JP6722442B2 - Compound, colored curable resin composition, color filter and liquid crystal display device - Google Patents

Description

The present invention relates to a compound having a cation and an anion in its molecule, a compound composed of a cation and an anion, a colored curable resin composition using the same, a color filter and a liquid crystal display device.

A coating film formed from the colored curable resin composition is desired to have excellent heat resistance and the like, and various techniques have been developed to improve the heat resistance and the like.
Patent Document 1 describes a colored curable resin composition containing a salt-forming compound composed of a triarylmethane-based basic dye and a counter compound thereof.

JP, 2014-170098, A

In Patent Document 1, a salt-forming compound is disclosed in terms of improving desired properties, but using a compound having both a cation and an anion in a molecule as a compound having heat resistance is not disclosed in Patent Document 1. Is not even taught.

Then, this invention makes it a subject to provide the colored curable resin composition which can form a coating film which has favorable heat resistance, and the compound used for this colored curable resin composition.

That is, the gist of the present invention is as follows.
[1] A compound (a) having a cation and an anion in the molecule,
At least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and an anion (b) containing oxygen as an essential element,
A compound comprising a cation (c) containing an alkaline earth metal.
[2] The compound according to [1], wherein the compound (a) is a xanthene compound (a1).
[3] The compound according to [2], wherein the xanthene compound (a1) is a compound represented by the formula (a1-1).

[In formula (a1-1), R ^{1 to} R ⁴ each independently have a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a substituent. Optionally represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is —O—, —CO—, —N(R ¹⁰ )—, It may be substituted with -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH-, or -NHCO-. However, adjacent -CH ₂ - is not to be replaced based on the same type at the same time, also the terminal -CH ₂ - is never to be replaced.
R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.
R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ¹⁰ 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. ]
[4] The compound according to any one of [1] to [3], wherein the cation (c) is at least one selected from the group consisting of magnesium cation, calcium cation, strontium cation, and barium cation.
[5] A colored curable resin composition containing the compound according to any one of [1] to [4], a resin, a polymerizable compound and a polymerization initiator.
[6] A color filter formed from the colored curable resin composition according to [5].
[7] A liquid crystal display device having the color filter according to [6].

According to the present invention, it is possible to provide a colored curable resin composition that can form a coating film with improved heat resistance and a compound used for the same.

1. Compound The compound of the present invention is a compound (a) having a cation and an anion in the molecule (hereinafter sometimes referred to as compound (a)) and at least one selected from the group consisting of tungsten, molybdenum, silicon and phosphorus. One element, an anion (b) containing oxygen as an essential element, and a cation (c) containing an alkaline earth metal.

1-1. Compound (a)
The compound (a) has a cation and an anion in the molecule. The cation and the anion in the molecule may have the same charge number or different charge numbers, and it is preferable that the cation and the anion have the same charge number in the molecule. More preferably, a cation and an anion each have the same charge number of 1 or more and 5 or less in the molecule, and still more preferably a cation and an anion each have the same charge number of 1 or more and 3 or less in the molecule, Particularly preferably, the cation and the anion each have one charge number in the molecule.

The compound (a) is preferably a xanthene compound (a1) or a squarylium compound (a2).

1-1-1. Xanthene compound As the xanthene compound (a1), a compound represented by the formula (a1-1) (hereinafter, sometimes referred to as “compound (a1)”) is preferable. The compound (a1) may be a tautomer thereof.

[In formula (a1-1), R ^{1 to} R ⁴ each independently have a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a substituent. Optionally represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is —O—, —CO—, —N(R ¹⁰ )—, It may be substituted with -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH-, or -NHCO-. However, adjacent -CH ₂ - is not to be replaced based on the same type at the same time, also the terminal -CH ₂ - is never to be replaced.
R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.
R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ¹⁰ 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. ]

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁴ and R ¹⁰ 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. , Linear alkyl groups such as decyl group, dodecyl group, hexadecyl group and icosyl group; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group A cycloaliphatic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group. The saturated hydrocarbon group of R ^{1 to} R ⁴ and R ¹⁰ has preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
Saturated methylene group contained in the hydrocarbon group (-CH ₂ -) is, -O -, - CO -, - N (R 10) -, - OCO -, - COO -, - OCONH -, - NHCOO-, It may be substituted with -CONH- or -NHCO-. However, adjacent -CH ₂ - is not to be replaced based on the same type at the same time, also the terminal -CH ₂ - is never to be replaced.

Examples of the group in which the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is replaced with —O— include the following (* represents a bond).

Examples of the group in which the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is replaced with —CO— include the following (* represents a bond).

Examples of the group in which the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is substituted with —NR ¹⁰ — include the following (* represents a bond).

Examples of the group in which the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is replaced with —OCO— include the following (* represents a bond).

Examples of the group in which the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is replaced with —COO— include the following (* represents a bond).

Examples of the group in which the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is replaced with —OCONH— include the following (* represents a bond).

Examples of the group in which the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is replaced with —NHCOO— include the following (* represents a bond).

Examples of the group in which the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is replaced with —CONH— include the following (* represents a bond).

Examples of the group in which the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is replaced with —NHCO— include the following (* represents a bond).

Examples of the substituent that the saturated hydrocarbon group represented by R ^{1 to} R ⁴ may have include an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include the followings.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.

The aromatic hydrocarbon group having 6 to 10 carbon atoms may have a substituent. The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R 7, -OH, -OR 7} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - ^{_{CO 2 H, -CO 2 R 7}} , -SR 7, -SO 2 R 7, -SO 3 R 7 and ^{_{-SO 2 N (R 8) (}} R 9) can be mentioned.
R ⁷ represents an alkyl group having 1 to 10 carbon atoms which may have a halogen atom. A methylene group contained in the alkyl group of carbon number 1-10, an oxygen atom, a carbonyl group or -N (R 7) ^- may be substituted with. However, adjacent methylene groups are not simultaneously substituted with the same type of group, and methylene groups at the ends are not substituted.
R ⁸ and R ⁹ each independently represent a hydroxy group or a saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or a hydrogen atom.
Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group.

Examples of -OR ⁷ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group. Are listed.

Examples of —CO ₂ R ⁷ include alkyloxycarbonyl and the like such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group.

Examples of —SR ⁷ include an alkylsulfanyl group such as a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an icosylsulfanyl group.
Examples of —SO ₂ R ⁷ include an alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁷ include alkyloxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group and icosyloxysulfonyl group.

—SO ₂ N(R ⁸ )(R ⁹ ) is, for example, 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 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-dimethylhexyl)sulfamoyl group, N-substituted sulfamoyl group such as N-(1,1,2,2-tetramethylbutyl)sulfamoyl group;
N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group Moyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group Examples thereof include N,N-2 substituted sulfamoyl groups and the like.

Examples of the alkyl group having 1 to ⁶ carbon atoms in R ⁵ and R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, an isopentyl group and a pentyl group. Of these, hydrogen atoms are preferable as R ⁵ and R ⁶ .

R ⁸ and R ⁹ may independently represent, together with a nitrogen atom, a 3- to 10-membered nitrogen-containing heterocycle. Examples of the heterocycle include the followings.

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

Z ⁺ is ⁺ N(R ¹⁰ ) ₄ , Na ⁺ or K ⁺ , and preferably ⁺ N(R ¹⁰ ) ₄ .
As the ⁺ N(R ¹⁰ ) ₄ , at least two of the four R ¹⁰ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹⁰ is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N(R ¹⁰ ) ₄ is present in the compound (a1), when R ¹⁰ is any of these groups, the color filter containing less foreign matter from the colored curable resin composition of the present invention containing the compound (a1). Can be formed.

Among these, as the _{^{substituent, -R 7, -SO 3 -,}} -SO 3 H, -SO 3 - Z + and ^{_{-SO 2 N (R 8) (}} R 9) are preferred, -R ^7, - SO ₃ ^- Z ⁺ and ^{_{-SO 2 N (R 8) (}} R 9) is more preferable. In this case, -R ⁷ is more preferably a monovalent alkyl group having 1 to 10 carbon atoms, further preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group or an ethyl group. The -SO ₃ in this case ^- as Z ^{+ _{is, -SO 3 - + N (R}} 10) 4 are preferred.

In the formula (a1-1), -SO ₃ ^- preferably is selected from the following formulas ^{(Z 5 -1) ~ (Z} 5 -5), more preferably formula (Z ⁵ -1).

As the compound represented by the formula (a1-1), a compound represented by the formula (a1-1-1) (hereinafter sometimes referred to as “compound (a1-1-1)”) is preferable. The compound (a1-1-1) may be a tautomer thereof.

[In the formula (a1-1-1),
R ^{1b to} R ^4b each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is , -O-, -CO-, -N(R< ^11b >)-, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ - is not to be replaced based on the same type at the same time, also the terminal -CH ₂ - is never to be replaced.
R ^1b and R ^2b may together form a ring containing a nitrogen atom, and R ^3b and R ^4b may together form a ring containing a nitrogen atom.
R ^5b and R ^6b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^11b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{1b to} R ^4b and R ^11b include the same as the saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁴ and R ¹⁰ . ..
Saturated methylene group contained in the hydrocarbon group (-CH ₂ -) is, -O -, - CO -, - N (R 11b) -, - OCO -, - COO -, - OCONH -, - NHCOO-, It may be substituted with -CONH- or -NHCO-. However, adjacent -CH ₂ - is not to be replaced based on the same type at the same time, also the terminal -CH ₂ - is never to be replaced.
The saturated hydrocarbon group for R ^{1b to} R ^4b may have a substituent, and examples of the substituent include an aromatic hydrocarbon group having 6 to 10 carbon atoms and a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.

In the compound (a1-1-1), of R ^1b to R ^4b, it is desirable R ^1b and R ^2b, R ^3b and R ^4b are the same saturated hydrocarbon groups, respectively, R ^1b and R ^2b, R ^{A combination in which 3b} and R ^4b are each a linear alkyl group is preferable, and a combination in which R ^1b and R ^2b and R ^3b and R ^4b are each a linear alkyl group having 1 to 5 carbon atoms is more preferable. More preferably, R ^1b and R ^2b , and R ^3b and R ^4b are a combination of two kinds selected from the group consisting of a methyl group, an ethyl group, a propyl group and a butyl group, respectively.

Examples of the ring formed by R ^1b and R ^2b together and the ring formed by R ^3b and R ^4b together include the followings.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^5b and R ^6b include those having 1 to 6 carbon atoms among the alkyl groups listed above. Of these, a hydrogen atom is preferable as R ^5b and R ^6b .

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

Moreover, as the compound represented by the formula (a1-1), a compound represented by the following formula (a1-1-2) (hereinafter sometimes referred to as “compound (a1-1-2)”) is preferable. The compound (a1-1-2) may be a tautomer thereof.

[In the formula (a1-1-2),
R ^1c and R ^4c each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, a plurality of R ^1c may be the same or different, and when q is 2 or more, a plurality of R ^4c may be the same or different.
R ^2c and R ^3c each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a methylene group ((methylene group) contained in the saturated hydrocarbon group ( -CH ₂ -) is, -O -, - CO -, - N (R 11c) -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or -NHCO- substituted with May be. However, adjacent -CH ₂ - is not to be replaced based on the same type at the same time, also the terminal -CH ₂ - is never to be replaced.
R ^1c and R ^2c may together form a ring containing a nitrogen atom, and R ^3c and R ^4c may together form a ring containing a nitrogen atom.
R ^5c and R ^6c each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^11c 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. ]

Examples of the alkyl group having 1 to 4 carbon atoms in R ^1c and R ^4c include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ^1c and R ^4c include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^1c and R ^4c include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.
Among them, R ^1c and R ^4c are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

The integer of 0-2 is preferable and, as for p and q, 1 or 2 is preferable.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in R ^2c , R ^3c and R ^11c 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. , Linear alkyl groups such as decyl group, dodecyl group, hexadecyl group and icosyl group; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group A cycloaliphatic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group. The monovalent saturated hydrocarbon group for R ^2c , R ^3c and R ^11c has preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
Saturated methylene group contained in the hydrocarbon group (-CH ₂ -) is, -O -, - CO -, - N (R 11c) -, - OCO -, - COO -, - OCONH -, - NHCOO-, It may be substituted with -CONH- or -NHCO-. However, adjacent -CH ₂ - is not to be replaced based on the same type at the same time, also the terminal -CH ₂ - is never to be replaced.
The saturated hydrocarbon group for R ^2c and R ^3c may have a substituent, and examples of the substituent include a halogen atom and an aromatic hydrocarbon group having 6 to 10 carbon atoms.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^5c and R ^6c include those having 1 to 6 carbon atoms among the alkyl groups listed above. Of these, a hydrogen atom is preferable as R ^5c and R ^6c .

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

Examples of the compound (a1) include compounds represented by the formula (I-1) to the formula (I-25). In the formulas (I-1) to (I-25), R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms. And more preferably a 2-ethylhexyl group.

Of the above compounds, compounds represented by formula (I-18) to formula (I-22) are preferable, and more preferably formula (I-18), formula (I-19), or formula (I-21). The compound represented by the formula (I-19) is more preferable.

1-1-2. Squalylium Compound The compound (a) of the present invention is preferably a squarylium compound (a2), more preferably a compound represented by the following formula (a2-1).

[In the formula (a2-1),
R ^{a1 to} R ^a4 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a saturated hydrocarbon having 1 to 20 carbon atoms. R ^a1 and R ^a5 , R ^a2 and R ^a6 , R ^a3 and R ^a7 , and R ^a4 and R ^a8 may each form a ring together with the carbon atom to which they are attached. , R ^a1 and R ^a9 , R ^a2 and R ^a10 , R ^a3 and R ^a11 , and R ^a4 and R ^a12 may form a ring together with the nitrogen atom and the carbon atom to which they are bonded. ..
R ^{a5 to} R ^a8 each independently represent a hydrogen atom, a hydroxy group, a —SH group, a —CF ₃ group or a —NHCO—R ^a23 .
R ^{a9 to} R ^a12 each independently represent an aromatic hydrocarbon group which may have a substituent, a saturated hydrocarbon group having 4 to 20 carbon atoms which may have a substituent, or a substituent. A methylene group which represents an unsaturated aliphatic hydrocarbon group having 4 to 20 carbon atoms and which may have, and which is a saturated hydrocarbon group or an unsaturated aliphatic hydrocarbon group, is an oxygen atom, a sulfur atom,- It may be replaced with N(R ^a24 )-, a sulfonyl group, or a carbonyl group. R ^a9 and R ^a10 and R ^a11 and R ^a12 may form a ring together with the nitrogen atom to which they are bonded.
R ^a23 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group constituting the monovalent saturated hydrocarbon group is an oxygen atom, a sulfur atom or —N( R ^a25 )−, a sulfonyl group or a carbonyl group may be substituted. However, adjacent methylene groups are not simultaneously substituted with the same type of group, and methylene groups at the ends are not substituted.
R ^a24 and R ^a25 each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

In formula (a2-1), examples of the halogen atom in R ^{a1 to} R ^a4 include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In Formula (a2-1), the aromatic hydrocarbon group represented by R ^{a1 to} R ^a4 preferably has 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms.
Further, the substituent which the aromatic hydrocarbon group represented by R ^{a1 to} R ^a4 may have is a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group or the like having 1 to 6 carbon atoms. Alkenyl group; C1-6 alkyloxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; And an alkyl group having 1 to 6 carbon atoms substituted with a fluorine atom such as a trifluoromethyl group; and the like.

Examples of the aromatic hydrocarbon group of R ^{a1 to} R ^a4 include aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, biphenylyl group, naphthyl group, anthryl group and phenanthryl group; benzyl group, phenylethyl group. Group, aralkyl group such as phenylbutyl group, aryloxy group such as phenoxy group, and the like.

The saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{a1 to} R ^a4 and R ^{a23 to} R ^a25 preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 carbon atom. ~8, particularly preferably 1 to 7 carbon atoms. Specifically, it has 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group. A straight-chain alkyl group having 3 to 20 carbon atoms such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group. A chain alkyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group.
The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a23 may have a substituent, and as the substituent, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a cyano group; a nitro group A carbamoyl group; a sulfamoyl group; a hydroxy group; an amino group and the like.

Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced with an oxygen atom include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. Group, an alkoxy group such as a pentyloxy group; and the like.
Further, the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced with an oxygen atom and a carbonyl group includes an alkyloxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group and a propoxycarbonyl group; an acetoxy group Groups having an ester bond such as an alkylcarbonyloxy group such as; an arylcarbonyloxy group such as a benzoyloxy group;

Further, as the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced by -N(R ^a24 )- or -N(R ^a25 )- and the carbonyl group, an N-methylcarbamoyl group, N- Ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec-butylcarbamoyl group, N-tert-butylcarbamoyl group, N-pentylcarbamoyl group, N-1 substituted carbamoyl group such as N-(1-ethylpropyl)carbamoyl group and N-(1,1-dimethylpropyl)carbamoyl group;
N,N-dimethylcarbamoyl group, N,N-ethylmethylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-propylmethylcarbamoyl group, N,N-isopropylmethylcarbamoyl group, N,N-tert-butyl Methylcarbamoyl group, N,N-butylethylcarbamoyl group, N,N-bis(1-methylpropyl)carbamoyl group, N,N-heptylmethylcarbamoyl group, N,N-bis(2-ethylhexyl)carbamoyl group, etc. N,N-2 substituted carbamoyl group;
Etc.

As the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced with a sulfonyl group with -N(R ^a24 )- or -N(R ^a25 )-, an N-methylsulfamoyl group, N -Ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group , N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group and the like. N-1 substituted sulfamoyl group;
N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-tert-butylmethylsulfamoyl group, N,N-bis A N,N-2 substituted sulfamoyl group such as (2-ethylhexyl)sulfamoyl group;
Etc.

Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is replaced with -N(R ^a24 )- or -N(R ^a25 )- include N-methylamino group, N-ethylamino group, N- Propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group, N-(1-ethyl Propyl)amino group, N-(1,1-dimethylpropyl)amino group, N-(1,2-dimethylpropyl)amino group dimethylhexyl)amino group, N-(1,1,2,2-tetramethylbutyl) ) N-alkylamino groups such as amino groups;
N,N-dimethylamino group, N,N-ethylmethylamino group, N,N-diethylamino group, N,N-propylmethylamino group, N,N-isopropylmethylamino group, N,N-tert-butylmethyl group N group such as amino group, N,N-butylethylamino group, N,N-bis(1-methylpropyl)amino group, N,N-heptylmethylamino group, N,N-bis(2-ethylhexyl)amino group , N-dialkylamino group;
N-methylaminomethyl group, N-ethylaminomethyl group, N-propylaminomethyl group, N-isopropylaminomethyl group, N-butylaminomethyl group, N-isobutylaminomethyl group, N-sec-butylaminomethyl group , N-tert-butylaminomethyl group, N-pentylaminomethyl group, N-(1-ethylpropyl)aminomethyl group, N-(1,1-dimethylpropyl)aminomethyl group, and other N-alkylaminomethyl groups ;
N,N-dimethylaminomethyl group, N,N-ethylmethylaminomethyl group, N,N-diethylaminomethyl group, N,N-propylmethylaminomethyl group, N,N-isopropylmethylaminomethyl group, N,N -Tert-butylmethylaminomethyl group, N,N-butylethylaminomethyl group, N,N-bis(1-methylpropyl)aminomethyl group, N,N-heptylmethylaminomethyl group, N,N-bis( N,N-dialkylaminomethyl group such as 2-ethylhexyl)aminomethyl group;
Etc.

A ring formed by R ^a1 and R ^a5 , R ^a2 and R ^a6 , R ^a3 and R ^a7 , R ^a4 and R ^a8 together with the carbon atom to which they are bonded is represented by the following formula. A structure etc. are mentioned. In the formula, R ^A1 represents the same group as R ^{a1 to} R ^a4 , R ^A2 represents the same group as R ^{a5 to} R ^a8, and R ^A3 represents the same group as R ^{a9 to} R ^a12 . * Represents a bond.

The ring formed by R ^a1 and R ^a9 , R ^a2 and R ^a10 , R ^a3 and R ^a11 , R ^a4 and R ^a12 together with the nitrogen atom and the carbon atom to which they are respectively bonded is represented by the following formula: The structure etc. which are represented are mentioned. In the formula, R ^A1 represents the same group as R ^{a1 to} R ^a4 , R ^A2 represents the same group as R ^{a5 to} R ^a8, and R ^A3 represents the same group as R ^{a9 to} R ^a12 . * Represents a bond.

The aromatic hydrocarbon group which may have a substituent in R ^{a9 to} R ^a12 preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, and 18 or less carbon atoms. Are preferred, and those having 15 or less carbon atoms are preferred. Examples of the aromatic hydrocarbon group represented by R ^{a9 to} R ^a12 include aryl groups having 6 to 12 carbon atoms such as phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group; benzyl group; Examples thereof include aralkyl groups having 7 to 12 carbon atoms such as phenylethyl group and phenylbutyl group. A phenyl group is particularly preferable as the aryl group, and a benzyl group is particularly preferable as the aralkyl group.
The aromatic hydrocarbon group represented by R ^{a9 to} R ^a12 may have a substituent, and examples of the substituent include an alkenyl group having 1 to 5 carbon atoms such as a vinyl group.
The aryl group preferably has a substituent at the o-position of the bond, and the aralkyl group preferably has a substituent at the o-position of the alkylene group. Examples of the aromatic hydrocarbon group which may have a substituent of R ^{a9 to} R ^a12 include groups represented by the following formulas. In the formula, * represents a bond.

Examples of the saturated hydrocarbon group having 4 to 20 carbon atoms in R ^{a9 to} R ^a12 include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, and icosyl group. A linear alkyl group such as a group; a branched alkyl group such as a 2-ethylhexyl group; Further, as the monovalent unsaturated aliphatic hydrocarbon group having 4 to 20 carbon atoms in R ^{a9 to} R ^a12 , for example, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, And linear alkenyl groups such as dodecenyl group, hexadecenyl group, and icosenyl group; and the like.
The saturated hydrocarbon group having 4 to 20 carbon atoms in R ^{a9 to} R ^a12 may have a substituent, and as the substituent, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a cyano group; a nitro group A carbamoyl group; a sulfamoyl group; a hydroxy group; an amino group and the like.

^{Examples of} the ring formed by R ^a9 and R ^a10 and R ^a11 and R ^a12 together with the nitrogen atom to which they are bonded include the structures represented by the following formulas.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^a24 and R ^a25 include a benzyl group, a phenylethyl group and a phenylbutyl group.

Among them, hydrogen atoms are preferable as R ^{a1 to} R ^a4 in the formula (a2-1).
R ^{a5 to} R ^a8 are preferably a hydrogen atom, a hydroxy group or —NHCO—R ^a23 , more preferably a hydrogen atom or a hydroxy group, and further preferably a hydrogen atom.
As R ^{a9 to} R ^a12 , each independently, an aromatic hydrocarbon group having 8 to 20 carbon atoms which may have a substituent or a saturated carbon group having 4 to 20 carbon atoms which may have a substituent. A hydrogen group is preferable, and a monovalent aromatic hydrocarbon group having 4 to 20 carbon atoms which may have a substituent is more preferable.
R ^a23 is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, and further preferably a saturated hydrocarbon group having 1 to 4 carbon atoms. ..
R ^a24 and R ^a25 are independently of each other, preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, and further preferably a saturated hydrocarbon group having 1 to 4 carbon atoms. It is a hydrocarbon group.

Examples of the groups represented by the following formulas (x-1) and (x-2) include groups represented by formulas (A1-1) to (A1-8).
In these formulas, * may represent a bond and >N−* may be >N ⁺ =*.

Examples of the groups represented by the formulas (x-1) and (x-2) include, in addition to the groups represented by the formulas (A1-1) to (A1-8) shown above, Examples thereof include groups represented by (A2-1) to (A2-7). * Represents a bonding hand, and >N−* may be >N ⁺ =*.

In Tables 1 to 4, as specific examples of the compound represented by the formula (a2-1), compounds (AI-1) to (AI-97) are listed based on the following formula (AI-a). It is not limited to this.

Note in the formula (AI-a) and Table 1 to 4, R ^a1 to R ^a8 are respectively synonymous with R ^a1 to R ^a8 in the formula ^{(a2-1), X a1, X} a2 , respectively, wherein It means a group represented by (x-1) or (x-2).

In Tables 1 to 4, (A1-1) to (A1-8) and (A2-1) to (A2-7) are formulas (A1-1) to (A1-8) and formula (A1-8), respectively. It means that it corresponds to a group represented by A2-1) to formula (A2-7). In formula (x-1) and formula (x-2), * may represent a bond and >N−* may be >N ⁺ =*. Furthermore, in Tables 1 to 4, NHCO-EHC is

Represents a group represented by. * Represents a binding hand.

From the viewpoint of availability of raw materials, compound (AI-16) to compound (AI-30) are more preferable, and among them, compound (AI-16), compound (AI-17) and compound (AI-22) are further preferable.

1-2. Anion (b)
The anion (b) is an anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus as essential elements.

As the anion, a heteropoly acid or isopoly acid anion compound containing tungsten as an essential element is preferable, and phosphotungstic acid, silicotungstic acid and tungsten-based isopoly acid anions are more preferable.

Examples of anions of heteropolyacids or isopolyacids containing tungsten as an essential element include, for example, Keggin-type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ³⁻ , Dawson-type phosphotungstic acid 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 as other examples, [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. Among them, the Keggin-type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ³⁻ is particularly preferable.

1-3. Cation (c)
The cation (c) is a cation containing an alkaline earth metal, and is preferably at least one selected from the group consisting of magnesium cation, calcium cation, strontium cation, and barium cation, and calcium cation or barium cation. Is more preferable. These may be derived from an alkaline earth metal halide capable of precipitating after formation of the target substance, and the alkaline earth metal halide is magnesium chloride, calcium chloride, strontium chloride, barium chloride or the like. I wish I had it.

When the compound of the present invention is A[compound (a)] ^a+b - ^.B [anion (b)] ^c - ^.C [cation (c)] ^d+ , the charge balance is Aa ^(+). =Bc ^(-) and Ab ^(-) =Cd ⁽⁺⁾ are preferable, and Bc ^(-) =Cd ⁽⁺⁾ is further preferable. The total number of charges of Aa ⁽⁺⁾ , Bc ^(-) , Ab ^(-) , and Cd ⁽⁺⁾ is preferably an even multiple, and Aa ⁽⁺⁾ , Bc ^(-) , Ab ^(-) , and Cd ⁽⁺⁾ are preferable. The total number of charges of ⁽⁺⁾ is more preferably 6, 8, 12, 16, 18, 24, or 36, and even more preferably 6, 8, or 12.
A is preferably an even multiple, more preferably 6, 8, 12, 16, 18, 24, or 36, and even more preferably 6, 8, or 12.
a represents a monovalent positive charge, and b represents a monovalent negative charge.
B is preferably an even multiple, more preferably 2 or 4, and even more preferably 2.
c is preferably 3, 4 or 6.
C is preferably 3, 4 or 6.
d is preferably an even multiple, and more preferably 2.

1-4. Examples of Compounds Containing Xanthene Compound Hereinafter, compounds in which the compound (a) includes a xanthene compound, the anion (b), and the cation (c) are exemplified.

1-5. Examples of Compounds Containing Squarylium Compound Hereinafter, compounds in which the compound (a) includes a squarylium compound, the anion (b), and the cation (c) are exemplified.
Hereinafter, Ra represents the following group.

The compound of the present invention has the formula (Xa-1a) to the formula (Xa-1h), the formula (Xa-2a) to the formula (Xa-2h), the formula (Xa-3a) to the formula (Xa-3h), the formula ( Xa-4a) to formula (Xa-4h) and formula (Xa-5a) to formula (Xa-5h) are preferred, and formulas (SQ-1a) to formula (SQ-1h) and formula (SQ). -2a) to formula (SQ-2h), formula (SQ-3a) to formula (SQ-3h) and formula (SQ-4a) to formula (SQ-4h) are preferable, and formulas are more preferable. It is selected from (Xa-5a) to formula (Xa-5h), and more preferably formula (Xa-5a).

The compound of the present invention can be used as a colorant.

2. Colored Curable Resin Composition In the present invention, the compound of the present invention (hereinafter sometimes referred to as a colorant (A1)), a resin (B), a polymerizable compound (C), and a polymerization initiator (D) are used. A colored curable resin composition containing is included.

Two or more kinds of colorants (A1) may be combined.
The content ratio of the colorant (A1) in the colorant is usually 1 to 100% by mass, preferably 3 to 100% by mass, more preferably 3 to 70% by mass, and 3 to 60% by mass. % Is more preferable.

In addition to the colorant (A1), a dye or a pigment may be included as the colorant (A2).
Dyes for the colorant (A2) include Color Index (The Society of Dyers and Colorists publication), Solvent, Acid, Basic, Reactive, and Direct (reactive). Examples thereof include compounds classified as Direct), Disperse, or Vat, and known dyes described in Dyeing Note (Shikiso Co., Ltd.). Further, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes and the like can be mentioned. Two or more kinds of these dyes may be used in combination.
Specific examples include dyes having the following color index (CI) numbers.
C. I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Disperse Yellow 51, 54, 76;
C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Reactive Orange 16;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 34, 102;
C. I. Disperse Violet 26, 27;
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. Acid Blue 25, 27, 40, 45, 78, 80, 112;
C. I. Direct Blue 40;
C. I. Disperse Blue 1, 14, 56, 60;
C. I. Solvent Green 1, 3, 5, 28, 29, 32, 33;
C. I. Acid Green 3, 5, 9, 25, 27, 28, 41;
C. I. Basic Green 1;
C. I. Bat green 1 etc. are mentioned.

The pigment of the colorant (A2) is not particularly limited, and known pigments can be used. Examples thereof include pigments classified as pigments by Color Index (published by The Society of Dyers and Colorists), and two or more kinds of them may be combined.
Specifically, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and the like;
C. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
Is mentioned.

The pigment may be rosin-treated, surface-treated with a pigment derivative having an acidic group or a basic group introduced therein, grafted on the surface of the pigment with a polymer compound, or atomized by a sulfuric acid atomization method, etc. Treatment, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by ion exchange method, and the like may be performed. The particle size of the pigment is preferably substantially uniform. The pigment can be made into a pigment dispersion liquid in a state of being uniformly dispersed in the pigment dispersant solution, by containing a pigment dispersant and performing a dispersion treatment. Each of the pigments may be subjected to a dispersion treatment alone, or a plurality of kinds of pigments may be mixed to perform a dispersion treatment.

Examples of the pigment dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples thereof include polyester-based, polyamine-based, acrylic-based surfactants and the like. You may use these pigment dispersants individually or in combination of 2 or more types. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Sols Perth (registered trademark) (manufactured by Zeneca Corporation), EFKA (registered trademark) ) (Manufactured by BASF), Azisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Chemie), and the like.
When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, a more evenly dispersed pigment dispersion tends to be obtained.

The content of the colorant (A1) in the colored curable resin composition is usually 0.01% by mass or more and 70% by mass or less, preferably 0.1% by mass or more and 60% by mass, based on the total amount of solids. % Or less, more preferably 0.2% by mass or more and 60% by mass or less, and particularly preferably 0.3% by mass or more and 50% by mass or less. When the content of the colorant (A1) is within the above range, desired spectrum and color density can be obtained more easily. In addition, in this specification, "the total amount of solid content" means the total amount of the components excluding the solvent from the colored curable resin composition of the present invention. The total amount of solid content and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography and gas chromatography.

When the colorant (A2) may be further contained, the ratio of the amount of the colorant (A1) used to the amount of the colorant (A2) used (colorant (A1) (solid content conversion)/colorant (A2)) (Solid content conversion) is preferably 0.1 or more and 100 or less, more preferably 0.5 or more and 50 or less, further preferably 1 or more and 25 or less, particularly preferably 1 or more and 10 or less, and most preferably It is 2 or more and 6 or less.

<Resin (B)>
The resin (B) contained in the colored curable resin composition of the present invention is preferably an alkali-soluble resin, and has a structure derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. Addition polymers having units are more preferred. Examples of such a resin include the following resins [K1] to [K6].
Resin [K1]: At least one kind (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)") and a cyclic ether structure having 2 to 4 carbon atoms And a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”) Resin [K2]: (a), (b), (a) And a copolymerizable monomer (c) (however, different from (a) and (b)) (hereinafter sometimes referred to as “(c)”) resin [K3]:(a ) And (c) copolymer resin [K4]: a resin obtained by reacting (b) with a copolymer of (a) and (c) resin [K5]: (b) and (c) Resin obtained by reacting (a) with a copolymer with (1) Resin (K6): (a) is reacted with a copolymer of (b) and (c), and carboxylic acid anhydride is further reacted. Resin obtained by

(A) is an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;
Unsaturated dicarboxylic acids such as maleic 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, etc. A bicyclo unsaturated compound containing a carboxy group of:
Unsaturated dicarboxylic acid anhydrides such as maleic anhydride;
An unsaturated acrylate containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid, may be mentioned.
Among them, acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an alkaline aqueous solution.

(B) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (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. .. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group. In addition, in this specification, "(meth)acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid, and the notations "(meth)acryloyl" and "(meth)acrylate" are also used. , Has the same meaning.

As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond Examples thereof include (b2) (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”).

As (b1), a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter may be 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), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and m-vinyl. Benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis( Glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris( Glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene and 2, 4,6-tris(glycidyloxymethyl)styrene may be mentioned.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth). Acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel), and represented by the formula (1). And a compound represented by the formula (2).

[In the formulas (1) and (2), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. It may be substituted.
X ^a and X ^b are each independently 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 compound represented by the formula (1) include compounds represented by the formula (1-1) to the formula (1-15), and among them, the formula (1-1) and the formula (1-3). , Compounds represented by formula (1-5), formula (1-7), formula (1-9) and formula (1-11) to formula (1-15) are preferable, and formula (1-1), The compounds represented by formula (1-7), formula (1-9) and formula (1-15) are more preferable.

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

The compound represented by the formula (1) and the compound represented by the formula (2) may each be used alone, or may be the compound represented by the formula (1) and the compound represented by the formula (2). You may use together. When these are used in combination, the ratio of the compound represented by the formula (1) and the compound represented by the formula (2) (the compound represented by the formula (1):the compound represented by the formula (2)) is mol. As a standard, it is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and further preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable.

As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable.

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

Examples of (c) include 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 technical field, it is referred to as “dicyclopentanyl(meth)acrylate” as a trivial name, and may also be referred to as “tricyclodecyl(meth)acrylate”. ), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (known in the art as a trivial name "dicyclopentenyl (meth)acrylate"), Dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth) ) (Meth)acrylic acid esters such as acrylates;
Hydroxy group-containing (meth)acrylic acid ester such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and itaconic acid diethyl;
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(cyclohexyl) Oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclo unsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3. A dicarbonylimide compound such as maleimide propionate or N-(9-acridinyl)maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride And the like; vinyl group-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; diene such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; ..

Among these, vinyl group-containing aromatic compounds, dicarbonyl imide compounds, and bicyclo unsaturated compounds are preferable from the viewpoint of copolymerization reactivity and heat resistance. Specifically, styrene, vinyltoluene, benzyl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N -Benzylmaleimide and bicyclo[2.2.1]hept-2-ene are preferred.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mol per 1 mol of the amount (a) used.

As the resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth ) Resin [K1] such as acrylate/(meth)acrylic acid copolymer; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth) Acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxy Tricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyltoluene copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth) Resin [K2] such as acrylic acid/styrene copolymer; benzyl(meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl(meth)acrylate/tricyclodecyl( Resin [K3] such as (meth)acrylate/(meth)acrylic acid copolymer; resin obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymer, tricyclodecyl ( Glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer with glycidyl (meth)acrylate added, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer Resin [K4] such as a resin to which (meth)acrylate is added; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid, tricyclodecyl (meth ) Resin [K5] such as a resin obtained by reacting (meth)acrylic acid with a copolymer of acrylate/styrene/glycidyl (meth)acrylate; to a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate A resin [K6] such as a resin obtained by further reacting a resin obtained by reacting (meth)acrylic acid with tetrahydrophthalic anhydride is mentioned.

The polystyrene equivalent weight average molecular weight of the resin (B) is usually 3,000 to 100,000, preferably 5,000 to 50,000, more preferably 5,000 to 35,000, and It is preferably 5,000 to 30,000, and particularly preferably 6,000 to 25,000. When the molecular weight is within the above range, the coating film hardness is improved, the residual film rate is high, the solubility of the unexposed area in the developing solution 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, more preferably 1.2 to 4, and further preferably 1. It is 3 to 3, and even more preferably 1.5 to 2.5.

The acid value (as solid content) of the resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 30 to 170 mg-KOH/g, and among them, 40 to 170 mg-KOH/g is preferable. Among them, 50 to 170 mg-KOH/g is preferable, 150 mg-KOH/g or less is more preferable, and 135 mg-KOH/g or less is further preferable.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined by, for example, titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, preferably 10 to 60% by mass, and more preferably 13 to 60% by mass, based on the total solid content. Of these, 17 to 55 mass% is preferable. When the content of the resin (B) is in the above range, the colored pattern can be easily formed, and the resolution of the colored pattern and the residual film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and/or an acid generated from a polymerization initiator, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, a (meth)acrylic acid ester. Compounds having a structure are preferred. The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-mentioned. (A), (b) and (c). Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate and triethylene glycol di(meth)acrylate. ) Acrylates, bis(acryloyloxyethyl) ethers of bisphenol A and 3-methylpentanediol di(meth)acrylates. As the polymerizable compound having three or more ethylenically unsaturated bonds, 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 Examples thereof include (meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.
Among these, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) in the colored curable resin composition of the present invention is usually 5 to 65% by mass, preferably 7 to 65% by mass, based on the total solid content, and It is preferably 10 to 60% by mass, more preferably 13 to 60% by mass, and particularly preferably 17 to 55% by mass. The content ratio of the resin (B) and the polymerizable compound (C) (resin (B):polymerizable compound (C)) is 20:80 to 80:20 by mass, and preferably 35:65. ~80:20. When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

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

Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-. On-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3- Yl]-3-Cyclopentylpropan-1-imine and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one -2-Imine is mentioned. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (all manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine And at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and N-benzoyloxy-1-(4- More preferred is phenylsulfanylphenyl)octan-1-one-2-imine.

Alkylphenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one. And 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.

The alkylphenone compounds are 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1 It may be an oligomer of 2-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone and benzyl dimethyl ketal.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl). -1,3,5-Triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis( Trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methyl) Phenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

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

Specific 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 (see, for example, JP-B-48-38403, JP-A-62-174204, etc.) and the phenyl group at the 4,4'5,5'-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (see, for example, JP-A-07-010913). Of these, compounds represented by the following formula and mixtures thereof are preferable.

Other polymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin compounds; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′. Benzophenone compounds such as -methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2- Examples thereof include quinone compounds such as ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with the below-mentioned polymerization initiation auxiliary agent (particularly amine-based polymerization initiation auxiliary agent).

Content of a polymerization initiator (D) is 0.1-40 mass parts normally with respect to 100 mass parts of total amounts of a resin (B) and a polymerizable compound (C), Preferably it is 0.1-30. Parts by mass, more preferably 1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass.

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

As the amine-based polymerization initiation aid, alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid. Aminobenzoic acid esters such as 2-dimethylaminoethyl and 2-ethylhexyl 4-dimethylaminobenzoate; N,N-dimethylparatoluidine, 4,4′-bis(dimethylamino)benzophenone (commonly called Michler's ketone), 4,4′ -Bis(diethylamino)benzophenone and 4,4'-bis(ethylmethylamino)benzophenone are mentioned, and among them, alkylaminobenzophenone such as 4,4'-bis(diethylamino)benzophenone; is preferable. Of these, alkylaminobenzophenone is preferable, and 4,4'-bis(diethylamino)benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

As the alkoxyanthracene-based polymerization initiation aid, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, Mention may be made of 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

As the carboxylic acid-based polymerization initiation aid, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl Examples include sulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When a polymerization initiation auxiliary agent is used, its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Parts by mass. When the content of the polymerization initiation aid 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)>
The solvent (E) is not limited, and solvents commonly used in the art can be used alone or in combination of two or more kinds. Specifically, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule, not containing -COO-), ether ester solvent (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O -, -CO- and COO--free solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, pyruvate. Mention may be made of methyl acidate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

As the ether solvent, 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, diethylene glycol methyl ethyl Examples include ethers, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 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 Examples include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Are listed.

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

Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

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

Two or more kinds of these solvents may be combined.

Among the above solvents, an organic solvent having a boiling point of 120° C. or higher and 210° C. or lower at 1 atm is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3 -Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide and N-methylpyrrolidone are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, di More preferred are propylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N,N-dimethylformamide and N-methylpyrrolidone.

The content of the solvent (E) is usually 70 to 95% by mass, preferably 75 to 92% by mass, and more preferably 75 to 90% by mass, based on the total amount of the colored curable resin composition. .. When the content of the solvent (E) is within the above range, the flatness at the time of application becomes good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed. ..

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

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

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

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

The content of the leveling agent is usually 0.0005% by mass or more and 0.6% by mass or less, preferably 0.001% by mass or more and 0.5% by mass or less, based on the total amount of the colored curable resin composition. Yes, more preferably 0.001 mass% or more and 0.2 mass% or less, still more preferably 0.002 mass% or more and 0.1 mass% or less, and particularly preferably 0.005 mass% or more and 0.07 mass% or more. It is not more than mass %. When the content of the leveling agent is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention may contain additives known in the art such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a compound (colorant (A1)), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E) and, if necessary, It can be prepared by mixing a leveling agent, a polymerization initiation aid and other components. In addition to the colorant (A1), a colorant (A2) such as a pigment or a dye can be further mixed. It is preferable to use the pigment in the state of a pigment dispersion liquid, which is previously mixed with a part or all of the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. .. At this time, part or all of the pigment dispersant and the resin (B) may be blended, if necessary.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Method of manufacturing color filter>
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, a printing method and the like. Among them, the photolithographic method is preferable. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithographic method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.

The thickness of the color filter to be produced can be appropriately adjusted depending on the purpose and application, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate, a resin plate, silicon, or a substrate on which aluminum, silver, a silver/copper/palladium alloy thin film or the like is formed is used. Other color filter layers, resin layers, transistors, circuits and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be manufactured as follows.

First, a colored curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or vacuum drying to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method and a slit and spin coating method.

Next, the colored composition layer is exposed through a photomask for forming an intended colored pattern. Use an exposure device such as a mask aligner or stepper because it can irradiate parallel rays uniformly on the entire exposed surface and can perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred. A colored pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution for development. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developing solution. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide. The developing method may be a paddle method, a dipping method, or a spray method. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

It is preferable to further post-bake the obtained colored pattern. The color filter having the colored pattern or the colored coating film thus obtained may be subjected to a surface coating treatment in order to impart various characteristics.

The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Next, the present invention will be described more specifically with reference to examples. In the examples,% and parts indicating the content or the amount used are based on mass unless otherwise specified.

[Example 1]
400 parts of methanol was added to 5.0 parts of the compound represented by formula (1-1), and the mixture was stirred at 20°C to 30°C for 1 hr to obtain a solution. 400 parts of ion-exchanged water was added to this solution and stirred for 2 hours to obtain a solution (1-1A). On the other hand, 28.8 parts of ion-exchanged water was added to 9.6 parts of phospho 12-tungstic acid trihydrogen, and the mixture was stirred at 20° C. to 30° C. for 1 hour. (1-1B) was obtained. The solution (1-1B) and 1.0 part of barium chloride were added to the solution (1-1A), and the mixture was stirred at 20°C to 30°C for 24 hours. The resulting precipitate was collected by filtration, washed twice with 200 parts of ion-exchanged water and then twice with 200 parts of methanol. The crystals collected by filtration were dried at 60° C. for 24 hours to obtain 6.3 parts of a compound represented by the formula (1-1P) (the compound represented by the formula (1-1P) is the compound represented by the formula (1-1)). It is synonymous with the compound represented by Xa-5a)).

[Synthesis of resin]
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85° C. with stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2. ^1.02,6 ]decane-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) (trade name "E-DCPA", manufactured by Daicel Corporation) 171 parts and propylene glycol monomethyl ether acetate 40 parts The solution dissolved in was added dropwise using a dropping pump over about 5 hours. On the other hand, a solution prepared by dissolving 26 parts of a polymerization initiator 2,2′-azobis(2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was put into the flask for about 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a solution of the copolymer (resin (B-1)) having a solid content of 43.5%. The obtained resin (B-1) had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mg-KOH/g.

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

[Preparation of colored curable resin composition]
Example 2
Compound (A1): compound represented by formula (1-1P) 0.8 part;
Alkali-soluble resin (B): Resin (B-1) (solid content conversion) 50 parts;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts;
Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyl oxime compound) 10 copies;
Solvent (E): 1-methyl-2-pyrrolidone 700 parts;
A leveling agent (F): 0.1 part of Megafac (registered trademark) F554 (manufactured by DIC Corporation) was mixed to obtain a colored curable resin composition.

Comparative Example 1
Dye (A1): 0.6 part of the compound represented by formula (1-1);
Alkali-soluble resin (B): Resin (B-1) (solid content conversion) 50 parts;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts;
Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyl oxime compound) 10 copies;
Solvent (E): Propylene glycol monomethyl ether acetate 700 parts;
A leveling agent (F): 0.1 part of Megafac (registered trademark) F554 (manufactured by DIC Corporation) was mixed to obtain a colored curable resin composition.

[Formation of pattern]
A colored curable resin composition was applied onto a 2-inch square glass substrate (Eagle XG; manufactured by Corning Incorporated) by a spin coating method, and then prebaked at 100° C. for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure device (TME-150RSK; manufactured by Topcon Corp.) was used in an atmosphere of 150 mJ/cm ^2. The light is irradiated with the exposure amount (reference of 365 nm). A photomask having a 100 μm line-and-space pattern is used. After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C. for 80 seconds, washed with water, and then 220° C. in an oven. After that, post-baking was performed for 20 minutes to obtain a pattern.

[Heat resistance evaluation]
The coating film of the colored curable resin composition was heated at 230° C. for 20 minutes, and the color difference (ΔEab*) before and after heating the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). As a result of heat resistance evaluation of the coating film obtained in Example 2, the color difference (ΔEab*) was 4.3. Further, as a result of carrying out heat resistance evaluation on Comparative Example 1 as well, the color difference (ΔEab*) was 12.9, and it was found that the compound of the present invention has excellent heat resistance.

By using the colored curable resin composition containing the present compound, a coating film having good heat resistance can be provided. The coating film is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Claims (6)

A compound (a) having a cation and an anion in the molecule,
At least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and an anion (b) containing oxygen as an essential element,
A compound consisting of a cation (c) containing an alkaline earth metal ,
The compound (a) is a compound represented by the formula (a1-1),
A compound characterized in that the anion (b) is an anion of phosphotungstic acid, silicotungstic acid or tungsten-based isopoly acid .

[In formula (a1-1), R ^{1 to} R ⁴ each independently have a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a substituent. Optionally represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group is —O—, —CO—, —N(R ¹⁰ )—, It may be substituted with -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH-, or -NHCO-. However, adjacent -CH ₂ - is not to be replaced based on the same type at the same time, also the terminal -CH ₂ - is never to be replaced.
R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.
R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ¹⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ] The cation (c), magnesium cations, calcium cations, claim 1 Symbol placement compound is at least one selected from the group consisting of strontium cation and a barium cation. The compound is A [compound (a)] ^a+b- ・B [anion (b)] ^c- ・C [cation (c)] ^d+ , The charge balance is Aa ⁽⁺⁾ =Bc ^(-) , Ab ^(-) =Cd ⁽⁺⁾ , Bc ^(-) =Cd ⁽⁺⁾ The compound according to claim 1 or 2, which satisfies the relationship. A compound according any one of claims 1 to 3, resin, a polymerizable compound and a polymerization initiator colored curable resin composition comprising a. A color filter formed from the colored curable resin composition according to claim 4 . A liquid crystal display device comprising the color filter according to claim 5 .