JP2017008287A - Compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem in which coating films formed from colored curable resin compositions comprising conventionally known compounds are insufficient in heat resistance and NMP resistance.SOLUTION: A compound comprises a polymer having a constitutional unit derived from (a) a cation represented by formula (A-I), and (b) an anion represented by formula (A-II).SELECTED DRAWING: None

Description

  The present invention relates to compounds useful as colorants.

  A dye is used as a colorant for a color filter included in a liquid crystal display device or a solid-state image sensor. As the dye, for example, Patent Document 1 describes a compound represented by the formula (8).

JP 2012-194466 A

  A coating film formed from a conventionally known colored curable resin composition containing the above compound has not been sufficiently satisfactory in terms of heat resistance and NMP resistance.

The present invention includes the following inventions.
[1] (a) a cation represented by the formula (AI), and
(B) A compound comprising a polymer having a structural unit derived from an anion represented by the formula (A-II).

[In Formula (AI), R ^{41 to} R ⁴⁶ are each independently a hydrogen atom, an amino group or a C 1-20 alkyl group which may be substituted with an amino group or a halogen atom; A group in which one oxygen atom is inserted between methylene groups between the methylene groups constituting the alkyl group, an aryl group having 6 to 20 carbon atoms which may be substituted, or a substituent; Or an aralkyl group having 7 to 30 carbon atoms. R ⁴¹ and R ⁴² may form a ring with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ may form a ring with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ^{42 46} may form a ring together with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom is inserted between methylene groups constituting the alkyl group. It may be.
^R55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms.
X1 represents an oxygen atom, —N (R ⁵⁷ ) —, or a sulfur atom.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

[In Formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
Y represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group is an oxygen atom. , —CO— or —N (R ⁵⁸ ) — may be substituted.
R ⁶¹ represents a hydrogen atom or a methyl group.
R ⁵⁸ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or a substituent. An aralkyl group having 7 to 30 carbon atoms which may be present. ]

[2] The compound according to [1], wherein X is a C 1-8 alkyl group substituted with a fluorine atom.
[3] The compound according to [1] or [2], wherein X is a nonafluorobutyl group.
[4] The compound according to any one of [1] to [3], wherein Y is an arylene group.
[5] The compound according to any one of [1] to [4], wherein Y is a phenylene group.
[6] A colored curable resin composition comprising the compound, resin, polymerizable compound and polymerization initiator according to any one of [1] to [5].
[7] A coating film formed using the colored curable resin composition according to [6].
[8] A color filter formed using the colored curable resin composition according to [6].
[9] A display device including the color filter according to [8].

  When the colored curable resin composition containing the compound of the present invention is used, a coating film excellent in heat resistance and NMP resistance can be provided.

  The compound of the present invention (hereinafter referred to as “compound (1)”) includes (a) a cation represented by formula (AI) (hereinafter, also referred to as “(a) cation”), and A polymer having a structural unit derived from an anion represented by formula (A-II) (hereinafter sometimes referred to as “(b-1) anion”) (hereinafter referred to as “(b) polymer”). There is.) The compound (1) of the present invention is useful as a colorant, and a coating film formed using a colored curable resin composition containing the compound (1) is excellent in heat resistance and NMP resistance. For this reason, a compound (1) is suitable as a coloring agent in a colored curable resin composition.

[In Formula (AI), R ^{41 to} R ⁴⁶ are each independently a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom; An alkyl group, a group in which one oxygen atom is inserted between the methylene groups constituting the alkyl group, an optionally substituted aryl group having 6 to 20 carbon atoms, or a substituted group. It represents an aralkyl group having 7 to 30 carbon atoms. R ⁴¹ and R ⁴² may form a ring with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ may form a ring with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ^{42 46} may form a ring together with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom is inserted between methylene groups constituting the alkyl group. It may be.
^R55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. X1 represents an oxygen atom, —N (R ⁵⁷ ) —, or a sulfur atom.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

[In Formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
Y represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group is an oxygen atom. , —CO— or —N (R ⁵⁸ ) — may be substituted.
R ⁶¹ represents a hydrogen atom or a methyl group.
R ⁵⁸ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or a substituent. An aralkyl group having 7 to 30 carbon atoms which may be present. ]

The alkyl group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ may be linear, branched or cyclic. Moreover, carbon number of this alkyl group becomes like this. Preferably it is 1-10, More preferably, it is 1-8, More preferably, it is C1-C6, Most preferably, it is C1-C4.
Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group.
The carbon number of the chain alkyl group is preferably 1-8, more preferably 1-6, and still more preferably 1-4.
The cyclic alkyl group may be monocyclic or polycyclic. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. Carbon number of a cyclic alkyl group becomes like this. Preferably it is 3-10, More preferably, it is 6-10.
Specific examples of the alkyl group represented by R ^{41 to} R ⁴⁶ include groups represented by the following formulas. In the following formula, * represents a bond with a nitrogen atom.

The hydrogen atom of the alkyl group represented by R ^{41 to} R ⁴⁶ may be substituted with an amino group or a halogen atom. Examples of such an amino group include a dialkylamino group such as a dimethylamino group. As for, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Examples of the alkyl group in which a hydrogen atom is substituted with an amino group or a halogen atom include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

Among the groups represented by R ^{41 to} R ⁴⁶ , examples of the group in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms are represented by the following formulae. Group. In the following formula, * represents a bond with a nitrogen atom. Among them, the group having an oxygen atom inserted between the methylene groups constituting the alkyl group is preferably a group having 2 to 10 carbon atoms, and more preferably a group having 2 to 6 carbon atoms. The alkyl group into which the oxygen atom is inserted is preferably linear. The number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

In R ^{41 to} R ⁴⁶ , the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and the aralkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. It is.
Examples of the aryl group represented by R ^{41 to} R ⁴⁶ include a phenyl group and a naphthyl group.
Examples of the aryl group in the aralkyl groups of R ^{41 to} R ⁴⁶ include a phenyl group and a naphthyl group. Examples of the aralkyl group include a group in which a bond of these aryl groups and an alkylene group are bonded. Carbon number of the alkylene group is preferably 1 to 10, more preferably 1 to 5, a chain alkylene group is preferable, and a linear alkylene group is more preferable. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group. Is mentioned.
Among the groups represented by R ^{41 to} R ⁴⁶ , in the aryl group and aralkyl group, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; chloromethyl group, trifluoromethyl group and the like A haloalkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; a sulfamoyl group; A C 1-6 alkylsulfonyl group such as a group; a sulfonamide group; a C 2-6 alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group;
Specific examples of the aryl group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bond with a nitrogen atom.

  Examples of the aralkyl group which may be substituted include a group in which an alkylene group such as a methylene group or an ethylene group is bonded to the bond of the aryl group.

Examples of the ring formed by combining R ⁴¹ and R ⁴² together with the nitrogen atom to which they are bonded include a 5-membered ring such as a pyrrolidine ring; a 6-membered ring such as a morpholine ring, piperidine ring, and piperazine ring;
Examples of the ring formed by combining R ⁴³ and R ⁴⁴ together with the nitrogen atom to which they are bonded include a 5-membered ring such as a pyrrolidine ring; a 6-membered ring such as a morpholine ring, piperidine ring, and piperazine ring.
Examples of the ring formed by combining R ⁴⁵ and R ⁴⁶ together with the nitrogen atom to which they are bonded include a 5-membered ring such as a pyrrolidine ring; a 6-membered ring such as a morpholine ring, piperidine ring and piperazine ring;

R ^{41 to} R ⁴⁶ are each independently an alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group, or an optionally substituted aralkyl group from the viewpoint of ease of synthesis. Preferably, independently of each other, an alkyl group having 1 to 8 carbon atoms or an aryl group represented by the following formula is more preferable. In the following formula, * represents a bond with a nitrogen atom.

The alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ may be linear, branched or cyclic, and is preferably linear. Examples of the alkyl group having 1 to 8 carbon atoms of R ^{47 to} R ⁵⁴ include groups having 1 to 8 carbon atoms among the groups exemplified as the alkyl group of R ^{41 to} R ⁴⁶ . The group having an oxygen atom inserted between the methylene groups (carbon atoms) constituting the alkyl group is more preferably a group having 1 to 6 carbon atoms. The alkyl group into which an oxygen atom is inserted is preferably linear, and the number of methylene groups between oxygen atoms is preferably 1 to 4, more preferably 2 to 3. As said group, group represented by a following formula is mentioned, for example. In the following formula, * represents a bond with a carbon atom.

R ^{47 to} R ⁵⁴ are each independently preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and independently of each other, a hydrogen atom, a methyl group, or fluorine. It is more preferably an atom or a chlorine atom, and further preferably a hydrogen atom.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^55, include the same groups as the groups exemplified as alkyl groups R ⁴⁷ to R ^54, specifically, for example, represented by the following formula Groups. In the following formula, * represents a bond with a carbon atom. Among these, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is further preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

An oxygen atom may be inserted between the methylene groups contained in the alkyl group of R ⁵⁵ , and examples of such groups include groups represented by the following formulae. In the following formula, * represents a bond. The alkyl group into which the oxygen atom is inserted is preferably linear. Moreover, as a methylene group number between oxygen atoms, 1-4 are preferable and 2-3 are more preferable.

In ^R55 , the aryl group has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.
The aryl group R ^55, a phenyl group, a naphthyl group and the like, with preference given to phenyl group.
In the aryl group of R ⁵⁵ , the substituent includes a halogen atom such as a fluorine atom, a chlorine atom or an iodine atom; a haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; a methoxy group or an ethoxy group An alkoxy group having 1 to 6 carbon atoms; a hydroxy group; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; a methoxycarbonyl group; And alkoxycarbonyl groups having 2 to 6 carbon atoms such as ethoxycarbonyl group;
Specific examples of the aryl group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bond with a carbon atom.

R ⁵⁵ is preferably an alkyl group having 1 to 10 carbon atoms or an optionally substituted aryl group, more preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, carbon, from the viewpoint of ease of synthesis. A haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an aryl group optionally substituted with a methylsulfonyl group, and more preferably the following formula It is an aryl group represented by. In the following formula, * represents a bond with a carbon atom.

Examples of the alkyl group having 1 to 10 carbon atoms of R ⁵⁷ include groups having 1 to 10 carbon atoms among the groups exemplified as the alkyl group having 1 to 20 carbon atoms of R ⁴¹ , preferably a hydrogen atom or carbon The alkyl group of number 1-8 is mentioned.

Moreover, as a cyclic structure containing X1, the group represented by a following formula is mentioned, for example. In the formula, R ⁴⁵ , R ⁴⁶ and R ⁵⁵ are as defined above, respectively, and * represents a bond with a carbon atom.

  Among these, as X1, an oxygen atom or a sulfur atom is preferable, and a sulfur atom is more preferable.

  Examples of the cation of the formula (AI) include a cation 1 to a cation 25 represented by the formula (A-I-1) represented by a combination of substituents described in Table 1 below.

  In Table 1, Ph1 to Ph12 each mean a group represented by the following formula.

  In Table 1, Ha1 means a group represented by the following formula.

  Among them, as the cation of the formula (AI), cation 1 to cation 6, cation 11 and cation 12 are preferable, and cation 1, cation 2 and cation 12 are more preferable.

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

[In formula (BI) and formula (CI), R ^{41 to} R ⁵⁵ each represent the same meaning as described above. ]

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

[In formula (B-II), formula (C-II) and formula (C-III), R ^{41 to} R ⁵⁵ each have the same meaning as described above. ]
It is preferable that the compound represented by Formula (C-II) and the compound represented by Formula (C-III) are the same.

The amount of the compound represented by the formula (CI) to be used is preferably 0.5 mol or more and 8 mol or less, more preferably 1 mol per 1 mol of the compound represented by the formula (BI). More than 3 moles.
The total amount of the compound represented by the formula (C-II) and the compound represented by the formula (C-III) is preferably 0 with respect to 1 mol of the compound represented by the formula (B-II). .5 mol or more and 8 mol or less, more preferably 1 mol or more and 3 mol or less.

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

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

  The above reaction is preferably performed in the presence of a condensing agent from the viewpoint of yield. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, thionyl chloride and the like.

  The amount of the condensing agent to be used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0 with respect to 1 part by mass of the compound represented by the formula (BI) or (B-II). .2 parts by mass or more and 5 parts by mass or less.

  The method for obtaining the target compound (AI) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, there is a method in which the reaction mixture is mixed with an alcohol (for example, methanol or the like), and the precipitated crystals are collected by filtration. The reaction mixture is preferably added to the alcohol. The temperature when adding the reaction mixture is preferably −100 ° C. or more and 50 ° C. or less, more preferably −80 ° C. or more and 0 ° C. or less. Moreover, after mixing, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The compound collected by filtration is preferably washed with water and then dried.

  Examples of the method for producing the compounds (BI) and (B-II) include various known methods, for example, the methods described in West German Patent Application P3928243.0.

  As a manufacturing method of compound (CI), (C-II), and (C-III), the well-known various methods, for example, the method described in patent document 1, is mentioned.

  The compound (1) of the present invention includes (b) a polymer having a structural unit derived from an anion represented by the following general formula (A-II) in addition to the cation (a).

[In the formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may be partially or entirely substituted with a halogen atom. Y represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof, and a methylene group constituting the aliphatic hydrocarbon group or the arylene group. May be substituted with an oxygen atom, —CO— or —N (R ⁵⁸ ) —. R ⁶¹ represents a hydrogen atom or a methyl group. R ⁵⁸ has an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or a substituent. It represents an aralkyl group having 7 to 30 carbon atoms. ]

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably a fluorine atom and a chlorine atom are mentioned, More preferably, a fluorine atom is mentioned.
In the formula (A-II), X is preferably an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom (particularly a fluorine atom) from the viewpoint of increasing the acidity of imide acid, It is more preferably a linear or branched perfluoroalkyl group having 2 to 8 carbon atoms in which all atoms are substituted with fluorine atoms. Examples of the perfluoroalkyl group include -CF ₃ ; -CF ₂ CF ₃ ; perfluoropropyl groups such as -CF ₂ CF ₂ CF ₃ and -CF (CF ₃ ) ₂ ; -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) ₂ , C 1-8 halofluoroalkyl groups such as perfluorobutyl groups such as —C (CF ₃ ) _3, etc., preferably —CF ₂ CF ₂ CF ₃ , Perfluoropropyl groups such as —CF (CF ₃ ) ₂ ; and perfluorobutyl groups such as —CF ₂ CF ₂ CF ₂ CF ₃ , —CF ₂ CF (CF ₃ ) ₂ , and —C (CF ₃ ) _3. More preferred are perfluorobutyl groups such as —CF ₂ CF ₂ CF ₂ CF ₃ , —CF ₂ CF (CF ₃ ) ₂ , —C (CF ₃ ) ₃ , and particularly preferred is —CF ₂ CF ₂ CF. ₂ CF ₃ is mentioned. Moreover, carbon number of X is 1-8, Preferably it is 2-8, More preferably, it is 3-8, More preferably, it is 4-8.

The divalent group for Y is preferably a linear or branched alkylene group, an arylene group, or an arylene alkylene group. Moreover, it is preferable that the carbon number of Y is 1-20, and it is more preferable that it is 1-10. Specifically, the linear or branched alkylene group preferably has 1 to 10 carbon atoms, the arylene group preferably has 6 to 20 carbon atoms, and the arylene alkylene group has 7 to 7 carbon atoms. 20 is preferable. The alkylene group may be linear or branched, and examples thereof include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and a butylene group.
Examples of the arylene group include a phenylene group and a naphthylene group.
Examples of the arylene alkylene group include an arylene methylene group, an arylene ethylene group, an arylene propylene group, an arylene butylene group, an arylene pentylene group, and an arylene hexylene group. The arylene alkylene group is preferably bonded to the sulfur atom on the arylene group side.
Further, the alkylene group include a methylene group constituting the arylenealkylene group is an oxygen atom, -CO- or -N (R ⁵⁸⁾ - may be replaced with.
R ⁵⁸ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have, and optionally having an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R ⁴¹ , or a substituent. Examples thereof include the same groups as the aryl group having 6 to 20 carbon atoms or the aralkyl group having 7 to 30 carbon atoms which may have a substituent.

  Among these, as Y, an arylene group or an arylene alkylene group having 7 to 10 carbon atoms is preferable, among which an arylene group, an arylmethylene group, an arylethylene group, an arylpropylene group, an arylenebutylene group, an arylenepentylene group, An arylene hexylene group is more preferred, an arylene group is further preferred, and a phenylene group is particularly preferred.

  Examples of (b-1) anions include anions represented by the following formulas (A-II-1) to (A-II-6).

  These (b-1) anions may be used alone or in combination of two or more.

Moreover, in the said (b) polymer, it is preferable at the point that the density | concentration of (a) cation becomes high in the compound (1) of this invention, so that the ratio of the structural unit derived from (b-1) anion becomes high. From the above viewpoint, in the polymer (b), the molar ratio between the structural unit derived from the (b-1) anion and the structural unit other than the structural unit derived from the (b-1) anion is 1/1 to 1 / It is preferably 10, more preferably 1/1 to 1/8, and preferably 1/1 to 1/7.
In the polymer (b), the proportion of the structural unit derived from the (b-1) anion is preferably 1 mol% or more and 90 mol% or less, and preferably 3 mol% or more and 50 mol% or less. More preferably, it is 5 mol% or more and 50 mol% or less.

  Compound (A-II) is represented, for example, by a compound represented by formula (D-II) (hereinafter sometimes referred to as “compound (D-II)”) and formula (E-II). It can be produced by reacting a compound (hereinafter sometimes referred to as “compound (E-11)”). Such a reaction may be performed in the presence of an organic solvent or may be performed without a solvent.

[In the formula (D-II) and the formula (E-II), X, Y and R ⁵¹ each represent the same meaning as described above. ]

  The amount of compound (E-II) to be used is preferably 0.5 mol to 8 mol, more preferably 1 mol to 4 mol, per 1 mol of compound (D-II).

  As reaction temperature, 0-50 degreeC is preferable and 5-30 degreeC is more preferable. The reaction time is preferably 1 to 12 hours, more preferably 3 to 6 hours.

  The reaction between the compound (D-II) and the compound (E-II) is preferably performed in an organic solvent from the viewpoint of yield. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitrated hydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone; and the like. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more, with respect to 1 part by mass in total of the compound (D-II) and the compound (E-II). It is 10 parts by mass or less.

  The above reaction is preferably carried out in the presence of an amine from the viewpoint of yield. Examples of the amine include trialkylamines such as triethylamine and diisopropylethylamine.

  When amine is used, the amount used is preferably 0.1 mol or more and 20 mol or less, more preferably 0.2 mol or more and 5 mol or less, relative to 1 mol of the compound (D-II).

  The method for obtaining the target compound (A-II) from the reaction mixture is not particularly limited, and various known methods can be employed. Examples of the technique include taking out the reaction mixture by mixing it with water and separating and concentrating the organic layer. The removed compound is preferably purified by column chromatography and then dried.

  As a method for producing compound (D-II), various known methods, for example, J. Org. Fluorine Chem. 128 (2007) 1353-1358. Can be mentioned.

  As a manufacturing method of a compound (E-II), various well-known methods, for example, Journal of Molecular Catalysis A: Chemical 311 (2009) 46-53. Can be mentioned.

  (B) In addition to the structural unit derived from the (b-1) anion, the polymer is a structural unit represented by the formula (A-III) (hereinafter referred to as “(b-2) epoxy group-containing compound”. It may have a structural unit derived from.

[In the above formula (A-III), R ⁷¹ represents a hydrogen atom or a methyl group.
A represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the methylene group constituting the aliphatic hydrocarbon group may be substituted with an oxygen atom or —CO—. ]

There is no restriction | limiting in particular as a bivalent aliphatic hydrocarbon group represented by A, For example, a linear or branched alkylene group is preferable. Examples of the alkylene group include linear alkylene groups such as methylene group, ethylene group, n-propylene group, and butylene group; branched alkylene groups such as isopropylene group and branched butylene group; and the like. Carbon number of the aliphatic hydrocarbon group of A is preferably 1-10, more preferably 1-5.
Examples of the group in which the methylene group of the aliphatic hydrocarbon group of A is substituted with an oxygen atom include a linear or branched oxyalkylene group, and the methylene group of the aliphatic hydrocarbon group of A is an oxygen atom and Examples of the group substituted with —CO— include a linear or branched carbonyloxyalkylene group. The methylene group bonded to the epoxy group is preferably not substituted with an oxygen atom or CO—, and the carbonyloxyalkylene group is preferably bonded to —C (CH ₂ ) R ⁶¹ on the carbonyl group side. Examples of the oxyalkylene group include an oxyethylene group, an oxypropylene group, and an oxybutylene group, and examples of the carbonyloxyalkylene group include a carbonyloxymethylene group. Among these, a carbonyloxyalkylene group is preferable from the viewpoint of availability of raw materials and production, and a carbonyloxymethylene group is particularly preferable.

  Examples of the (b-2) epoxy group-containing compound include glycidyl (meth) acrylate. These compounds may be used alone or in combination of two or more.

Moreover, the higher the ratio of the (b-2) epoxy group-containing compound, the more the NMP resistance of the color filter containing the colorant can be improved. From such a viewpoint, the proportion of the structural unit derived from the (b-2) epoxy group-containing compound in the polymer (b) is preferably 10 mol% or more and 99 mol% or less, more preferably 50 mol%. It is 97 mol% or less, More preferably, it is 50 mol% or more and 95 mol% or less.
Moreover, it is preferable that the ratio of the structural unit derived from the (b-1) anion and the structural unit derived from the (b-2) epoxy group-containing compound is 1/1 to 1/7.
Moreover, the sum total of the ratio of the structural unit derived from the (b-1) anion and the (b-2) epoxy group containing compound in (b) polymer becomes like this. Preferably it is 50 mol% or more, More preferably, it is 70 mol. % Or more, more preferably 90 mol% or more.

  In addition to the structural unit derived from the (b-1) anion and the (b-2) epoxy group-containing compound, the (b) polymer is a compound containing a functional group having another ethylenically unsaturated bond (hereinafter, It may have a structural unit derived from “(b-3) an ethylenically unsaturated bond-containing compound”.

The functional group having an ethylenically unsaturated bond is preferably a functional group having an ethylenic double bond, specifically, a vinyl group, an allyl group, a (meth) acryl group, or a (meth) acryloyl group. And vinyl cycloalkyl group. Among these, a vinyl group, an allyl group, a (meth) acryl group, and a (meth) acryloyl group are preferable from the viewpoints of reactivity and ease of synthesis.
The (b-3) ethylenically unsaturated bond-containing compound is preferably a compound containing a functional group having one ethylenically unsaturated bond in the molecule from the viewpoint of ease of production.

Examples of the (b-3) ethylenically unsaturated bond-containing compound 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 (referred to in the art as “dicyclopentanyl (meth) acrylate” as a common name. Tricyclodecyl (meth) a May be referred to relations. "), Tricyclo (Meta) acrylate (the art," dicyclopentenyl (meth as trivial name) [5.2.1.0 ^{2, 6]} decene-8-yl acrylate " Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) ) (Meth) acrylic acid esters such as acrylate and benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
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 and vinylidene chloride And the like; esters such as acrylamide, methacrylamide and vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Of these, vinyl group-containing aromatic hydrocarbons such as styrene and alkyl (meth) acrylates such as methyl (meth) acrylate are preferred from the viewpoint of copolymerization reactivity and availability.

The molecular weight of the polymer (b) having the structural unit derived from the (b-1) anion is the compatibility with the coating film of the colored curable resin composition and the (a) cation concentration contained in the colorant. From the viewpoint of ensuring, the weight average molecular weight (Mw) is preferably 2000 or more and 30000 or less. Further, the weight average molecular weight (Mw) is more preferably 7000 or more, further preferably more than 10,000, particularly preferably 11,000 or more, more preferably 25000 or less, and further preferably 20000 or less. (B) In the colored curable resin composition, the content of the resin (B) described later can be reduced as the weight average molecular weight (Mw) of the polymer increases.
The molecular weight distribution (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 2.0.
In addition, the molecular weight of (b) polymer can be estimated as a molecular weight converted using styrene as a standard substance using a size exclusion chromatography (SEC) method.

  Here, the (b-1) anion is a counter anion of the (a) cation. In the compound of the present invention, the ratio (cation / anion) between the (a) cation and the structural unit derived from the (b-1) anion is preferably 0.8 or more and 1 or less on a molar basis. More preferably, it is 0.85 or more, More preferably, it is less than 1, More preferably, it is 0.95 or less. When the ratio (cation / anion) is 1 or less (particularly less than 1), the structural unit derived from (a) cation and (b-1) anion is present in an equivalent amount on a molar basis, or (a) from cation (B-1) there are more structural units derived from anions, and it is possible to further suppress residual counter anions in the raw material salt of (a) cation ((a) salt containing cation) described later.

  In the compound (1) of the present invention, the total of (a) cation and (b) polymer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 98% by mass. % Or more.

The production method of the (b) polymer is performed by polymerizing (preferably radical polymerization) the (b-1) anion, and (b-1) an anion salt and (b-2) containing an epoxy group It is preferable to radically polymerize the compound.
The radical polymerization is preferably carried out in the presence of a reaction solvent. Examples of the reaction solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[Method for producing colorant]
The compound (1) of the present invention comprises, for example, a salt (hydrochloride, phosphate, sulfate, benzenesulfonate) containing a cation in the solution of the polymer (b) obtained as described above. , Naphthalene sulfonate, perchlorate, BF ₄ salt, PF ₆ salt, etc.) and salt exchange.
Specifically, it can be synthesized by dissolving the polymer (b) in a reaction solvent as necessary, adding the salt containing the (a) cation, stirring, and then removing the purified precipitate by filtration. (A) The cation is 80 mol% to 100 mol% (preferably 85 mol% or more and less than 100 mol%) with respect to the structural unit derived from the anion represented by the formula (A-II) in the polymer (b). And more preferably 85 mol% or more and less than 95 mol%).
Examples of the reaction solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, 2-ethoxyethanol, and 1-methoxy-2-propanol. Such alcohols, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile and the like. The reaction temperature is preferably, for example, 0 to 40 ° C.

The colored curable resin composition of the present invention preferably contains the compound (1) of the present invention as a colorant (hereinafter sometimes referred to as “colorant (A)”), and further contains a resin (B). More preferably, the colored curable resin composition of the present invention further contains a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). The colored curable resin composition of the present invention preferably further contains a leveling agent (F).
The colored curable resin composition of the present invention preferably further contains a polymerization initiation assistant (D1).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
As the colorant (A), the compound (1) of the present invention may be used alone, but for the purpose of toning, that is, to adjust the spectral characteristics, other dyes (A1) and pigments (P) are used. Or a mixture thereof.

  Examples of the dye (A1) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamides of acid dyes. of Dyers and Colorists)) and known dyes described in dyeing notes (Color Dyeing). In addition, according to chemical structure, azo dyes, cyanine dyes, other triarylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes Quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferably used.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 162;
C. I. Solvent Red 45, 49, 125, 130, 218;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339,341,345,346,349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 17, 19, 30, 102;
C. I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes,

C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 2 5,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. C. such as Disperse Yellow 54, 76 I. Disperse dyes,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. C. such as Basic Green 1; I. Basic dyes,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; I. Reactive dyes,
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Vat dye,
Etc.
Of these, blue dyes, violet dyes and red dyes are preferred.
These dyes may be used alone or in combination of two or more.

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

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

If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The pigments preferably have a uniform particle size.
The pigment can be made into a pigment dispersion in a state where the pigment dispersant is uniformly dispersed in the solution by carrying out a dispersion treatment by containing the pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

The content rate of the compound (1) of this invention becomes like this. Preferably it is 1 to 100 mass% with respect to the total amount of a coloring agent (A), More preferably, it is 10 to 100 mass%.
When the dye (A1) is contained, the content thereof is preferably 0.5% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 90% by mass or less, with respect to the total amount of the colorant (A). It is. When the pigment (P) is contained, the content thereof is preferably 35% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 70% by mass or less with respect to the total amount of the colorant (A). More preferably, it is 1 mass% or more and 50 mass% or less.
The content of the colorant (A) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and further preferably 5% by mass with respect to the total amount of the solid content. % To 50% by mass. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

  In this specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as “resin (B)”) is derived from at least one monomer (Ba) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. A copolymer containing a structural unit is preferred.
Examples of such a resin (B) include the following resins [K1] to [K6].
Resin [K1] at least one monomer (Ba) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(Ba)”); A copolymer of a monomer (Bb) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(Bb)”);
Resin [K2] (Ba), (Bb), and monomer (Bc) copolymerizable with (Ba) (however, different from (Ba) and (Bb)) (hereinafter referred to as “(Bc)”) In some cases)
Resin [K3] Copolymer of (Ba) and (Bc);
Resin [K4] Resin obtained by reacting (Bb) with a copolymer of (Ba) and (Bc);
Resin [K5] Resin obtained by reacting (Ba) with a copolymer of (Bb) and (Bc);
Resin [K6] A resin obtained by reacting a copolymer of (Bb) and (Bc) with (Ba) and further reacting with a carboxylic acid anhydride.

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

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

  Examples of (Bb) include a monomer (Bb1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(Bb1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. A monomer (Bb2) (hereinafter sometimes referred to as “(Bb2)”), a monomer (Bb3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(Bb3)”), etc. Can be mentioned.

  As (Bb1), for example, a monomer (Bb1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(Bb1-1)”) And a monomer (Bb1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(Bb1-2)”).

  (Bb1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. Specifically, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl ( (Meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6 -Bis (Glycizi Ruoxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4, Examples include 5-tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) styrene.

  Examples of (Bb1-2) include vinylcyclohexene monooxide, 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 Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), represented by the formula (II) And a compound represented by the formula (III).

[In Formula (II) and Formula (III), R ^a and R ^b each 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 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 alkyl group having 1 to 4 carbon atoms of R ^a and R ^b include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which the hydrogen atom in R ^a and R ^b is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- Examples include hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group. It is done.
Examples of R ^a and R ^b include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, 1- A hydroxyethyl group and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group having 1 to 6 carbon atoms of R ^c include a linear or branched alkanediyl group, such as a methylene group, an ethylene group, a propane-1,2-diyl group, and a butane-1,4. -Linear alkanediyl groups such as diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group; branched alkanediyl groups such as propane-1,2-diyl group; It is done.
The X ^a and X ^b, a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- and * -R ^c -NH- and the like, preferably a single bond, * -R ^c - and * -R ^c -O- and the like, more preferably a single bond and * -R ^c -O- may be mentioned, specifically, more preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O— are particularly preferable, and a single bond and * —CH ₂ CH ₂ —O— are particularly preferable (* represents a bond with O).

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), and the formula (II-11) to the formula (II-) are preferable. The compound represented by 15) is mentioned, More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) is mentioned.

  Examples of the compound represented by the formula (III) include compounds represented by any one of the formulas (III-1) to (III-15). Among them, the formula (III-1), the formula (III-3), the formula (III-5), the formula (III-7), the formula (III-9), and the formula (III-11) to the formula (III-) are preferable. 15), and more preferably compounds represented by formula (III-1), formula (III-7), formula (III-9) and formula (III-15).

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

  (Bb2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. As (Bb2), 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  (Bb3) is preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (Bb3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

  (Bb) is preferably (Bb1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (Bb1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 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 this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) ) (In the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Cyclo [5.2.1.0 ^{2, 6]} decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid ester of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. A bicyclo unsaturated compound;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and 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 and vinylidene chloride Halogenated hydrocarbons such as: vinyl group-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; .
Among these, (Bc) is preferably a vinyl group-containing aromatic compound, a dicarbonylimide derivative, or a bicyclounsaturated compound from the viewpoint of copolymerization reactivity and heat resistance. Specifically, styrene, vinyl toluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N -Benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

In the resin [K1], the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1]
Structural unit derived from (Ba); 2 to 60 mol%
Structural unit derived from (Bb); 40 to 98 mol%
It is preferable that
Structural unit derived from (Ba); 10-50 mol%
Structural unit derived from (Bb); 50-90 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter are excellent. Tend.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

Specifically, a predetermined amount of (Ba) and (Bb), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to obtain a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used.
Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). As the solvent, any solvent that dissolves each monomer may be used. Examples of the solvent (E) for the colored curable resin composition of the present invention include a solvent described later.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. Among these, by using the solvent contained in the colored curable resin composition of the present invention as a solvent in this polymerization, the solution after the reaction is used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the production process of the colored curable resin composition of the present invention can be simplified, which is preferable.

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (Ba); 2 to 45 mol%
Structural unit derived from (Bb); 2-95 mol%
Structural unit derived from (Bc); 1 to 65 mol%
It is preferable that
Structural unit derived from (Ba); 5 to 40 mol%
Structural unit derived from (Bb); 5 to 80 mol%
Structural unit derived from (Bc); 5-60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, There is a tendency to be excellent in heat resistance and mechanical strength.

  Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

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

Resin [K4] obtains a copolymer of (Ba) and (Bc), and (Ba) has a carboxylic acid and / or carboxylic acid anhydride (Ba) having a cyclic ether having 2 to 4 carbon atoms of (Bb). It can manufacture by adding to.
First, a copolymer of (Ba) and (Bc) is produced in the same manner as described for the production method of the resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same as that described for the resin [K3].

Next, the C2-C4 cyclic ether which (Bb) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (Ba) in the copolymer.
Subsequent to the production of the copolymer of (Ba) and (Bc), the atmosphere in the flask is replaced with nitrogen to air, and (Bb), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
As usage-amount of (Bb), 5-80 mol is preferable with respect to 100 mol of (Ba), and 10-75 mol is more preferable. By adjusting the amount of (Bb) used within this range, the storage stability of the colored curable resin composition, the developability when forming the pattern, and the solvent resistance, heat resistance, and mechanical strength of the resulting pattern are obtained. And the balance of sensitivity tends to be good. Since the reactivity of the cyclic ether is high and unreacted (Bb) hardly remains, (Bb1) is preferable as (Bb1) used in the resin [K4], and (Bb1-1) is more preferable.
As the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (Ba), (Bb), and (Bc). As a usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (Ba), (Bb), and (Bc).
The reaction conditions such as the charging method of each reagent, the reaction temperature, and the reaction time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

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

Furthermore, as a second step, the cyclic ether derived from (Bb) of the copolymer of (Bb) and (Bc) under the same conditions as in the method for producing the resin [K4], the carboxylic acid of (Ba) or Resin [K5] can be obtained by reacting carboxylic anhydride.
In the second stage, the amount of (Ba) to be reacted with the copolymer of (Bb) and (Bc) is preferably 5 to 80 mol with respect to 100 mol of (Bb). Since the reactivity of the cyclic ether is high and unreacted (Bb) hardly remains, (Bb1) is preferable as (Bb1) used in the resin [K5], and (Bb1-1) is more preferable.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl. Resin [K1] such as (meth) 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 - epoxytricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide / 2-hydroxy Ethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl - Resin [K2] such as 3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid Copolymer, resin such as benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; glycidyl in benzyl (meth) acrylate / (meth) acrylic acid copolymer (Meth) acrylate added resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4] such as a resin obtained by adding ricidyl (meth) acrylate, a resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer A resin obtained by reacting a tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid; a tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer; Resin [K5] such as resin reacted with (meth) acrylic acid; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and (meth) acrylic acid reacted with tetrahydrophthalic acid Examples thereof include a resin [K6] such as a resin reacted with an anhydride.

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

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is within the above range, the hardness of the coating film formed from the colored curable resin composition is improved, the residual film ratio during development is high, the solubility in the developer in the unexposed area is good, and coloring The pattern resolution tends to improve.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

  The content of the resin (B) is preferably 5 to 65% by mass, more preferably 6 to 60% by mass, and further preferably 7 to 55% by mass with respect to the total amount of the solid content. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution and remaining film ratio of the colored pattern tend to be improved. The resin (B) may be more or less than the compound (1).

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

  Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. And the above-mentioned (Ba), (Bb) and (Bc).

  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, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

  Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. .
Further, the content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 33: 67-80: 20.
Further, the content ratio of the total of the compound (1) and the resin (B) of the present invention to the polymerizable compound (C) [the total of the compound and the resin (B): the polymerizable compound (C)] is On the basis, it is preferably 70:30 to 40:60, more preferably 70:30 to 50:50.
When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

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

  The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

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

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one And other commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF).
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyldimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

  The biimidazole compound is preferably, for example, a compound represented by the formula (d5).

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

Examples of the aryl group having 6 to 10 carbon atoms of R ^{13 to} R ¹⁸ include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable.
Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably a chlorine atom is mentioned. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example, Preferably a methoxy group is mentioned.

  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 (trialkoxy) Phenyl) biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.) and a phenyl group at the 4,4 ′, 5,5′-position are substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913). Among these, compounds represented by the following formula and mixtures thereof are preferable.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -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-methylpheny ) 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.

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.
These are preferably used in combination with a polymerization initiation aid (D1) (among others) described below.

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

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

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

  Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylbenzoate Aminobenzoic acid esters such as aminoethyl and 2-dimethylhexyl 4-dimethylaminobenzoate; N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis ( Diethylamino) benzophenone and alkylaminobenzophenone such as 4,4′-bis (ethylmethylamino) benzophenone; and the like, among them, preferably alkylaminobenzophenone, more preferably 4 4'-bis (diethylamino) benzophenone. Moreover, you may use commercial items, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, Examples include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

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

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used individually or in combination of 2 or more types. Examples of the solvent (E) include ester solvents (solvents containing —COO— in the molecule and not containing —O—), ether solvents (solvents containing —O— in the molecule and not containing —COO—). , Ether ester solvent (solvent containing —COO— and —O— in the molecule), ketone solvent (solvent containing —CO— in the molecule and not containing —COO—), alcohol solvent (OH in the molecule) And a solvent that does not contain -O-, -CO-, and -COO-), an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

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

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

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.
Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, di Propylene glycol methyl ether acetate, ethyl lactate, 3-methoxy Butyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone and N- methylpyrrolidone is more preferred.

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

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) .

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

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002%, based on the total amount of the colored curable resin composition. The content is from 0.1% by mass to 0.1% by mass, more preferably from 0.005% by mass to 0.07% by mass. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. It can be prepared by mixing a leveling agent (F), a polymerization initiation assistant (D1) and other components used as necessary.
The pigment in the case of containing the pigment (P) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
It is preferable to prepare a solution by dissolving compound (1) in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.
When the dye (A-1) is used, the dye (A-1) may be dissolved in part or all of the solvent (E) in advance to prepare a solution. Further, the solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.

<Manufacturing method of coloring pattern, coating film and 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, and among them, a photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the colored pattern forming method, a coating film (in particular, a colored coating film) that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and coating film (in particular, the colored coating film) formed as described above can be used as the color filter of the present invention.
The film thickness of the colored pattern, coating film or color filter to be produced is not particularly limited and can be appropriately adjusted according to the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm. More preferably, it is 0.5 to 6 μm.

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

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

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be irradiated with parallel rays uniformly and the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. It is preferable.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Furthermore, it is preferable to post-bake the obtained colored pattern. As post-baking temperature, 150-250 degreeC is preferable and 160-235 degreeC is more preferable. As post-baking time, 1-120 minutes are preferable and 10-60 minutes are more preferable.

  The compound of this invention can manufacture the coating film excellent in heat resistance and NMP tolerance with the colored curable resin composition using this. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
In the following, NMR was measured with an FT-NMR apparatus trade name “MR-400” manufactured by Agilent Technologies. ^{In 1} H-NMR, a sample was dissolved in deuterated disulfide under conditions of room temperature, pulse width of 5.8 μs (45 ° pulse), uptake time of 3.5 seconds, waiting time of 3.5 seconds, and integration number of 16 times. The deuterated dimethyl sulfoxide signal was used as the internal standard for chemical shift (δ2.50). ¹⁹ F-NMR was prepared by dissolving a sample in deuterated disulfide under the conditions of room temperature, pulse width 4.75 μs (45 ° pulse), uptake time 0.84 seconds, waiting time 3.6 seconds, and integration number 32 times. It was measured. Separately measured hexafluorobenzene signal was used as an external standard for chemical shift (δ-163.0).
In the following, the structure of the compound was confirmed by mass spectrometry (LC; 1200 type manufactured by Agilent Technologies, MASS; LC / MSD type manufactured by Agilent Technologies). The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the SEC method under the following conditions.
Equipment: HLC-8120 manufactured by Tosoh Corporation
Column; TSKgel α4000 + α3000 + α2500 + TSKGuardcolumn
Column temperature: 40 ° C
Solvent: 50 mM LiBr / DMF
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.1% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-1, F-4, F-288, A-2500, A-500, A-5000

[Synthesis Example 1]
The following reaction was performed in a nitrogen atmosphere. After charging 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a condenser and a stirrer, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, followed by stirring for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4′-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours. When water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of the compound represented by the formula (BP3). The yield was 53%.

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

[Synthesis Example 3]
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer is charged with 8.2 parts of the compound represented by the formula (BI-7), 10.0 parts of the compound represented by the formula (BP3) and 20.0 parts of toluene. Then, 12.2 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18). The yield was 100%.

Identification of compound represented by formula (A-II-18) (mass spectrometry) ionization mode = ESI +: m / z = 687 [M-Cl] ⁺
(NMR)
¹ H-NMR δ 7.7-7.1 (m, 21H), 6.96 (t, 1H), 6.8-6.6 (br, 4H), 4.4-4.2 (br, 1H) ), 4.0-3.8 (br, 1H), 3.40 (s, 6H), 2.30 (s, 3H), 1.27 (t, 3H)
¹⁹ F-NMR δ-109.0 (s)

[Synthesis Example 4]
(Synthesis of nonafluorobutanesulfonamide)
158 parts of 0.4M ammonia tetrahydrofuran solution (manufactured by Sigma-Aldrich Japan Co., Ltd.) was added to the flask in a nitrogen atmosphere. While this flask was immersed in a dry ice / 2-propanol bath and cooled, 10.0 parts of nonafluorobutanesulfonic acid fluoride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring. After completion of dropping, stirring was continued for 1 hour while cooling. After raising the temperature to room temperature, 8.95 parts of water and 17.9 parts of dichloromethane were added, transferred to a separatory funnel, and hydrochloric acid was added until the aqueous layer became neutral, followed by liquid separation. The collected organic layer was washed with 17.9 parts of saturated brine and dried over anhydrous magnesium sulfate. The organic layer was distilled and dried to obtain 3.92 parts of nonafluorobutanesulfonamide with a yield of 38%.
About the said nonafluorobutane sulfonamide, it confirmed that it was the target compound from the following analysis result.
(Mass spectrometry) Ionization mode = ESI−: m / z = 298 [M−H] ⁻
(NMR)
¹ H-NMR δ 9.14 (br, 2H)
¹⁹ F-NMR δ-76.3 (t), -110.1 (t), -117.2 (t), -121.7 (td)

[Synthesis Example 5]
(Synthesis of (p-vinylphenyl) nonafluorobutanesulfonylimidic acid triethylamine salt)
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed to form a nitrogen atmosphere. 10.0 parts of p-vinylbenzenesulfonic acid sodium salt hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.), N, 1.84 parts of N-dimethylformamide and 72.5 parts of acetonitrile were added. While stirring, 11.8 parts of thionyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise in an ice bath.
After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 3 hours. The reaction was stopped with an aqueous sodium hydrogen carbonate solution, and a liquid separation operation was performed with an aqueous sodium hydrogen carbonate solution and ethyl acetate. The separated organic layer was washed with 18 weight percent saline and then dried over anhydrous magnesium sulfate. The organic layer was distilled and dried under reduced pressure to obtain 8.32 parts of p-vinylbenzenesulfonyl chloride in a yield of 82%.
Next, an appropriate amount of nitrogen was flowed into a flask equipped with a dropping funnel and a stirrer to form a nitrogen atmosphere, and 10.0 parts of nonafluorobutanesulfonamide synthesized in Synthesis Example 2, 118 parts of dichloromethane, and 13.3 parts of triethylamine were added. . While stirring, 8.32 parts of p-vinylbenzenesulfonyl chloride was added dropwise in an ice bath. Two hours after the dropwise addition, the temperature was raised to room temperature, and stirring was further continued for 5 hours. The reaction was stopped with ion exchange water, and the organic layer was washed with ion exchange water. The extract was dried over anhydrous magnesium sulfate, filtered, and purified by column chromatography to obtain 11.7 parts of the desired product in a yield of 63%.
The (p-vinylphenyl) nonafluorobutanesulfonylimidic acid triethylamine salt represented by the following structural formula (M-1) was confirmed to be the target compound from the following analysis results.

(Mass spectrometry)
Ionization mode = ESI +: (m / z) 103 [(CH ₂ CH ₃ ) ₃ NH] ⁺
Ionization mode = ESI−: (m / z) 464 [M−H] ⁻
(NMR)
¹ H-NMR δ 8.83 (br, 1H), 7.73 (d, J = 8.3 Hz, 2H), 7.58 (d, J = 8.3 Hz, 2H), 6.79 (dd, 1H) ), 5.96 (d, 1H), 5.38 (d, 1H), 3.09 (q, 6H), 1.17 (t, 9H)
¹⁹ F-NMR δ-76.3 (t), -109.0 (t), -117.0 (t), -121.6 (t)

[Synthesis Example 6]
(Synthesis of (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt)
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed to form a nitrogen atmosphere. 10.0 parts of p-vinylbenzenesulfonic acid sodium salt hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.), N, 1.84 parts of N-dimethylformamide and 72.5 parts of acetonitrile were added. While stirring, 11.8 parts of thionyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise in an ice bath.
After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 3 hours. The reaction was stopped with an aqueous sodium hydrogen carbonate solution, and a liquid separation operation was performed with an aqueous sodium hydrogen carbonate solution and ethyl acetate. The separated organic layer was washed with 18 weight percent saline and then dried over anhydrous magnesium sulfate. The organic layer was distilled and dried under reduced pressure to obtain 8.32 parts of p-vinylbenzenesulfonyl chloride in a yield of 82%.
Next, an appropriate amount of nitrogen was flowed into a flask equipped with a dropping funnel and a stirrer to form a nitrogen atmosphere, and 10.0 parts of trifluoromethanesulfonamide (Tokyo Chemical Industry Co., Ltd.), 243 parts of dichloromethane, and 24.8 parts of triethylamine were added. added. While stirring, 17.7 parts of p-vinylbenzenesulfonyl chloride was added dropwise in an ice bath. After raising the temperature to room temperature 2 hours after dropping, the reaction was stopped with ion-exchanged water, and the organic layer was washed with ion-exchanged water. The extract was dried over anhydrous magnesium sulfate, filtered, and purified by column chromatography to obtain 23.2 parts of the desired product in a yield of 80%.
The (p-vinylphenyl) trifluoromethanesulfonylimido triethylamine salt represented by the following structural formula (M-2) was confirmed to be the target compound from the following analysis results.

(Mass spectrometry)
Ionization mode = ESI +: (m / z) 103 [(CH ₂ CH ₃ ) ₃ NH] ⁺
Ionization mode = ESI−: (m / z) 314 [M−H] ⁻
(NMR)
¹ H-NMR δ 8.83 (br, 1H), 7.72 (d, 1H), 7.58 (d, 1H), 6.79 (dd, 1H), 5.95 (d, 1H), 5 .39 (d, 1H), 3.09 (m, 6H), 1.17 (t, 9H)
¹⁹ F-NMR δ-73.8 (s)

[Synthesis Example 7]
(Synthesis of polymer 1)
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed to form a nitrogen atmosphere, 10.0 parts of (p-vinylphenyl) nonafluorobutanesulfonylimidic acid triethylamine salt, 27.0 parts of cyclohexanone, 7.5 parts of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and heated to 100 ° C. with stirring. Next, a solution obtained by dissolving 0.12 part of α, α′-azoisobutyronitrile (manufactured by Kanto Chemical Co., Inc.) in cyclohexanone was dropped into the flask over 15 minutes using a dropping funnel. After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for 3 hours, and then cooled to room temperature. 106 parts of acetone was added to the solution and stirred, and the mixture was added dropwise to 3300 parts of hexane to precipitate a copolymer. It was washed with hexane and dried to obtain 12.9 parts of resin. The polymer 1 was confirmed to be the target compound by ¹ H-NMR analysis, and the ratio of p and q in the following structural formula (P-1) was found to be 1: 1.2. The weight average molecular weight of the polymer 1 was 12000, the number average molecular weight was 8500, and the molecular weight distribution was 1.4.

[Synthesis Example 8]
(Synthesis of polymer 2)
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was passed to form a nitrogen atmosphere, 10.0 parts of (p-vinylphenyl) nonafluorobutanesulfonylimidic acid triethylamine salt, 27.1 parts of cyclohexanone, 19.6 parts of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and heated to 100 ° C. with stirring. Next, a solution obtained by dissolving 0.10 parts of α, α′-azoisobutyronitrile (manufactured by Kanto Chemical Co., Inc.) in cyclohexanone was dropped into the flask over 12 minutes using a dropping funnel. After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for 3 hours, and then cooled to room temperature. To the solution, 221 parts of acetone was added and stirred, and dropped into 4850 parts of hexane to precipitate a copolymer. It was washed with hexane and dried to obtain 22.6 parts of resin. The polymer 2 was confirmed to be the target compound by ¹ H-NMR analysis, and the ratio of p and q in the following structural formula (P-2) was found to be 1: 6.7. The weight average molecular weight of the polymer 2 was 10,300, the number average molecular weight was 7,500, and the molecular weight distribution was 1.4.

[Synthesis Example 9]
(Synthesis of Polymer 3)
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, 10.0 parts of (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, 37.1 parts of cyclohexanone, methacrylic acid. 13.5 parts of glycidyl acid (Tokyo Chemical Industry Co., Ltd.) was added and heated to 100 ° C. with stirring. Next, a solution obtained by dissolving 0.15 part of α, α′-azoisobutyronitrile (manufactured by Kanto Chemical Co., Inc.) in cyclohexanone was dropped into the flask over 15 minutes using a dropping funnel. After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for 3 hours, and then cooled to room temperature. 110 parts of acetone was added to the solution and stirred, and the resulting solution was added dropwise to 4850 parts of hexane to precipitate a copolymer. Washing with hexane and drying gave 17.2 parts of resin in 74% yield. The polymer 3 was confirmed to be the target compound by ¹ H-NMR analysis, and the ratio of p and q in the following structural formula (P-3) was found to be 1: 2.3. The weight average molecular weight of the polymer 3 was 23000, the number average molecular weight was 11000, and the molecular weight distribution was 2.1.

[Example 1]
(Synthesis of Colorant 1)
10.0 parts of the polymer 1 is dissolved in 102 parts of dimethyl sulfoxide, and the cationic dye represented by the following structural formula (Q-1) is calculated from the copolymerization ratio of the polymer 1 (M- 90 mol% amount with respect to the number of moles of the structural unit derived from the compound represented by 1) was added and stirred at 900 hPa at 40 ° C for 30 minutes using an evaporator. 1030 parts of water was added, and the precipitate was collected by filtration and washed with water. The precipitate was dried under reduced pressure to obtain 7.1 parts of colorant 1 represented by the following structural formula (Q-2) in a yield of 38%.

[Example 2]
(Synthesis of Colorant 2)
10.0 parts of the polymer 2 is dissolved in 23.4 parts of dimethyl sulfoxide, and the cationic dye represented by the structural formula (Q-1) is calculated from the copolymerization ratio of the polymer 2 (M The amount of 90 mol% with respect to the number of moles of the structural unit derived from the compound represented by -1) was added, and the mixture was stirred at 900 hPa at 40 ° C for 30 minutes using an evaporator. 2320 parts of water was added, and the precipitate was collected by filtration and washed with water. The precipitate was dried under reduced pressure to obtain 23.6 parts of Colorant 2 represented by the following structural formula (Q-3) in a yield of 80%.

Example 3
(Synthesis of Colorant 3)
10.0 parts of the polymer 3 is dissolved in 101 parts of dimethyl sulfoxide, and a cationic dye represented by the following structural formula (Q-1) is calculated from the copolymerization ratio of the polymer 3 (M-2 ) Was added in an amount of 90 mol% based on the number of moles of the structural unit derived from the compound, and the mixture was stirred at 900 hPa at 40 ° C. for 30 minutes using an evaporator. 1000 parts of water was added, and the precipitate was collected by filtration and washed with water. The precipitate was dried under reduced pressure to obtain 15.4 parts of colorant 3 represented by the following structural formula (Q-4) in a yield of 82%.

[Synthesis Example 10]
(Synthesis of Colorant 4)
10.0 parts of polymer 3 is dissolved in 159 parts of dimethyl sulfoxide, and Victoria Pure Blue BOH (CI-42595) (Hodogaya Chemical Co., Ltd.), which is a cationic dye represented by the following structural formula (R-1) 90% by mol with respect to the number of moles of the structural unit derived from the compound represented by the structural formula (M-2) calculated from the copolymerization ratio of the polymer 1, and 40 ° C. at 900 hPa using an evaporator Stir for 30 minutes. 1600 parts of water was added, and the precipitate was collected by filtration and washed with water. The precipitate was dried under reduced pressure to obtain 16.4 parts of colorant 4 represented by the following structural formula (R-2) in a yield of 71%.

[Synthesis Example 11]
(Synthesis of Resin B-1)
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was flushed with an appropriate amount of nitrogen and replaced with a nitrogen atmosphere. 141 parts by weight of ethyl lactate (Tokyo Chemical Industry Co., Ltd.), propylene glycol monomethyl ether acetate (Tokyo Chemical Industry) 178 parts by weight were added and heated to 85 ° C. with stirring. Next, 38 parts by weight of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 25 parts by weight of E-DCPA (manufactured by Daicel Corporation), 137 parts by weight of cyclohexylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-hydroxyethyl A mixed solution of 50 parts by weight of methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 338 parts by weight of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped over 5 hours. Meanwhile, a mixed solution in which 5 parts by weight of 2,2-azobisisobutyronitrile (manufactured by Kanto Chemical Co., Ltd.) was dissolved in 88 parts by weight of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was taken over 6 hours. And dripped. After completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature, and a copolymer having a B-type viscosity (23 ° C.) of 23 mPas, a solid content of 25.6% by weight, and a solution acid value of 28 mg-KOH / g, a resin B-1 was obtained. The resulting copolymer had a weight average molecular weight Mw of 8000 and a dispersity of 2.1.

0.097 g of the compound represented by the formula (Q-2) is dissolved in acetonitrile to a volume of 100 cm ³ , 2 cm ^{3 of} which is diluted with acetonitrile to a volume of 250 cm ³ (concentration: 0.0078 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.3 (arbitrary unit) at λmax = 618 nm.

0.099 g of the compound represented by the formula (Q-3) is dissolved in acetonitrile to a volume of 100 cm ³ , 2 cm ^{3 of} which is diluted with ion-exchanged water to a volume of 250 cm ³ (concentration: 0.079 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 0.7 (arbitrary unit) at λmax = 621 nm.

0.097 g of the compound represented by formula (Q-4) was dissolved in acetonitrile to a volume of 100 cm ^3, and diluted with 2 cm ^{3 of} acetonitrile to a volume of 250 cm ³ (concentration: 0.0078 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.1 (arbitrary unit) at λmax = 619 nm.

0.050 g of the compound represented by the formula (R-2) was dissolved in chloroform to a volume of 50 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 250 cm ³ (concentration: 0.080 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.6 (arbitrary unit) at λmax = 610 nm.

(Preparation of colored curable resin composition)
Example 4
Colorant (A): 11 parts of a compound represented by formula (Q-2);
Alkali-soluble resin (B): 13 parts of resin (B-1);
Polymerizable compound (C): Photocurable monomer (NK ester A95550: Shin-Nakamura Chemical Co., Ltd.) 12 parts;
Polymerization initiator (D): Photopolymerization initiator (OXE01: manufactured by BASF Japan Ltd.) 3.1 parts;
Solvent (E): 68 parts 4-hydroxy-4-methyl-pentanone;
Solvent (E): 10 parts of propylene glycol monomethyl ether;
Solvent (E): 58 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.025 part;
Fluorosurfactant (Megafac F-554; manufactured by DIC Corporation) 0.034 parts;
Antioxidant (G):
(Sumilyzer GP: Sumitomo Chemical Co., Ltd.) 1.6 parts;
Silane coupling agent (H):
(KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.4 parts was mixed to obtain a colored curable resin composition.

Example 5
Colorant (A): 23 parts of a compound represented by formula (Q-3);
Alkali-soluble resin (B): 8.4 parts of resin (B-1);
Polymerizable compound (C): Photocurable monomer (NK ester A95550: Shin-Nakamura Chemical Co., Ltd.) 16 parts;
Polymerization initiator (D): Photopolymerization initiator (OXE01: manufactured by BASF Japan Ltd.) 3.9 parts;
Solvent (E): 84 parts of 4-hydroxy-4-methyl-pentanone;
Solvent (E): 12 parts of propylene glycol monomethyl ether;
Solvent (E): 97 parts of propylene glycol monomethyl ether acetate;
And leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.032 parts;
Fluorosurfactant (Megafac F-554; manufactured by DIC Corporation) 0.042 parts;
Antioxidant (G):
(Sumilyzer GP: Sumitomo Chemical Co., Ltd.) 2.0 parts;
Silane coupling agent (H):
(KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part was mixed to obtain a colored curable resin composition.

Example 6
Colorant (A): 11 parts of a compound represented by formula (Q-4);
Alkali-soluble resin (B): 13 parts of resin (B-1);
13 parts of a polymerizable compound (C) photocurable monomer (NK ester A9550: manufactured by Shin-Nakamura Chemical Co., Ltd.);
Polymerization initiator (D): 3.1 parts of photopolymerization initiator (OXE01: manufactured by BASF Japan Ltd.);
Solvent (E): 68 parts 4-hydroxy-4-methyl-pentanone;
Solvent (E): 10 parts of propylene glycol monomethyl ether;
Solvent (E): Propylene glycol monomethyl ether acetate 59 parts;
Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.025 part;
Fluorosurfactant (Megafac F-554; manufactured by DIC Corporation) 0.034 parts;
Antioxidant (G):
(Sumilyzer GP: Sumitomo Chemical Co., Ltd.) 1.6 parts;
Silane coupling agent (H):
(KBM-503: Shin-Etsu Chemical Co., Ltd.) 0.4 part was mixed and the colored curable resin composition was obtained.

Comparative Example 1
Colorant (A): 15 parts of a compound represented by formula (R-2);
Alkali-soluble resin (B): 12 parts of resin (B-1);
Polymerizable compound (C): Photocurable monomer (NK ester A95550: Shin-Nakamura Chemical Co., Ltd.) 14 parts;
Polymerization initiator (D): Photopolymerization initiator (OXE01: manufactured by BASF Japan Ltd.) 3.4 parts;
Solvent (E): 73 parts of 4-hydroxy-4-methyl-pentanone;
Solvent (E): 10 parts of propylene glycol monomethyl ether;
Solvent (E): 71 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.027 parts;
Fluorosurfactant (Megafac F-554; manufactured by DIC Corporation) 0.037 parts;
Antioxidant (G):
(Sumilyzer GP: Sumitomo Chemical Co., Ltd.) 1.7 parts;
Silane coupling agent (H):
(KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part was mixed to obtain a colored curable resin composition.

[Production of color filters]
The colored curable resin composition was applied on a 2-inch square glass substrate (# 1737; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), exposure was performed in an air atmosphere with an exposure amount of 60 mJ / cm ² (based on 365 nm). A photomask was not used. The exposed colored composition layer was post-baked in an oven at 230 ° C. for 20 minutes to prepare a color filter (film thickness: 2 to 5 μm).

[Heat resistance evaluation]
The coating film of the colored photosensitive resin composition was heated at 230 ° C. for 1 hour, and the color difference (ΔEab *) before and after the heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The results of carrying out the above heat resistance evaluations on the coating films obtained in Examples 1 to 3 and Comparative Example 1 were compared with the improvement rate based on ΔEab * of the coating film obtained in Comparative Example 1 ({ΔEab * ( Comparative Example 1) -ΔEab * (Example)} / ΔEab * (Comparative Example 1)), the coating film obtained in Example 4 had an improvement rate of 62.3% and the coating obtained in Example 5 The improvement rate of the film was 36.3%, and the improvement rate of the coating film obtained in Example 6 was 65.1%.

[NMP resistance evaluation]
A central 1.9 centimeter square of the coating film of the colored photosensitive resin composition is cut off and immersed in N-methylpyrrolidone at 80 ° C. for 5 minutes, and the color difference (ΔEab *) before and after the coating film is immersed is measured by a colorimeter (OSP). -SP-200; manufactured by OLYMPUS). The results of carrying out the above NMP resistance evaluation on the coating films obtained in Examples 1 to 3 and Comparative Example 1 were compared with the improvement rate based on ΔEab * of the coating film obtained in Comparative Example 1 ({ΔEab * ( Comparative Example 1) -ΔEab * (Example)} / ΔEab * (Comparative Example 1)), the coating film obtained in Example 4 had an improvement rate of 49%, and the coating film obtained in Example 5 The improvement rate was 68%, and the improvement rate of the coating film obtained in Example 6 was 46%.

When the colored curable resin composition containing the compound of the present invention is used, a coating film excellent in heat resistance and NMP resistance can be provided. The coating film is useful as a color filter, and the color filter is useful as a color filter used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Claims (9)

(A) a cation represented by the formula (AI), and
(B) A compound comprising a polymer having a structural unit derived from an anion represented by the formula (A-II).

[In Formula (AI), R ^{41 to} R ⁴⁶ are each independently a hydrogen atom, an amino group or a C 1-20 alkyl group which may be substituted with an amino group or a halogen atom; A group in which one oxygen atom is inserted between methylene groups between the methylene groups constituting the alkyl group, an aryl group having 6 to 20 carbon atoms which may be substituted, or a substituent; Or an aralkyl group having 7 to 30 carbon atoms.
R ⁴¹ and R ⁴² may form a ring with the nitrogen atom to which they are bonded, R ⁴³ and R ⁴⁴ may form a ring with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ^{42 46} may form a ring together with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom is inserted between methylene groups constituting the alkyl group. It may be.
^R55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms.
X1 represents an oxygen atom, —N (R ⁵⁷ ) —, or a sulfur atom.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

[In Formula (A-II), X represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom.
Y represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a combination thereof, and the methylene group constituting the aliphatic hydrocarbon group is an oxygen atom. , —CO— or —N (R ⁵⁸ ) — may be substituted.
R ⁶¹ represents a hydrogen atom or a methyl group.
R ⁵⁸ represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or a substituent. An aralkyl group having 7 to 30 carbon atoms which may be present. ]   The compound according to claim 1, wherein X is a C 1-8 alkyl group substituted with a fluorine atom.   The compound according to claim 1 or 2, wherein X is a nonafluorobutyl group.   The compound according to any one of claims 1 to 3, wherein Y is an arylene group.   Y is a phenylene group, The compound in any one of Claims 1-4.   A colored curable resin composition comprising the compound according to claim 1, a resin, a polymerizable compound, and a polymerization initiator.   The coating film formed using the colored curable resin composition of Claim 6.   A color filter formed using the colored curable resin composition according to claim 6.   A display device comprising the color filter according to claim 8.