy group having 7 to 16 carbon atoms, carbon It is a substituted amino group of formula 1-12.

Specific examples of R ^{71 to} R ⁷⁸ in formula (1c) are shown below.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

As an unsubstituted alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group Tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1-methyl Heptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n- Decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, -Tetradecyl group, n-pentadecyl group, 1-heptyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octylnonyl group, n-octadecyl group, 1-nonyldecyl group, 1-decylundecyl group, n-eicosyl group , N-docosyl group, n-tetracosyl group, 1-adamantyl group, cyclopentyl group, cyclohexyl group, norbornyl group, and the like, straight-chain, branched or cyclic alkyl groups consisting only of carbon atoms and hydrogen atoms.
Examples of the substituent in the alkyl group include an alkyloxy group having 1 to 16 carbon atoms, an alkyloxyalkyloxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, a halogen atom, a halogenoalkyloxy group, and an aryloxy group. .
Specific examples of the alkyl group having a substituent include a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, an n-hexyloxymethyl group, a (2-ethylbutyloxy) methyl group, an n-octyloxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2′-ethylhexyloxy) Ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexane Siloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (N-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- (2′-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2′-ethylhexyl) Oxy) propyl group, 3- (n-decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxybutyl group, 4-n Hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group, 5-n-propoxypentyl Group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxy Heptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxidedecyl group, tetrahydrofurfuryl group, etc. An alkyl group having an alkyloxy group;
(2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) methyl group, (2-n-hexyloxyethoxy) methyl group, (3-methoxypropyloxy) methyl Group, (3-ethoxypropyloxy) methyl group, (3-n-butyloxypropyloxy) methyl group, (3-n-pentyloxypropyloxy) methyl group, (4-methoxybutyloxy) methyl group, (6 -Methoxyhexyloxy) methyl group, (10-ethoxydecyloxy) methyl group, 2- (2'-methoxyethoxy) ethyl group, 2- (2'-ethoxyethoxy) ethyl group, 2- (2'-n- Butoxyethoxy) ethyl group, 3- (2′-ethoxyethoxy) propyl group, 3- (2′-methoxypropyloxy) propyl group, 3- (2 ′ Isopropyloxy) propyl group, 3- (3'-methoxy) propyl group, 3- (such as 3'-ethoxy-propyloxy) propyl group, an alkyl group having alkyloxyalkyl group;
For example, benzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4′-methylbenzyloxy) ethyl group, 2- (2′-methylbenzyloxy) ethyl group, 2- ( 4′-fluorobenzyloxy) ethyl group, 2- (4′-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4′-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, An alkyl group having an aralkyloxy group, such as a 2- (benzyloxymethoxy) ethyl group and a 2- (4′-methylbenzyloxymethoxy) ethyl group;
Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyloxymethyl group Group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-methoxyphenyl) Oxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2- (2′-naphthyloxy) ) Ethyl group, 3-phenyloxypropyl group, 3- (2′-naphthyloxy) propyl group, 4-phenyloxy Sibutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-tert-butylphenyloxy) pentyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3′-chlorophenyloxy) decyl group, 2- (2′-phenyloxyethoxy) ethyl group, 3- (2′-phenyloxyethoxy) propyl group, 4- (2 ′ -An alkyl group having an aryloxy group, such as a phenyloxyethoxy) butyl group;
n-butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octyl Thioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group Alkylthio groups such as 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, 8-methylthiooctyl group, etc. Having an alkyl group;
Fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n-propyl 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 1,1-dihydro- Perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1, 1-dihydro-perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1-dihydro-perfluoro- -Tetradecyl group, 1,1-dihydro-perfluoro-n-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 2,2 -Bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group, 2,2,2-trichloro An alkyl group having a halogen atom such as an ethyl group;
Fluoromethyloxymethyl group, 3-fluoro-n-propyloxymethyl group, 6-fluoro-n-hexyloxymethyl group, trifluoromethyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1, 1-dihydro-perfluoro-n-propyloxymethyl group, 2-hydro-perfluoro-2-propyloxymethyl group, 1,1-dihydro-perfluoro-n-butyloxymethyl group, 1,1-dihydro- Perfluoro-n-pentyloxymethyl group, 1,1-dihydro-perfluoro-n-hexyloxymethyl group, 1,1-dihydro-perfluoro-n-octyloxymethyl group, 1,1-dihydro-perfluoro -N-decyloxymethyl group, 1,1-dihydro-perfluoro-n-tetradecyloxime Group, 2,2-bis (trifluoromethyl) propyloxymethyl group, 3-chloro-n-propyloxymethyl group, 2- (8-fluoro-n-octyloxy) ethyl group, 2- (1,1 -Dihydro-perfluoroethyloxy) ethyl group, 2- (1,1,3-trihydro-perfluoro-n-propyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n-pentyloxy) Ethyl group, 2- (6-fluoro-n-hexyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n-octyloxy) ethyl group, 3- (4-fluorocyclohexyloxy) propyl group, 3- (1,1-dihydro-perfluoroethyloxy) propyl group, 3- (1,1-dihydro-perfluoro-n-dodecyloxy) propyl group, 4- ( -Fluoro-n-hexyloxy) butyl group, 4- (1,1-dihydro-perfluoroethyloxy) butyl group, 6- (2-chloroethyloxy) hexyl group, 6- (1,1-dihydro-perfluoro An alkyl group having a halogenoalkyloxy group, such as an ethyloxy) hexyl group;
Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-ethylphenyloxymethyl group, 4-n-propylphenyloxymethyl group, 4-n -Butylphenyloxymethyl group, 4-tert-butylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-octylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4-methoxy Phenyloxymethyl group, 4-ethoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-n-pentyloxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 3-fluorophenyloxymethyl group, 2- Fluorophenyloxymethyl group, 3, -Difluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-chlorophenyloxymethyl group, 4-phenylphenyloxymethyl group, 1-naphthyloxymethyl group, 2-naphthyloxymethyl group, 2-furyloxymethyl group, 1-phenyloxyethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-n-hexylphenyl) Oxy) ethyl group, 2- (4′-methoxyphenyloxy) ethyl group, 2- (4′-n-butoxyphenyloxy) ethyl group, 2- (4′-fluorophenyloxy) ethyl group, 2- (4 '-Chlorophenyloxy) ethyl group, 2- (4'-bromophenyloxy) ethyl group, 2- (1'-naphthyloxy) Group, 2- (2′-naphthyloxy) ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3- (4′-methylphenyloxy) propyl group, 3- (2′-naphthyloxy) ) Propyl group, 4-phenyloxybutyl group, 4- (2′-ethylphenyloxy) butyl group, 4-phenyloxypentyl group, 5-phenyloxypentyl group, 5- (4′-tert-butylphenyloxy) Pentyl group, 6-phenyloxyhexyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3′-methylphenyloxy) decyl group, etc. And an alkyl group having an aryloxy group.

  Examples of the unsubstituted alkoxy group include alkoxy groups derived from specific examples of the alkyl group. Examples of the substituent in the substituted alkoxy group include the same substituents as the alkyl groups listed above.

As the unsubstituted aryl group, phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group, and 8-fluoranthenyl group.
In the substituted aryl group, examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, an aryl group, and a halogen atom.
Specific examples of the aryl group having a substituent include 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4- (4′-tert-butyl). (Cyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, alkyl group such as 2,4-dimethylphenyl group An aryl group;
4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2- Alkoxy groups such as isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group And an aryl group having an aryloxy group;
4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4- (2′-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1-phenyl- An aryl group having an aryl group such as a 2-naphthyl group and a 7-phenyl-1-pyrenyl group;
4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2 An aryl group having a halogen atom such as a methyl-3-chlorophenyl group, a 2-methoxy-4-fluorophenyl group, or a 2-fluoro-4-methoxyphenyl group;
Furthermore, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl group 4-ethylthiophenyl group, 4-cyanophenyl group, 3-cyanophenyl group and the like.

  Examples of the unsubstituted aryloxy group include aryloxy groups derived from specific examples of the aryl group. Examples of the substituent in the substituted aryl group include the same substituents as the above-mentioned aryl.

As the substituted or unsubstituted aralkyloxy group, benzyloxy group, α-methylbenzyloxy group, phenethyloxy group, α-methylphenethyloxy group, α, α-dimethylbenzyloxy group, α, α-dimethylphenethyloxy group , An aralkyloxy group having an unsubstituted or alkyl group, such as 4-methylphenethyloxy group, 4-methylbenzyloxy group, 4-isopropylbenzyloxy group;
Aralkyloxy group having aryl group or aralkyl group such as 4-benzylbenzyloxy group, 4-phenethylbenzyloxy group, 4-phenylbenzyloxy group; 4-methoxybenzyloxy group, 4-n-tetradecyloxybenzyloxy group 4-n-heptadecyloxybenzyloxy group, 3,4-dimethoxybenzyloxy group, 4-methoxymethylbenzyloxy group, 4-vinyloxymethylbenzyloxy group, 4-benzyloxybenzyloxy group, 4-phenethyloxy An aralkyloxy group having a substituted oxy group such as a benzyloxy group;
Aralkyloxy groups having a hydroxyl group such as 4-hydroxybenzyloxy group, 4-hydroxy-3-methoxybenzyloxy group; 4-fluorobenzyloxy group, 3-chlorobenzyloxy group, 3,4-dichlorobenzyloxy group, etc. An aralkyloxy group having a halogen atom;
Examples include 2-furfuryloxy group, diphenylmethyloxy group, 1-naphthylmethyloxy group, 2-naphthylmethyloxy group and the like.

Specific examples of the amino group having a substituent include N-methylamino group, N-ethylamino group, Nn-butylamino group, N-cyclohexylamino group, Nn-octylamino group, and Nn-. An amino group having an alkyl group such as a decylamino group;
N-benzylamino group, N-phenylamino group, N- (3-methylphenyl) amino group, N- (4-methylphenyl) amino group, N- (4-n-butylphenyl) amino group, N- ( 4-methoxyphenyl) amino group, N- (3-fluorophenyl) amino group, N- (4-chlorophenyl) amino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group, etc. An amino group having an aralkyl group or an aryl group;
N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-butylamino group, N, N-di-n-hexylamino group, N, N-di-n-octylamino group N, N-di-n-decylamino group, N, N-di-n-dodecylamino group, N-methyl-N-ethylamino group, N-ethyl-Nn-butylamino group, N-methyl- An amino group having two alkyl or aralkyl groups as substituents, such as an N-phenylamino group, an N-ethyl-N-phenylamino group, and an Nn-butyl-N-phenylamino group;
N, N-diphenylamino group, N, N-di (3-methylphenyl) amino group, N, N-di (4-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino group, N, N-di (4-tert-butylphenyl) amino group, N, N-di (4-n-hexylphenyl) amino group, N, N-di (4-methoxyphenyl) amino group, N, N- Di (4-ethoxyphenyl) amino group, N, N-di (4-n-butoxyphenyl) amino group, N, N-di (4-n-hexyloxyphenyl) amino group, N, N-di (1 -Naphthyl) amino group, N, N-di (2-naphthyl) amino group, N-phenyl-N- (3-methylphenyl) amino group, N-phenyl-N- (4-methylphenyl) amino group, N -Phenyl-N- (4-octylphenyl) amino group N-phenyl-N- (4-methoxyphenyl) amino group, N-phenyl-N- (4-ethoxyphenyl) amino group, N-phenyl-N- (4-n-hexyloxyphenyl) amino group, N- Phenyl-N- (4-fluorophenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N- (3- And an amino group having two aryl groups as substituents such as a phenylphenyl) amino group and an N-phenyl-N- (4-phenylphenyl) amino group.

In the formula (1c), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, or a metal oxide atom, more preferably two A hydrogen atom, a divalent metal atom, or a metal oxide atom, and more preferably a divalent metal atom or a metal oxide atom.
Examples of the monovalent metal atom represented by M include Na, K, and Li.
Examples of the divalent metal atom represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, and Sn. Etc.
Examples of the trivalent substituted metal atom represented by M include Al—Cl, Ga—Br, Ga—I, In—Cl, Al—C ₆ H ₅ , In—C ₆ H ₅ , Mn (OH), Mn [OSi (CH ₃ ) ₃ ], Fe—Cl, and the like can be given.
Examples of the metal oxide atom represented by M include VO, MnO, TiO and the like.
In the formula (1c), M is more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO and TiO, still more preferably Cu, Ni, Pd and VO. Cu, Pd and VO are preferable.

  Specific examples of the compound (1c) include compounds represented by the formula (2-1) to the formula (2-38).

  As the tetraazaporphyrin dye, a compound represented by the formula (2-29) is preferable. A composition containing this tetraazaporphyrin dye can form a high-contrast coating film or pattern, and generates less foreign matter.

The content of the compound (A1) is preferably 0.5% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 80% by mass or less, with respect to the total amount of the colorant (A).
The content of the dye (A2) is preferably 1 to 100 parts by mass, and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the compound (A1).

<Colorless metal complex (F)>
The colored curable resin composition 2 may contain a colorless metal complex (F). Moreover, the colored curable resin composition 1 of this invention may contain the colorless metal complex (F).

  Examples of the colorless metal complex (F) include a zinc complex represented by the formula (10).

[In Formula (10), R ^{81 to} R ⁸⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group]

Examples of the alkyl group for R ^{81 to} R ⁸⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Specific examples of the zinc complex represented by the formula (10) include complexes having the substituents shown in the following table. Among these, zinc complex (10) -18 is preferable in terms of improving heat resistance.

In Table, - ^t C ₄ H ₉ represents a tert- butyl group.

  The content of the colorless metal complex is more preferably from 0.1 parts by weight to 40 parts by weight, more preferably from 0.1 parts by weight to 30 parts by weight, based on 100 parts by weight of the colorant (A). More preferably, it is 5 parts by mass or more and 15 parts by mass or less.

  The colored curable resin composition 0 includes the compound (A1) as a colorant (A), and further includes a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). May be included.

  The colored curable resin composition 1 includes a compound (A1) and at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye as a colorant (A), and further a resin (B ), A polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

  The colored curable resin composition 2 includes the compound (A1) as a colorant (A), and further includes a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). And a colorless metal complex (F).

These colored curable resin compositions preferably further contain a polymerization initiation assistant (D1), a leveling agent (H), and an antioxidant (J).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
The colored curable resin composition of the present invention includes, in addition to the compound (A1) of the present invention and the dye (A2), as a colorant (A), for color matching, that is, to adjust spectral characteristics. Other dyes, pigments (P), or mixtures thereof may be included.

  Examples of the dye include oil-soluble dyes, acid dyes, basic dyes, and the like, and any of direct dyes and mordant dyes may be used. The acid dye may be an amine salt or a sulfonamide derivative.

Examples of the dye include compounds classified as dyes by Color Index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (color dyeing company). Examples thereof include dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferably used.
More specifically,
C. I. Solvent Red 45, 49, 125, 130, 218;
C. I. Solvent Blue 4, 5, 37, 67, 70;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 422, 426;
C. I. Acid Violet 6, 7, 9, 30, 102;
C. I. Acid Blue 18, 29, 42, 59, 60, 70, 72, 74, 82, 92, 102, 113, 117, 120, 126, 131, 142, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 242, 243, 256, 259, 267, 285, 296, 315, 335; I. Acid dyes,
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 182, 184, 204, 207, 211, 213, 218, 221, 222, 232, 233, 243, 246, 250;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 212, 213, 214 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247 248,249,250,251,252,256,257,259,260,274,275,293;
C. I. Basic Red 1, 10;
C. I. Basic Blue 3, 9, 24, 25, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. et al. I. Basic dyes,
C. I. Reactive Red 36; I. Reactive dyes,
C. I. Modern Red 1, 9, 12, 14, 17, 18, 19, 22, 23, 24, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43, 46, 48, 53 56, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 9, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 77, 83 ;
C. et al. I. Modern dyes,
Is mentioned.
Of these, blue dyes, violet dyes and red dyes are preferred.
These dyes may be used alone or in combination of two or more.

Moreover, in the classification | category by a chemical structure, a xanthene dye is preferable.
A known substance can be used as the xanthene dye. As the xanthene dye, a compound represented by the formula (1) (hereinafter, the compound may be referred to as “compound (1)”) is preferable.

[In Formula (1), R < ¹ > and R < ² > represents the phenyl group which may have a substituent each independently.
R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ¹ and R ³ together with the nitrogen atom to which they are attached may represent a ring containing a nitrogen atom, or R ² and R ⁴ together with the nitrogen atom to which they are attached A ring containing may be represented.
R ⁵ _{is, -OH, -SO 3 H, -SO} 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ Represents.
R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or may represent a 3- to 10-membered nitrogen-containing heterocycle together with a nitrogen atom.
R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

In R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ of R ⁵ , examples of the monovalent saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, C1-C20 linear alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, C3-C20 branched alkyl group such as neopentyl group and 2-ethylhexyl group; C3-C20 such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group Of the alicyclic saturated hydrocarbon group.

Therefore, in R ⁵ ,
Examples of —CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.
—SO ₂ NR ⁹ R ¹⁰ includes a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl , N-(1,3-dimethylbutyl) sulfamoyl group, N
-(3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl , N-substitution such as N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group Sulfamoyl group; N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropyl Methylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N Bis (1-methylpropyl) sulfamoyl group, N, such as N- heptyl methylsulfamoyl group N, etc. N-2-substituted sulfamoyl group.

In R ⁸ , the hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group is —O—, —CO— or It may be replaced by —NR ¹¹ —.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the saturated hydrocarbon group substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

R ⁹ and R ¹⁰ may represent a 3- to 10-membered nitrogen-containing heterocycle together with a nitrogen atom. Examples of the heterocyclic ring include the following.

Examples of the aralkyl group having 7 to 10 carbon atoms representing R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
As the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable.

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent include a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 8, -SR 8, -SO 2 R ⁸ , —SO ₃ R ⁸ and —SO ₂ NR ⁹ R ¹⁰ may be mentioned. Among these substituents, —R ⁸ is preferable, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable. -SO ₃ in this case ^- Z ^{+ _{The, -SO 3 - + N (R}} 11) 4 are preferred.
—R ⁸ , —CO ₂ R ⁸ , —SO ₃ R ⁸ , and —SO ₂ NR ⁹ R ¹⁰ are the same as described above.
Examples of —OR ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group.
Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

In R ³ and R ⁴ , the monovalent saturated hydrocarbon group includes carbon such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. A linear alkyl group having 1 to 10 carbon atoms; a branched alkyl group having 3 to 10 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group An alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group;
In R ³ and R ⁴ , the hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group is —O—, — CO— or —NR ¹¹ — may be substituted.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the saturated hydrocarbon group substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

As R ³ and R ⁴ , an unsubstituted monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are preferable. Further preferred.

R ¹ and R ³ may form a ring together with the nitrogen atom to which they are bonded, and R ² and R ⁴ may form a ring together with the nitrogen atom to which they are bonded. Good. Examples of the ring containing a nitrogen atom include the following.

Examples of the alkyl group having 1 to 6 carbon atoms representing R ⁶ and R ⁷ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, and tert-butyl. Group, isopentyl group, neopentyl group and the like.

The _{^{R 5, -SO 3 H, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are preferred.
R ⁶ and R ⁷ are preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.
m is preferably an integer of 0 to 2, and more preferably 0 or 1.

  As the compound (1), a compound represented by the formula (2) is preferable.

Wherein ^{(2), R 21, R} 22, R 23 and R ²⁴ each independently represents an alkyl group having 1 to 4 carbon atoms.
p and q represent the integer of 0-5 each independently. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different. ]
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ²¹ , R ²² , R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert group. -A butyl group etc. are mentioned.
R ²¹ and R ²² are preferably, independently of each other, a methyl group and an ethyl group. R ²³ and R ²⁴ are more preferably a methyl group.

  As the compound (1), a compound represented by the formula (3) is preferable.

[In formula (3), R ³¹ and R ³² each independently represents an alkyl group having 1 to 4 carbon atoms.
R ³³ and R ³⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³¹ , R ³² , R ³³ and R ³⁴ are the same as those described above.
R ³¹ and R ³² are preferably each independently a methyl group or an ethyl group. R ³³ and R ³⁴ are preferably each independently a hydrogen atom or a methyl group.

  Examples of compound (1) include compounds represented by formula (1-1) to formula (1-7), respectively. Especially, the compound represented by Formula (1-1) is preferable at the point which is excellent in the solubility to an organic solvent.

The pigment (P) is not particularly limited, and known pigments can be used. Examples of the pigment (P) include pigments classified as pigments by the Color Index (published by The Society of Dyers and Colorists).
As the pigment (P),
C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  The pigment (P) is preferably a phthalocyanine pigment or a dioxazine pigment, more preferably C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6 and Pigment Violet 23, and more preferably C.I. I. At least one selected from the group consisting of CI Pigment Blue 15: 6 and CI Pigment Violet 23. By including the pigment, it is easy to optimize the transmission spectrum, and the heat resistance, light resistance and chemical resistance of the color filter are improved.

The colored curable resin composition of the present invention preferably contains a blue pigment.
If necessary, the pigment is atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, etc., sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. The pigments preferably have a uniform particle size.

As the pigment, a pigment dispersion in which the pigment is uniformly dispersed in a solvent may be used.
The pigment dispersion can be obtained by mixing a pigment and a pigment dispersant in a solvent.
In the above mixing, when two or more kinds of pigments are mixed, they may be mixed alone or a plurality of kinds may be mixed.
The pigment dispersant may be any of cationic, anionic, nonionic, and amphoteric dispersants, and examples thereof include polyester dispersants, polyamine pigments, acrylic pigment dispersants, and the like.
These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.

It does not specifically limit as said solvent, The solvent similar to the solvent in the colored curable resin composition of this invention is mentioned.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in which the pigment is uniformly dispersed in the solvent tends to be obtained.

The content of the colorant (A) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and further preferably 5% by mass with respect to the total amount of the solid content. % Or more and 50% by mass or less. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.
In this specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as “resin (B)”) is derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. A copolymer containing structural units.

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

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

(B) includes a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. It is done.
(B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

(B) includes a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a monomer having an oxetanyl group and an ethylenically unsaturated bond. (B2) (hereinafter sometimes referred to as “(b2)”), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), and the like. .
As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).
As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.
Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (II), and Formula (III) The compound etc. which are represented by these are mentioned.

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

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

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

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

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

  The compound represented by the formula (II) and the compound represented by the formula (III) may be used alone or in combination with the compound represented by the formula (II) and the compound represented by the formula (III). May be. When these are used in combination, the content ratio of the compound represented by the formula (II) and the compound represented by the formula (III) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

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

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

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

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

In the resin [K1], the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40-98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
It is more preferable that
In the resin [K1], if the ratio of the structural units is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter are improved. There is a tendency to excel.
Resin [K1] is described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document. It can be produced with reference to the cited references.

As a specific method for producing the resin [K1], a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and oxygen is replaced with nitrogen, thereby removing oxygen. And heating and keeping warm while stirring.
In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. Examples of the polymerization initiator include azo compounds (such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide). Any solvent may be used as long as it dissolves each monomer. Examples of the solvent (E) for the colored curable resin composition of the present invention include the solvents described later.
In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction is used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, There is a tendency to be excellent in heat resistance and mechanical strength.
Resin [K2] can be produced in the same manner as the method described for producing resin [K1] except that a predetermined amount of (c) is used.

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

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same as that described for the resin [K3].
Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making it within this range, the storage stability of the colored curable resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern are improved. Tend. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

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

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

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

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Resin such as decyl (meth) acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- ( A) Resin such as acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer , Benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer, etc. resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) Resin with acrylate added, Resin with glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, Tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / Glycidyl (meth) acrylate on (meth) acrylic acid copolymer Resin [K4] such as added resin; resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / styrene / Resin [K5] such as a resin obtained by reacting a copolymer of glycidyl (meth) acrylate with (meth) acrylic acid; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) acrylic acid And resin [K6] such as a resin obtained by further reacting tetrahydrophthalic anhydride with the resin reacted with.

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

  The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

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

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

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. And the above-mentioned (a), (b) and (c) are mentioned.
Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meta). ) Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.
Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.
The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 15 to 55% by mass with respect to the total amount of the solid content. is there.
The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is on a mass basis, preferably 20:80 to 80:20, more preferably 35. : 65-80: 20.
When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.
The O-acyloxime compound is a compound having a structure represented by the formula (d1). Hereinafter, * represents a bond.

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

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

Examples of the compound having the structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) ) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, and the like. It is done. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy ) Phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d2).

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

[In the formula (d5), R ^{13 to} R ¹⁸ represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable.
Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, Preferably it is a methoxy group.
Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) Biimidazole (for example , Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), an imidazole compound in which the phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group (for example, JP, 7-10913, A) etc. are mentioned. Among these, compounds represented by the following formula and mixtures thereof are preferable.

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) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2- Methylphenyl) Sulfonyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

  These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

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

  The content of the polymerization initiator (D) is preferably 0.01 to 40 parts by mass, more preferably 0.05 with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is -35 mass parts, More preferably, it is 0.1-32 mass parts, More preferably, it is 1-30 mass parts.

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.
Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

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

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.
As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.
Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.
Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.
Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.
Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.
Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable, propylene glycol monomethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone , Propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl Chromatography ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N- methylpyrrolidone is more preferred.

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

<Leveling agent (H)>
Examples of the leveling agent (H) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) .
Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).
Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.
When the leveling agent (H) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002%, based on the total amount of the colored curable resin composition. It is not less than 0.1% by mass and more preferably not more than 0.005% by mass and not more than 0.07% by mass. When the content of the leveling agent (H) is in the above range, the flatness of the color filter can be improved.

<Antioxidant (J)>
From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use an antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.
Examples of the phenolic antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox. 1076 (Irganox 1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corp.), Irganox 1330 (Irganox 1330: 3, 3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Corp.), Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Corporation), Irganox 3790 (Irganox 3790: 1,3,5-tris ((4-t -Butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by BASF)), Irganox 1035 ( Irganox 1035: thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corp.), Irganox 1135 (Irganox 1135: benzenepropanoic acid, 3,5- Bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Corporation), Irganox 15 0L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF Corp.), Irganox 3125 (Irganox 3125, manufactured by BASF Corp.), Irganox 565 (Irganox 565: 2, 4-bis (n-octylthio) -6- (4-hydroxy 3 ′, 5′-di-t-butylanilino) -1,3,5-triazine, manufactured by BASF Corporation), ADK STAB AO-80 (ADK STAB AO) -80: 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10- Tetraoxaspiro (5,5) undecane, manufactured by ADEKA Co., Ltd.), Sumilizer BHT, Sumitomo Chemical Co., Ltd. ), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilyzer GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, manufactured by Cytec Co., Ltd.) and vitamin E (Manufactured by Eisai Co., Ltd.).
Examples of the phosphorus antioxidant include Irgafos 168 (Irgafos 168: Tris (2,4-di-t-butylphenyl) phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: Tris [2-[[ 2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (manufactured by BASF Corporation), Irgaphos 38 (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corp.), ADK STAB 329K (manufactured by ADEKA Corp.), ADK STAB PEP36 (Manufactured by ADEKA), ADK STAB PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (Clari Antton), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE) and Sumilizer GP (Sumilizer GP: 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] dioxaphosphine (Manufactured by Sumitomo Chemical Co., Ltd.).
Examples of the sulfur-based antioxidant include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkyl mercaptopropionic acids of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. An ester compound etc. are mentioned.

<Other ingredients>
The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and the like, if necessary. .

<Method for producing colored curable resin composition>
The colored curable resin composition 0 of the present invention is used as necessary (compound (A1), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E)), and as necessary. It can be prepared by mixing the leveling agent (H), the polymerization initiation assistant (D1), the antioxidant (J), and other components.
The colored curable resin composition 1 of the present invention comprises a compound (A1), a dye (A2), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a necessity. It can be prepared by mixing the leveling agent (H), the polymerization initiation assistant (D1), the antioxidant (J), and other components used accordingly.
The colored curable resin composition 2 of the present invention comprises a compound (A1), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a colorless metal complex (F), and a solvent (E), In addition, it can be prepared by mixing a leveling agent (H), a polymerization initiation auxiliary agent (D1), an antioxidant (J), and other components used as necessary.

The pigment in the case of containing the pigment (P) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The colorant (A) such as the compound (A1) or the dye (A2) is preferably prepared in advance by dissolving in part or all of the solvent (E). The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the purpose and application, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 0.5 to. 6 μm.

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

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

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.
A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.
Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

  In the following, the structure of the compound was confirmed by NMR (Agilent 400-MR), mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type), UV-VIS (JASCO V-650). .

Synthesis example 1
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 32.2 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, 31.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 49.9 parts of a compound represented by the formula (BI-2). Yield 51%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 0.13 part of tris (dibenzylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.27 part of XPhos (manufactured by Aldrich), t-butoxy sodium (Tokyo Chemical Industries 20.2 parts, 4,4'-dichlorobenzophenone (Tokyo Chemical Industry Co., Ltd.) 24.0 parts, 2,6-xylidine (Tokyo Chemical Industry Co., Ltd.) 23.2 parts, and toluene (Nacalai Tesque) ) After charging 123.3 parts, the reaction solution was prepared by stirring at room temperature for 30 minutes. The reaction solution was then heated to 80 ° C. and stirred for 2 hours. The reaction solution was ice-cooled, and the precipitated solid was filtered off to obtain a yellow solid 1. After adding 123.9 parts of toluene to the filtrate to adjust the organic layer, the operation of separating and washing the organic layer with 123.9 parts of tap water was repeated three times. The washed organic layer was dehydrated with magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a yellow solid 2. The obtained yellow solid 1 and yellow solid 2 were purified by column chromatography, respectively. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 37.2 parts of a compound represented by the formula (C-IV-2) (yield 93%).

Identification of compound represented by formula (C-IV-2) ( ¹ H NMR; 400 MHz; δ value (ppm, TMS standard); DMSO); 2.14 (12H, s), 6.42 (4H, m ), 7.08-7.15 (6H, m), 7.52 (4H, br.d, J = 7.1 Hz), 8.05 (2H, br.s)
(Mass spectrometry) ionization mode = ESI +: m / z = 421.5 [M + H] ⁺
Exact Mass: 420.2

  The following reaction was performed in a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (C-IV-2) and 74.7 parts of N, N-dimethylformamide were added to a flask equipped with a condenser and a stirrer, and the mixed solution was ice-cooled. . 8.0 parts of t-butoxypotassium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, followed by stirring for 1 hour under ice cooling. 11.1 parts of ethyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise little by little and stirred at room temperature for 2 hours. After adding 300 parts of tap water and 300 parts of ethyl acetate to the reaction solution, a liquid separation operation was performed to obtain an organic layer. The obtained organic layer was dehydrated with magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a yellow solid. The resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.2 parts of the compound represented by the formula (C-I-2) (yield 81%).

Identification of compound represented by formula (C-I-2) (mass spectrometry) ionization mode = ESI +: m / z = 477.5 [M + H] ⁺
Exact Mass: 476.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 6.7 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-2) and 50. After adding 0 part, 25.5 parts of phosphorus oxychloride was then added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 16.9 parts of a compound represented by the formula (A-II-2) (yield 100%).

Identification of compound represented by formula (A-II-2) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); −109.0 (1F, br.s)

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-2), 4.6 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100.0 parts of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Further, the obtained blue-green solid was purified by column chromatography. The purified blue-green solid was dried at 60 ° C. under reduced pressure to obtain 6.3 parts of a compound represented by the formula (A-I-2) (yield 48%).

Identification of compound represented by formula (A-I-2) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); −74.7 (6F, s), −109.0 (1F, br.s)
(UV-VIS)
0.10 g of the compound represented by formula (A-I-2) was dissolved in chloroform to a volume of 100 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 250 cm ³ (concentration: 0.008 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 0.7 (arbitrary unit) at λmax = 618 nm.

Synthesis example 2
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) (trade name “E-DCPA”, manufactured by Daicel Corporation) 171 parts propylene glycol monomethyl ether acetate 40 parts The solution dissolved in was dropped over about 5 hours using a dropping pump. On the other hand, a solution obtained by dissolving 26 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in the flask over another 5 hours using another dropping pump. It was dripped. After completion of the dropping of the polymerization initiator, the temperature is maintained at the same temperature for about 3 hours, and then cooled to room temperature, and a copolymer having a solid content of 43.5% (hereinafter referred to as “resin (B-1 ) ") Was obtained. The weight average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH / g.

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

Synthesis example 3
A 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer was flowed with an appropriate amount of nitrogen to be replaced with a nitrogen atmosphere. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.02,6] dec-8 or / and 9-yl acrylate (trade name “E-DCPA”, manufactured by Daicel Corporation) ) A mixed solution of 25 parts, cyclohexyl maleimide 137 parts, 2-hydroxyethyl methacrylate 50 parts, and propylene glycol monomethyl ether acetate 338 parts was added dropwise over 5 hours. On the other hand, a mixed solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature, and a copolymer having a B-type viscosity (23 ° C.) of 23 mPas, a solid content of 25.6% by weight, and a solution acid value of 28 mg-KOH / g The copolymer was referred to as “resin (B-2)”). The produced resin (B-2) had a weight average molecular weight Mw of 8,000 and a molecular weight distribution of 2.1.

Synthesis example 4
The following reaction was performed in a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (C-IV-2) and 74.7 parts of N, N-dimethylformamide were added to a flask equipped with a condenser and a stirrer, and the mixed solution was ice-cooled. . 8.0 parts of t-butoxypotassium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, followed by stirring for 1 hour under ice cooling. Normal butyl iodide (Tokyo Kasei Kogyo Co., Ltd.) (13.1 parts) was added dropwise little by little and stirred at room temperature for 2 hours. After adding 300 parts of tap water and 300 parts of ethyl acetate to the reaction solution, a liquid separation operation was performed to obtain an organic layer. The obtained organic layer was dehydrated with magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a yellow solid. The resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 8.3 parts of a compound represented by the formula (C-I-3) (yield 66%).

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 6.0 parts of the compound represented by the formula (B-I-2), 10.0 parts of the compound represented by the formula (C-I-3) and 50. After adding 0 part, 22.8 parts of phosphorus oxychloride was then added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Furthermore, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 16.2 parts of a compound represented by the formula (A-II-3) (yield 100%).

Identification of compound represented by formula (A-II-3) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); −74.7 (6F, s), −109.1 (1F, br.s)

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-3), 4.3 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100.0 parts of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Further, the obtained blue-green solid was purified by column chromatography. The purified blue-green solid was dried at 60 ° C. under reduced pressure to obtain 9.5 parts of a compound represented by the formula (AI-3) (yield 74%).

Identification of compound represented by formula (AI-3) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); −74.8 (6F, s), −109.1 (1F, br.s)
(UV-VIS)
0.10 g of the compound represented by the formula (AI-3) was dissolved in chloroform to a volume of 100 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 250 cm ³ (concentration: 0.008 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 0.8 (arbitrary unit) at λmax = 621 nm.

Reference synthesis example 1
The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 0.13 part of tris (dibenzylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.27 part of XPhos (manufactured by Aldrich), t-butoxy sodium (Tokyo Chemical Industry Co., Ltd.) 20.2 parts, 4,4'-dichlorobenzophenone (Tokyo Chemical Industry Co., Ltd.) 24.0 parts, o-toluidine (Tokyo Chemical Industry Co., Ltd.) 20.5 parts, and toluene (Nacalai Tesque Co., Ltd.) 123 After adding 3 parts, the reaction solution was prepared by stirring at room temperature for 30 minutes. The reaction solution was then heated to 80 ° C. and stirred for 2 hours. The reaction solution was ice-cooled, and the precipitated solid was filtered off to obtain a yellow solid 1. After adding 123.9 parts of toluene to the filtrate to adjust the organic layer, the operation of separating and washing the organic layer with 123.9 parts of tap water was repeated three times. The washed organic layer was dehydrated with magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a yellow solid 2. The obtained yellow solid 1 and yellow solid 2 were purified by column chromatography, respectively. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 16.2 parts of a compound represented by the formula (C-IV-4) (43% yield).

Identification of compound represented by formula (C-IV-4) (mass spectrometry) ionization mode = ESI +: m / z = 393.5 [M + H] ⁺
Exact Mass: 392.2

  The following reaction was performed in a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (C-IV-4) and 80.1 parts of N, N-dimethylformamide were added to a flask equipped with a condenser and a stirrer, and the mixed solution was ice-cooled. . After adding 8.6 parts of t-butoxy potassium (manufactured by Tokyo Chemical Industry Co., Ltd.) gradually over 30 minutes under ice cooling, the mixture was stirred for 1 hour under ice cooling. 11.9 parts of ethyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise little by little and stirred at room temperature for 2 hours. After adding 300 parts of tap water and 300 parts of ethyl acetate to the reaction solution, a liquid separation operation was performed to obtain an organic layer. The obtained organic layer was dehydrated with magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a yellow solid. The resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 11.1 parts of a compound represented by the formula (C-I-4) (yield 97%).

Identification of compound represented by formula (CI-4) ( ¹ H NMR; 400 MHz; δ value (ppm, TMS standard); DMSO); 1.13 (6H, br.t, J = 7.0 Hz) 2.04 (6H, s), 3.64 (4H, m), 6.42 (4H, br.d, J = 9.0 Hz), 7.14 (2H, br.dd, J = 7. 4, 1.4 Hz), 7.27 (4H, m), 7.36 (2H, br.d, J = 7.2, 2.0 Hz), 7.50 (4H, br.d, J = 9) .0Hz)

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 7.1 parts of the compound represented by the formula (BI-2), 18.1 parts of the compound represented by the formula (CI-4), and 50. After adding 0 part, 10.7 parts of phosphorus oxychloride was then added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 17.4 parts of a compound represented by the formula (A-II-4) (yield 100%).

Identification of compound represented by formula (A-II-4) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); −109.0 (1F, br.s)

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-4), 4.8 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100.0 parts of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Further, the obtained blue-green solid was purified by column chromatography. The purified blue-green solid was dried at 60 ° C. under reduced pressure to obtain 3.0 parts of the compound represented by the formula (AI-4) (yield 23%).

Identification of compound represented by formula (AI-4) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); −74.7 (6F, s), −108.9 (1F, br.s)
(UV-VIS)
0.10 g of the compound represented by the formula (AI-4) was dissolved in chloroform to a volume of 100 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 250 cm ³ (concentration: 0.008 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 0.5 (arbitrary unit) at λmax = 619 nm.

Reference synthesis example 2
The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 0.13 part of tris (dibenzylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.27 part of XPhos (manufactured by Aldrich), t-butoxy sodium (Tokyo Chemical Industry Co., Ltd.) 20.2 parts, 4,4′-dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), 25.8 parts, 2-isopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene (manufactured by Nacalai Tesque) After charging 123.3 parts, the reaction solution was prepared by stirring at room temperature for 30 minutes. The reaction solution was then heated to 80 ° C. and stirred for 2 hours. The reaction solution was ice-cooled, and the precipitated solid was filtered off to obtain a yellow solid 1. After adding 123.9 parts of toluene to the filtrate to adjust the organic layer, the operation of separating and washing the organic layer with 123.9 parts of tap water was repeated three times. The washed organic layer was dehydrated with magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a yellow solid 2. The obtained yellow solid 1 and yellow solid 2 were purified by column chromatography, respectively. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 27.2 parts of a compound represented by the formula (C-IV-5) (yield 64%).

Identification of compound represented by formula (C-IV-5) ( ¹ H NMR; 400 MHz; δ value (ppm, TMS standard); DMSO); 1.14 (12H, d, J = 6.8 Hz), 3 .23 (2H, br.qq, J = 6.8, 6.8 Hz), 6.73 (4H, br.d, J = 8.8 Hz), 7.19 (6H, m), 7.38 ( 2H, m), 7.55 (4H, br.d, J = 8.8 Hz), 8.16 (2H, br.s)
(Mass spectrometry) ionization mode = ESI +: m / z = 449.2 [M + H] ⁺
= ESI−: m / z = 447.2 [M−H] ⁻
Exact Mass: 448.3

  The following reaction was performed in a nitrogen atmosphere. 10.0 parts of the compound represented by the formula (C-IV-5) and 70.1 parts of N, N-dimethylformamide were added to a flask equipped with a condenser and a stirrer, and the mixed solution was ice-cooled. . 7.5 parts of potassium t-butoxy (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, and then stirred for 1 hour under ice cooling. 12.3 parts of butyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise little by little and stirred at room temperature for 2 hours. After adding 300 parts of tap water and 300 parts of ethyl acetate to the reaction solution, a liquid separation operation was performed to obtain an organic layer. The obtained organic layer was dehydrated with magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a yellow solid. The resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 12.2 parts of a compound represented by the formula (C-I-5) (yield 98%).

Identification of compound represented by formula (CI-5) (mass spectrometry) ionization mode = ESI +: m / z = 561.3 [M + H] ⁺
Exact Mass: 560.4

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 5.7 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-5) and 50. After adding 0 part, 21.7 parts of phosphorus oxychloride was then added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 15.9 parts of a compound represented by the formula (A-II-5) (yield 100%).

Identification of compound represented by formula (A-II-5) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); −109.1 (1F, br.s)

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-5), 4.2 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100.0 parts of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Further, the obtained blue-green solid was purified by column chromatography. The purified blue-green solid was dried at 60 ° C. under reduced pressure to obtain 3.6 parts of the compound represented by the formula (AI-5) (yield 28%).

Identification of compound represented by formula (AI-5) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); −74.7 (6F, s), −109.1 (1F, br.s)
(UV-VIS)
0.10 g of the compound represented by the formula (AI-5) was dissolved in chloroform to a volume of 100 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 250 cm ³ (concentration: 0.008 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 0.7 (arbitrary unit) at λmax = 624 nm.

Reference synthesis example 3
The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 0.03 part of tris (dibenzylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.06 part of XPhos (manufactured by Aldrich), t-butoxy sodium (Tokyo Chemical Industry Co., Ltd.) 1.5 parts, 1.8 parts of 4,4′-dichlorobenzophenone (Tokyo Chemical Industry Co., Ltd.), 1.9 parts of 2,6-difluoroaniline (Tokyo Chemical Industry Co., Ltd.) and toluene (Nacalai Tesque) 9.3 parts) was added, and then stirred at room temperature for 30 minutes to prepare a reaction solution. The reaction solution was then heated to 80 ° C. and stirred for 2 hours. The reaction solution was ice-cooled, and the precipitated solid was filtered off to obtain a yellow solid 1. After adding 123.9 parts of toluene to the filtrate to adjust the organic layer, the operation of separating and washing the organic layer with 123.9 parts of tap water was repeated three times. The washed organic layer was dehydrated with magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a yellow solid 2. The obtained yellow solid 1 and yellow solid 2 were purified by column chromatography, respectively. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 3.1 parts of a compound represented by the formula (C-IV-6). Yield 98%

Identification of compound represented by formula (C-IV-6) ( ¹ H NMR; 400 MHz; δ value (ppm, TMS standard); DMSO); 6.74 (4H, br.d, J = 8.6 Hz) 7.15-7.35 (6H, m), 7.61 (4H, br.d, J = 8.6 Hz), 8.53 (2H, br.s)
( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); 114.3 (4F, br.t, J = 6.8 Hz)
(Mass spectrometry) ionization mode = ESI +: m / z = 437.5 [M + H] ⁺
Exact Mass: 436.1

  The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 2.5 parts of the compound represented by the formula (C-IV-6) and 18.3 parts of N, N-dimethylformamide, and the mixed solution was ice-cooled. . 1.9 parts of t-butoxypotassium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, followed by stirring for 1 hour under ice cooling. 2.7 parts of ethyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise little by little and stirred at room temperature for 2 hours. After adding 86 parts of tap water and 76 parts of ethyl acetate to the reaction solution, a liquid separation operation was performed to obtain an organic layer. The obtained organic layer was dehydrated with magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain a yellow solid. The resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 2.0 parts of a compound represented by the formula (C-I-6). Yield 71%

Identification of the compound represented by the formula (C-I-6) ( ¹ H NMR; 400 MHz; δ value (ppm, TMS standard); DMSO); 1.37 (6H, t, J = 7.0 Hz), 3 .69 (4H, q, J = 7.0 Hz), 6.64 (4H, br.d, J = 9.0 Hz), 7.28 (4H, br.dd, J = 8.0, 7.5 Hz) ), 7.44-7.53 (2H, m), 7.58 (4H, br.d, J = 9.0 Hz)
( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); 113.9 (4F, br.t, J = 7.5 Hz)
(Mass spectrometry) ionization mode = ESI +: m / z = 493.5 [M + H] ⁺
Exact Mass: 492.2

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 6.5 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-6) and 50. After adding 0 part, 24.7 parts of phosphorus oxychloride was then added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 16.7 parts of a compound represented by the formula (A-II-6). Yield 100%

Identification of compound represented by formula (A-II-6) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); 109.1 (1F, br.s), 114.2 (4F, br.s)

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-6), 4.5 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100.0 parts of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Further, the obtained blue-green solid was purified by column chromatography. The purified blue-green solid was dried at 60 ° C. under reduced pressure to obtain 10.2 parts of a compound represented by the formula (AI-6). Yield 79%

Identification of compound represented by formula (AI-6) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); 74.7 (6F, s) 109.1 (1F, br.s), 114.2 (4F, br.s)

(UV-VIS)
0.10 g of the compound represented by the formula (AI-6) was dissolved in chloroform to a volume of 100 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 250 cm ³ (concentration: 0.008 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 0.7 (arbitrary unit) at λmax = 601 nm.

Comparative Synthesis Example 1
The following reaction was performed in a nitrogen atmosphere. After charging 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a condenser and a stirrer, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, followed by stirring for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4′-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours. When the water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of a compound represented by the formula (CI-7). Yield 53%

Identification of compound represented by formula (CI-7) ( ¹ H NMR; 400 MHz; δ value (ppm, TMS standard); DMSO); 3.34 (6H, s), 6.83 (4H, br .D, J = 9.0 Hz), 7.20-7.28 (6H, m), 7.43 (4H, br.dd, J = 8.5, 7.5 Hz), 7.58 (4H, br.d, J = 9.0 Hz)

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 8.2 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (CI-7) and 20.20 parts of toluene. After adding 0 parts, 12.2 parts of phosphorus oxychloride was then added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain an organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-7). Yield 100%

Identification of compound represented by formula (A-II-7) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); 109.0 (1F, br.s)
(Mass spectrometry) ionization mode = ESI +: m / z = 687.3 [M-Cl] ⁺
Exact Mass: 722.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-7), 5.9 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100.0 parts of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 13.2 parts of a compound represented by the formula (AI-7). Yield 86%

Identification of compound represented by formula (AI-7) ( ¹⁹ F NMR; 380 MHz; δ value (ppm, hexafluorobenzene standard); DMSO); 74.7 (6F, s) 109.0 (1F, br.s)

(UV-VIS)
0.35 g of the compound represented by the formula (AI-7) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.8 (arbitrary unit) at λmax = 620 nm.

(Preparation of colored curable resin composition)
Example 1
Colorant (A): 26 parts of a dye represented by the formula (A-I-2);
Alkali-soluble resin (B): 53 parts of resin (B-1) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts;
Were mixed to obtain a colored curable resin composition.

Comparative Example 1
Colorant (A): 26 parts of a dye represented by the formula (A-III-1);

Alkali-soluble resin (B): 53 parts of resin (B-1) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
In addition, 0.15 part of leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored curable resin composition.

[Production of color filters]
The colored curable resin composition was applied on a 2-inch square glass substrate (# 1737; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), exposure was performed at an exposure amount (based on 365 nm) of 150 mJ / cm ^{2 in} an air atmosphere. A photomask was not used. The colored composition layer after exposure was post-baked in an oven at 180 ° C. for 20 minutes to produce a color filter (film thickness: 2.8 μm).

[Heat resistance evaluation]
The coating film of the colored photosensitive resin composition was heated at 230 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). As a result of performing the above heat resistance evaluation about the coating film obtained in Example 1, the color difference ((DELTA) Eab *) was 3.5. Moreover, as a result of carrying out heat resistance evaluation similarly about the comparative example 1, color difference ((DELTA) Eab *) was 12.1 and it turned out that this-application compound is excellent in heat resistance.

Example 2
Colorant (A): 20 parts of a compound represented by the formula (A-I-2);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.
As a result of producing a coating film of the colored composition in the same manner as in Example 1 and evaluating the heat resistance, the color difference (ΔEab *) of the coating film of the colored composition was 2.7.

Comparative Example 2
Colorant (A): 20 parts of a compound represented by the formula (AI-7);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the colored composition coating film was 3.8.

[Additional heat resistance evaluation]
The coating film of the colored photosensitive resin composition after the heat resistance evaluation was heated at 230 ° C. for 60 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). And measured. As a result of performing the above additional heat resistance evaluation for the coating film obtained in Example 2, the color difference (ΔEab *) was 0.7. Moreover, as a result of carrying out additional heat resistance evaluation similarly about the comparative example 2, color difference ((DELTA) Eab *) was 1.5 and it turned out that this-application compound is excellent in heat resistance.

Example 3
Colorant (A): 20 parts of a compound represented by the formula (AI-3);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.
As a result of producing a coating film of the colored composition in the same manner as in Example 1 and evaluating the heat resistance, the color difference (ΔEab *) of the coating film of the colored composition was 1.6. Subsequently, as a result of additional heat resistance evaluation, the color difference (ΔEab *) of the coating film of the colored composition was 0.8.

Example 4
Colorant (A): 16 parts of a compound represented by formula (A-I-2);
Colorant (A): 4 parts of a compound represented by formula (3-11);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the colored composition coating film was 2.0. Subsequently, as a result of additional heat resistance evaluation, the color difference (ΔEab *) of the coating film of the colored composition was 0.8.

Example 5
Colorant (A): 16 parts of a compound represented by the formula (AI-3);
Colorant (A): 4 parts of a compound represented by formula (3-11);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.
As a result of preparing a coating film of the colored composition in the same manner as in Example 1 and evaluating the heat resistance, the color difference (ΔEab *) of the coating film of the colored composition was 1.5. Subsequently, as a result of additional heat resistance evaluation, the color difference (ΔEab *) of the coating film of the colored composition was 0.8.

Reference example 1
Colorant (A): 20 parts of a compound represented by formula (AI-4);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.

Reference example 2
Colorant (A): 20 parts of a compound represented by the formula (AI-5);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.

Reference example 3
Colorant (A): 20 parts of a compound represented by the formula (AI-6);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.

Reference example 4
Colorant (A): 16 parts of a compound represented by the formula (AI-4);
Colorant (A): 4 parts of a compound represented by formula (3-11);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.

Reference Example 5
Colorant (A): 16 parts of a compound represented by the formula (AI-5);
Colorant (A): 4 parts of a compound represented by formula (3-11);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.

Reference Example 6
Colorant (A): 16 parts of a compound represented by the formula (AI-6);
Colorant (A): 4 parts of a compound represented by formula (3-11);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 23 parts of propylene glycol monomethyl ether;
Solvent (E): 4 parts of ethyl lactate;
Solvent (E): 16 parts methyl 3-methoxypropionate;
And leveling agent (H): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (H): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Antioxidant (J): Phosphorous antioxidant (Sumilyzer GP; manufactured by Sumitomo Chemical Co., Ltd.) 3.4 parts;
Were mixed to obtain a colored curable resin composition.

  From the compound of the present invention, a color filter having excellent heat resistance can be provided. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) or a solid-state image sensor.

Claims (10)

A compound represented by formula (AI).
[In the formula (AI), the counter ion Y represents an m-valent anion.
R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ^9A and R ^10A each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aralkyl group.
R ^11A and R ^12A each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^11A and R ^12A is an alkyl group having 1 to 10 carbon atoms.
R ^13A and R ^14A each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms. However, at least one of R ^13A and R ^14A is an alkyl group having 1 to 10 carbon atoms.
R ^15A , R ^16A , R ^17A , R ^18A , R ^19A and R ^20A each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
In R ^{1A to} R ^20A , an oxygen atom may be inserted between the methylene groups constituting the alkyl group.
R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic hydrocarbon group.
R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an optionally substituted aromatic hydrocarbon group.
In R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the alkyl group may have an oxygen atom inserted between the methylene groups constituting the alkyl group.
m represents an integer of 1 to 14. ] The compound according to claim 1, wherein the counter ion is a fluorine-containing anion having a fluorine atom. The compound according to claim 1, wherein the counter ion is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements. The compound (A- I ), resin (B), polymeric compound (C), polymerization which consist of the ion and counter ion which are represented by the formula (A- I ) of any one of Claims 1-3 A colored curable resin composition comprising an initiator (D) and a solvent (E). The colored curable resin composition according to claim 4 , comprising at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye. The colored curable resin composition according to claim 4 or 5 , comprising a colorless metal complex (F). Further, the colored curable resin composition according to any one of claims 4-6 containing a blue pigment. Coating film formed from the colored curable resin composition according to any one of claims 4-7. A color filter formed from the colored curable resin composition according to any one of claims 4-7. A display device comprising the color filter according to claim 9 .