JP2017114955A - Novel cyanine compound and coloring curable resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel salt forming coloring agent capable of providing a color filter excellent in heat resistance.SOLUTION: There is provided a compound represented by the formula (A-I). A ring Zand a ring Zare each independently a substituted/unsubstituted heterocycle and N has a structure with onium, a counter anion Xis anion containing B, anion containing Al or anion containing at least one element of W, Mo, Si or P and O as essential elements, b1 is an integer of 1 to 20, Rto Rare each independently H, halogen, cyano group, substituted/unsubstituted C1 to 8 aliphatic hydrocarbon, substituted/unsubstituted C6 to 12 aromatic hydrocarbon or the like, u is an integer of 1 to 3, Rand Rare each independently H, substituted/unsubstituted C1 to 20 aliphatic hydrocarbon, substituted/unsubstituted aromatic hydrocarbon or the like, Rand Rare H, halogen or substituted/unsubstituted C1 to 6 hydrocarbon, p1 and p2 are each independently an integer of 0 to 2 and Ato Aare each independently CH or N.SELECTED DRAWING: None

Description

  The present invention relates to a novel cyanine compound and a colored curable resin composition containing the same.

A coating film formed from a colored curable resin composition containing a colorant is desired to have good heat resistance, and various techniques have been developed to improve heat resistance.
Patent Document 1 describes a colored curable resin composition containing a compound comprising a triarylmethane-based basic dye and a counter compound thereof.

JP 2014-170098 A

  In colored curable resin compositions containing triarylmethane-based and xanthene-based colorants as shown in these documents, various studies have already been conducted on heat resistance and the like, but in other colorants, Research on heat resistance is still not enough.

The present invention includes the following inventions.
[1] A cyanine compound represented by formula (AI) or formula (A-II).

[In the formulas (AI) and (A-II),
Ring Z ¹ to ring Z ⁶ each independently represent an optionally substituted heterocyclic ring. Ring Z ¹ and ring Z ² are independent of each other, or at least two of ring Z ³ , ring Z ⁴ , ring Z ^5, and ring Z ⁶ have a structure in which a nitrogen atom is oniumated.
R ^{a1 to} R ^a9 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a substituent. Represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have, and two selected from R ^a1 , R ^a2 and R ^a3 , or from each of R ^{a4 to} R ^a6 _and R ^{a7 to} R ^a9 Two selected may combine with each other to form a ring.
u, v, and w represent an integer of 0 or more and 3 or less.
R ^{a10 to} R ^a11 , R ^{a14 to} R ^a15 and R ^{a18 to} R ^a19 are each independently a monovalent aliphatic carbon atom having 1 to 20 carbon atoms which may have a hydrogen atom, a hydrogen atom or a substituent. A hydrogen group, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aralkyl group is represented.
R ^{a12 to} R ^a13 , R ^{a16 to} R ^a17 and R ^{a20 to} R ^a21 each independently represent a hydrogen atom, a halogen atom, or a monovalent fatty acid having 1 to 6 carbon atoms which may have a substituent. R ^a12 and R ^a13 , R ^a16 and R ^a17 , or R ^a20 and R ^a21 are bonded to each other to represent a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
p1 to p6 each independently represent an integer of 0 or more and 2 or less.
A ^{1 to} A ¹² each independently represent —C (H) — or a nitrogen atom.
The counter anions ^Xb1- and ^Xc1- contain an anion containing a boron atom, an anion containing an aluminum atom, and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements. An anion is represented, b1 and c1 represent the integer of 1-20.
n and m are determined so as to be equal to the positive charge caused by the ring Z ¹ and / or the ring Z ² , or the onium nitrogen atom of the ring Z ³ to the ring Z ⁶ .
L ¹ represents an optionally substituted divalent hydrocarbon group having 1 to 16 carbon atoms. ]
[2] The counter anions X ^b1− and X ^c1− are anions ^containing , independently of each other, at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements [1] ] The cyanine compound of description.
[3] The cyanine compound according to [1] or [2], wherein the counter anions ^Xb1- and ^Xc1- are anions of heteropolyacid or isopolyacid containing tungsten as an essential element, independently of each other.
[4] The cyanine compound according to any one of [1] to [3], wherein the compound represented by the formula (AI) is a compound represented by the formula (A-III).

[In the formula (A-III),
Ring Z ⁷ to ring Z ¹² each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
R ^{a1 to} R ^a9 , u, v, w, X ^b1- , X ^c1- , b1, c1, n, m, R ^{a10 to} R ^a13 , R ^{a15 to} R ^a17 , R ^{a19 to} R ^a21 , p1 to p6, L ¹ represents the same meaning as described above. ]
[5] In the formula (A-III),
Ring Z ⁷ to Ring Z ⁹ each independently represent a benzene ring or a naphthalene ring which is unsubstituted or substituted with a methyl group, an ethyl group, a chlorine atom or a trifluoromethyl group,
R ^a10 , R ^a11 , R ^a15 and R ^a19 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be unsubstituted or substituted with a halogen atom;
R ^a12 , R ^a13 , R ^a16 , R ^a17 , R ^a20 and R ^a21 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may be unsubstituted or substituted with a halogen atom. Represent,
The cyanine compound according to [4], wherein p1 and p2 each independently represent 2.
[6] R ^{a1 to} R ^a9 in the formulas (AI) to (A-III) each independently have a hydrogen atom, a cyano group, a halogen atom or a substituent having 1 to 1 carbon atoms. 8 represents a monovalent aliphatic hydrocarbon group, or two selected from R ^{a1 to} R ^a3 , R ^{a4 to} R ^a6 , and R ^{a7 to} R ^a9 are bonded to each other to form a ring [1 ] The cyanine compound in any one of [5].
[7] A colored curable resin composition comprising the cyanine compound according to any one of [1] to [6], a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
[8] A color filter formed using the colored curable resin composition according to [7].
[9] A display device including the color filter according to [8].

  The novel cyanine compound according to the present invention is excellent as a colored curable resin composition used for a color filter of a display device such as a liquid crystal display device because the color filter containing the novel cyanine compound has good heat resistance.

  The cyanine compound according to the present invention is represented by formula (AI) or formula (A-II). In the present specification, the invention is described in detail by using a compound having a specific resonance structure, and this resonance structure includes all other resonance structures.

[In the formulas (AI) and (A-II),
Ring Z ¹ to ring Z ⁶ each independently represent an optionally substituted heterocyclic ring. Ring Z ¹ and ring Z ² are independent of each other, or at least two of ring Z ³ , ring Z ⁴ , ring Z ^5, and ring Z ⁶ have a structure in which a nitrogen atom is oniumated.
R ^{a1 to} R ^a9 each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a substituent. ² represents an aromatic hydrocarbon group having 6 to 12 carbon atoms, and two selected from R ^a1 , R ^a2 and R ^a3 , or 2 selected from R ^{a4 to} R ^a6 _and R ^{a7 to} R ^a9 May combine with each other to form a ring.
u, v, and w represent an integer of 1 to 3.
R ^{a10 to} R ^a11 , R ^{a14 to} R ^a15 , and R ^{a18 to} R ^a19 are each independently a hydrogen atom, a hydrogen atom, or an ^optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, It represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms or an optionally substituted aralkyl group having 7 to 10 carbon atoms.
R ^{a12 to} R ^a13 , R ^{a16 to} R ^a17 , and R ^{a20 to} R ^a21 each independently represent a hydrogen atom, a halogen atom, or an ^optionally substituted aliphatic hydrocarbon having 1 to 6 carbon atoms. R ^a12 and R ^a13 , R ^a16 and R ^a17 , or R ^a20 and R ^a21 are bonded to each other to represent a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
p1 to p6 each independently represent an integer of 0 to 2.
A ^{1 to} A ¹² each independently represent —C (H) — or a nitrogen atom.
The counter anions ^Xb1- and ^Xc1- are each independently ^required to contain an anion containing a boron atom, an anion containing an aluminum atom, and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen. An anion contained as an element is represented, and b1 and c1 represent an integer of 1 to 20.
n and m are determined so as to be equal to the positive charge caused by the ring Z ¹ and / or the ring Z ² , or the onium nitrogen atom of the ring Z ³ to the ring Z ⁶ .
L ¹ represents an optionally substituted divalent hydrocarbon group having 1 to 16 carbon atoms. ]

<Cation site>
Ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ , and ring Z ⁶ each independently represent a heterocyclic ring which may be substituted. The heterocycle includes at least one heteroatom as a ring component, and may be monocyclic or polycyclic.
The hetero atom may be an atom selected from Group 15 or Group 16 elements in the periodic table, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.
Examples of the heterocyclic ring include an indole ring, a benzoindole ring, an indolenine ring, a benzoindolenin ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, and a quinoline ring. There are 8 heterocycles.
The heterocyclic ring represented by ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ is preferably an indole ring, a benzoindole ring, an indolenine ring or a benzoindolenine ring. A ring or an indolenine ring is more preferable.

As the substituent that the heterocyclic ring represented by ring Z ¹ to ring Z ⁶ may have,
C1-C6 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl Group;
Fragrance having 6 to 12 carbon atoms such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, naphthyl group Group hydrocarbon group;
An aralkyl group having 7 to 10 carbon atoms such as a benzyl group;
An alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group;
An aryloxy group having 6 to 10 carbon atoms such as a phenoxy group;
An aralkyloxy group having 7 to 10 carbon atoms such as a benzyloxy group;
Groups having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group;
Methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group An alkylsulfamoyl group having 1 to 8 carbon atoms such as a famoyl group, n-butylsulfamoyl group, di-n-butylsulfamoyl group, 2-ethylhexylsulfamoyl group;
An alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Vinyl group, allyl group, propen-2-yl group, methallyl group, but-3-en-1-yl group, but-3-en-2-yl group, but-3-en-3-yl group, penta An alkenyl group having 2 to 6 carbon atoms such as a -4-en-1-yl group;
Nitro group; cyano group; and the like.
When the substituent has a hydrogen atom, the hydrogen atom is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group. , Isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; aryloxy group such as phenoxy group, benzyloxy group; carboxy group; cyano group; nitro group; acryloyloxy group; methacryloyloxy group It may be substituted by.
The heterocyclic ring represented by ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ has 1 to 6 carbon atoms which may be substituted with a halogen atom as a substituent. It is preferable to have one or two aliphatic hydrocarbon groups.

A ^{1 to} A ¹² each independently represent —C (H) — or a nitrogen atom.

*-(CR ^a1 = CR ^a2 ) u-CR ^a3 = *, *-(CR ^a4 = CR ^a5 ) v-CR ^a6 = * or *-(in formulas (A-I) to (A-IV) CR ^a7 = CR ^a8 ) In the main skeleton represented by w-CR ^a9 = *, R ^{a1 to} R ^a9 each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a substituent. Represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, R ^{a1 to} R ^a3 , R ^{a4 to} R Two ^members selected from ^a6 and R ^{a7 to} R ^a9 may be bonded to each other to form a ring.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{a1 to} R ^a9 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. A linear alkyl group having 1 to 8 carbon atoms; a branched chain having 3 to 20 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group An alkyl group; an alicyclic saturated hydrocarbon group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group;
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R ^{a1 to} R ^a9 include a phenyl group and a naphthyl group.
Among the groups represented by R ^{a1 to} R ^a9 , ^examples of the substituent in the aliphatic hydrocarbon group and the aromatic hydrocarbon group include halogen atoms such as fluorine atom, chlorine atom and iodine; carbon such as methoxy group and ethoxy group An alkoxy group having 1 to 6 carbon atoms; a hydroxy group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; It is done.
In particular, the aromatic hydrocarbon group carbon having 6 to 12 carbon atoms which may have a substituent represented by R ^{a1 to} R ^a9 includes a phenyl group, an o-tolyl group, an m-tolyl group, p- Examples include tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, naphthyl group and the like.

Examples in which two selected from R ^{a1 to} R ^a3 , R ^{a4 to} R ^a6 , and R ^{a7 to} R ^a9 are bonded to each other to form a ring include R ^a1 and R ^a3 (similarly, R ^a4 and R ^a6 , R ^a7 and R ^a9 ) are ^combined to form a ring; R ^a2 and R ^a3 (similarly, R ^a5 and R ^a6 , R ^a8 and R ^a9 ) are ^combined to form a ring; R ^a1 And R ^a2 (similarly, R ^a4 and R ^a5 , R ^a7 and R ^a8 ) may be ^combined to form a ring.
More preferably, R ^a1 and R ^a3 (similarly, R ^a4 and R ^a6 , R ^a7 and R ^a9 ) are linked to form a ring. For example, the formula (Body-1) to the formula (Body-5) The 4- to 8-membered ring having at least one carbon-carbon double bond as shown in FIG. 5 is preferable, and the 6-membered ring formula (Body-3) is more preferable.
In formulas (Body-1) to (Body-5), R ^a2 is the same as described above, and R ^{a4 to} R ^a6 and R ^{a7 to} R ^a9 are read as R ^a5 and R ^a8 , respectively. . In the formulas (Body-1) to (Body-5), R ^a2 , R ^a5 and R ^a8 are preferably halogen atoms, and more preferably chlorine atoms.

  u, v, and w are integers of 1 to 3, preferably 1 or 2, and preferably 1 in terms of lightness of the obtained color filter.

Among them, R ^{a1 to} R ^a9 each independently represent a hydrogen atom, a cyano group, a halogen atom or an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, or R ^{a1 to} R ^a3. , R ^{a4 to} R ^a6 and R ^{a7 to} R ^a9 are preferably bonded to each other to form a ring,
R ^{a1 to} R ^a9 are each independently more preferably a hydrogen atom, a cyano group or a halogen atom,
More preferably, R ^a1 , R ^a2 , R ^a4 , R ^a5 , R ^a7 and R ^a8 are hydrogen atoms, and R ^a3 , R ^a6 and R ^a9 are hydrogen atoms or cyano groups.

R ^a10 , R ^a11 , R ^a14 , R ^a15 , R ^a18 and R ^a19 are each independently a hydrogen atom, an ^optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted group. Represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an optionally substituted aralkyl group having 7 to 10 carbon atoms.

^Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R ^a10 , R ^a11 , R ^a14 , R ^a15 , R ^a18 and R ^a19 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, C1-C20 linear alkyl groups such as heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and icosyl; isopropyl, isobutyl, sec-butyl, tert-butyl, C3-C20 branched alkyl group such as isopentyl group, neopentyl group and 2-ethylhexyl group; carbon number such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group 3-20 alicyclic saturated hydrocarbon groups; vinyl, propenyl, butenyl, pentenyl, hexenyl, 3-methyl Alkenyl groups having 1 to 8 carbon atoms such as ru-butenyl group, 4-methyl-pentenyl group and 5-methyl-hexenyl group; and the like.

The methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group is —O—, —CO—, —NR ¹¹ —, —OCO—, —COO—, —OCONH—, —NHCOO—, —CONH. It may be substituted with-or -NHCO-.

R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include the same groups as the saturated hydrocarbon group having 1 to 20 carbon atoms in R ^a10 , R ^a11 , R ^a14 , R ^a15 , R ^a18 and R ^a19 . A methyl group is preferred. Examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group, a phenylethyl group, and a phenylbutyl group.

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

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

Examples of the group in which the methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group is substituted with —NR ¹¹ — include the following (* represents a bond).

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

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

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

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

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

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

^{R a10, R a11, R a14} , R a15, aromatic in R ^a18 and R ^a19 hydrocarbon group, and, ^{R a10, R a11, R a14} , R a15, aromatics in the aralkyl group in R ^a18 and R ^a19 Examples of the hydrocarbon group include a phenyl group, a naphthyl group, and a tolyl group.

When the group represented by R ^a10 , R ^a11 , R ^a14 , R ^a15 , R ^a18 and R ^a19 is an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aralkyl group, it may have a substituent. The substituent includes a halogen atom such as a fluorine atom, a chlorine atom or iodine; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydroxy group; a sulfamoyl group; 6 alkylsulfonyl groups; C1-C6 alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group.
Specific examples of the aliphatic hydrocarbon group which may be substituted include, for example, halogen such as fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluoroethyl group, trifluoroethyl group, trifluoropropyl group and chlorobutyl group. An aliphatic hydrocarbon group substituted with an atom; an aliphatic hydrocarbon group substituted with a hydroxy group such as a hydroxymethyl group, a hydroxyethyl group, or a hydroxypropyl group.
Specific examples of the aromatic hydrocarbon group which may be substituted include groups represented by the following formulae. In the following formula, * represents a bond.
Specific examples of the aralkyl group which may be substituted include groups in which a methylene group is bonded to the bond of each specific example of the following aromatic hydrocarbon group.

Among them, R ^a10 , R ^a11 , R ^a14 , R ^a15 , R ^a18 and R ^a19 are each independently an aliphatic hydrocarbon having 1 to 10 carbon atoms which may be substituted with a halogen atom (more preferably a chlorine atom). A group in which the methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group may be substituted with —OCO— is preferable,
More _{preferably, * - (CH 2) x1} -CH 3, * - (CH 2) x2 -CF 3, * - (CH 2) x3 -CH 2 OH, * - (CH 2) x4 -CH = CH 2 Or * — (CH ₂ ) _x5 —OCO—C (CH ₃ ) H═CH ₂ (wherein, x1 to x5 are each independently an integer of 0 to 5, and an integer of 0 to 3 is More preferred),
More _{preferably, * - (CH 2) x1} -CH 3 or * - (CH ₂₎ a _x2 -CF _3,
Particularly preferred is a methyl group.

R ^a12 , R ^a13 , R ^a16 , R ^a17 , R ^a20 and R ^a21 each independently represent a hydrogen atom, a halogen atom, or a monovalent fatty acid having 1 to 6 carbon atoms which may have a substituent. Represents a group hydrocarbon group.

^Examples of the halogen atom in R ^a12 , R ^a13 , R ^a16 , R ^a17 , R ^a20 and R ^a21 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

The aliphatic hydrocarbon group having 1 to 6 carbon atoms in R ^a12 , R ^a13 , R ^a16 , R ^a17 , R ^a20 and R ^a21 may be any of an alkyl group, an alkenyl group and an alkynyl group, preferably an alkyl group The group may be any of linear, branched, and cyclic.

^{Examples of} the linear or branched aliphatic hydrocarbon group (preferably an alkyl group) in R ^a12 , R ^a13 , R ^a16 , R ^a17 , R ^a20 and R ^a21 include, for example, a methyl group, an ethyl group, n- Linear alkyl groups such as propyl, n-butyl, n-pentyl, n-hexyl and n-heptyl; i-propyl, sec-butyl, isobutyl, tert-butyl, 1 -Methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, tert-pentyl group, 1,3-dimethylbutyl group, Branched alkyl groups such as 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, branched heptyl group, 1-methylheptyl group; Examples thereof include chain alkenyl groups such as a nyl group and a hexenyl group.

The cyclic aliphatic hydrocarbon group in R ^a12 , R ^a13 , R ^a16 , R ^a17 , R ^a20 and R ^a21 includes a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclobutylmethyl group, a cyclopentyl group, and a cyclohexyl group. And monocyclic cycloalkyl groups such as
In addition, some carbon atoms of the aliphatic hydrocarbon group may be replaced with oxygen atoms, nitrogen atoms, or the like.

^{Examples of} the substituent that the aliphatic hydrocarbon group in R ^a12 , R ^a13 , R ^a16 , R ^a17 , R ^a20 and R ^a21 may have include an aryl group (for example, a carbon number of 6 to 10), an alkyloxy group ( For example, carbon number 1-10), aryloxy group (for example, carbon number 6-10), acyloxy group (for example, carbon number 1-10), halogen atom, acylamino group, alkyloxycarbonyl group (for example, carbon number 2-11), An aminocarbonyl group, a hydroxy group, a cyano group, etc. are mentioned.

Further, one R ^a12 and one R ^a13 are bonded to each other, and one R ^a16 and one R ^a17 are bonded to each other, or one R ^a20 and one R ^a21 are May be bonded to each other to represent an aliphatic hydrocarbon group having 2 to 6 carbon atoms. There is no restriction | limiting in particular as a bivalent aliphatic hydrocarbon group, For example, a linear or branched alkylene group is preferable. Examples of the alkylene group include a linear alkylene group such as a methylene group, an ethylene group, an n-propylene group, and a butylene group; a branched alkylene group such as an isopropylene group and a branched butylene group; and the like.

  p1 to p6 each independently represent an integer of 0 to 2, preferably 1 or 2, and more preferably 2.

Among them, R ^a12 , R ^a13 , R ^a16 , R ^a17 , R ^a20 and R ^a21 are each independently a monovalent fatty ^acid having 1 to 6 carbon atoms which may be substituted with a halogen atom (more preferably a chlorine atom). Is more preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms which may be substituted with a halogen atom (more preferably a chlorine atom), more preferably a methyl group or a trivalent group. A fluoromethyl group;

The cyanine compound according to the present invention may be dimerized as shown in Formula (A-II) and Formula (A-IV) described below. In formula (A-II) and formula (A-IV), L ¹ represents an optionally substituted divalent hydrocarbon group having 1 to 16 carbon atoms. Examples of the divalent hydrocarbon group represented by L ¹ include:
Alkanediyl groups such as methylene group, ethylene group, ethanediyl group, propanediyl group, butanediyl group, tetramethylene group, pentamethylene group, hexamethylene group;
A divalent alicyclic hydrocarbon group such as a cyclopentanediyl group, a cyclohexanediyl group, or a cyclohexenediyl group;
and divalent aromatic hydrocarbon groups such as an o-phenylene group, an m-phenylene group, a p-phenylene group, and a naphthylene group.
Examples of the substituent that the divalent hydrocarbon group may have include an amino group, a carboxy group, a cyano group, a nitro group, a halogen atom, and a hydroxy group.

L ¹ may be bonded to any position of ring Z ³ and ring Z ⁵ , but more preferably R ^a14 and R ^a18 are bonded to form a divalent hydrocarbon group. .

Among them, L ¹ is preferably an alkanediyl group having 1 to 16 carbon atoms, more preferably an alkanediyl group having 1 to 10 carbon atoms, still more preferably an alkanediyl group having 3 to 8 carbon atoms, and an alkane having 3 or 4 carbon atoms. A diyl group is particularly preferred. L ¹ is preferably unsubstituted.

  The compound represented by the formula (AI) is preferably a compound represented by the formula (A-III), and the compound represented by the formula (A-II) is represented by the formula (A-IV). It is preferable that it is a compound represented.

[In Formula (A-III) and Formula (A-IV),
Ring Z ⁷ to ring Z ¹² each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
R ^{a1 to} R ^a9 , u, v, w, X ^b1- , X ^c1- , b1, c1, n, m, R ^{a10 to} R ^a13 , R ^{a15 to} R ^a17 , R ^{a19 to} R ^a21 , p1 to p6, L ¹ represents the same meaning as described above. ]

As the substituents for ring Z ⁷ to ring Z ^12, the same substituents as for ring Z ¹ and ring Z ² are used.
Fatty acids having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group Group hydrocarbon group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
An aliphatic hydrocarbon group having 1 to 6 carbon atoms substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;
Etc. are preferable.

When ring Z ⁷ to ring Z ¹² are benzene rings, the hydrogen atom at the 5-position and / or the 6-position in formula (Z ³ -N) and formula (Z ⁴ -N) may be substituted with the substituent. More preferably, the 5-position hydrogen atom in the formulas (Z ³ -N) and (Z ⁴ -N) is preferably substituted.

Among them, the ring Z ⁷ to the ring Z ¹² are preferably a benzene ring or a naphthalene ring which is unsubstituted or substituted with a methyl group, an ethyl group, a chlorine atom or a trifluoromethyl group, more preferably an unsubstituted group or a methyl group or an ethyl group. , A benzene ring substituted with a chlorine atom or a trifluoromethyl group, and more preferably a benzene ring in which a hydrogen atom at the 5-position is substituted with a methyl group.

<Counter anion>
Counter anion X ^B1- and X ^c1- is in cyanine compounds, independently of one another, an anion comprising boron atoms, anions containing Arumiumu atoms, and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus An anion containing oxygen as an essential element. These counter anions are preferable from the viewpoint of heat resistance.

  Examples of the anion containing a boron atom and the anion containing an aluminum atom include an anion represented by the formula (4).

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

  The group having two substituents formed by releasing protons from a monovalent proton-donating substituent is selected from compounds having at least two monovalent proton-donating substituents (for example, a hydroxy group, a carboxylic acid group, etc.). And groups in which protons are released from each of the two proton-donating substituents. Examples of the compound leading to the group include catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, and 2,2′- which may have a substituent. Biphenol, 3-hydroxy-2-naphthoic acid optionally having substituent, 2-hydroxy-1-naphthoic acid optionally having substituent, 1-hydroxy optionally having substituent 2-naphthoic acid, optionally substituted binaphthol, optionally substituted salicylic acid, optionally substituted benzylic acid and optionally substituted mandel Examples include acids.

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

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

  As benzylic acid which may have a substituent,

  Examples of the mandelic acid that may have a substituent include those described below.

As the anion represented by the formula (4), an anion represented by the following formula is preferable.
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or An alkoxy group having 1 to 4 carbon atoms is represented.
Examples of the halogen atom represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ 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 is mentioned.
Examples of the haloalkyl group having 1 to 4 carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include trifluoromethyl group, trichloromethyl group, tribromomethyl group, tetrafluoroethyl group, tetrachloroethyl group and tetra A bromoethyl group etc. are mentioned.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a sec-butoxy group. And a tert-butoxy group.

  Specifically, the anion (BC-1) to anion (BC-24) having a substituent described in Table 1 and the anion represented by the formula (BC-25), represented by the formula (BC-26) An anion represented by formula (BC-27), an anion represented by formula (BC-28), and the like. In Table 1, tBu represents a tert-butyl group.

  As an anion represented by Formula (4), an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), and an anion (BC) -27) is preferable, an anion (BC-1), an anion (BC-2) and an anion (BC-25) are more preferable, and an anion (BC-1) and an anion (BC-2) are still more preferable.

  When an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements is used as a counter anion, the heat resistance and solvent resistance of the cyanine compound can be improved. Such a counter anion is preferably an anion of a heteropolyacid or isopolyacid containing tungsten as an essential element, particularly an anion of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid.

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

An anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus is also preferable.
Examples of such an anion comprising at least one element selected from the group consisting of silicon and phosphorus and oxygen include SiO ₃ ²⁻ and PO ₄ ³⁻ .

In particular, phosphotungstic anions such as Keggin-type phosphotungstate ions and Dawson-type phosphotungstate ions; silicotungstate anions such as Keggin-type silicotungstate ions, [W ₁₀ O ₃₂ ] ^{4 -} is preferably tungsten-based isopoly anions such as phosphotungstic acid anion and tungsten-based isopoly acid anion is particularly preferred.

  The valences b1 and c1 of the counter anion can be set from the range of 1 to 20, preferably from the range of 2 to 10, and more preferably from the range of 3 to 6.

The n of the counter anion is determined to be equal to the positive charge resulting from the onium nitrogen atom of ring Z ¹ and / or ring Z ² , and is more preferably 1.
The counter anion m is determined so as to be equal to a positive charge resulting from the onium nitrogen atom in the ring Z ³ to the ring Z ⁶ , and is more preferably 2.

Among them, the counter anions X ^b1− and X ^c1− are preferably anions containing, independently of each other, at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, An anion of heteropolyacid or isopolyacid containing tungsten as an essential element is more preferable, an anion of phosphotungstic acid, an anion of silicotungstic acid, or an anion of tungsten-based isopolyacid, [PW ₁₂ O ₄₀ ] ³⁻ , [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , [SiW ₁₂ O ₄₀ ] ^4- or [W ₁₀ O ₃₂ ] ^4- are particularly preferred, and [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^{6 -} and still more preferably more. From the viewpoint of heat resistance, it is particularly preferable to use an anion of heteropolyacid or isopolyacid containing tungsten as an essential element.

Such a cyanine compound is preferably a compound represented by Formulas (A-1) to (A-400),
More preferably, it is a compound represented by Formulas (A-1) to (A-200) and Formulas (A-241) to (A-400),
More preferably, Formula (A-9) to (A-20), Formula (A-41) to (A-44), Formula (A-49) to (A-52), Formula (A-89) to (A-92), Formulas (A-129) to (A-132), Formulas (A-169) to (A-172), Formulas (A-249) to (A-252), Formula (A-265) ) To (A-268), formulas (A-273) to (A-280), formulas (A-289) to (A-292), formulas (A-329) to (A-332), formula (A) -361) to (A-364) and compounds represented by formulas (A-369) to (A-372),
Particularly preferred are compounds represented by formulas (A-41) to (A-44) and formulas (A-49) to (A-52),
Still more preferred are compounds represented by formulas (A-41) to (A-44).

In the above table, the main skeleton and the counter anions X ^b1- and X ^c1- have the following meanings, respectively. Note that * represents a bond with ring Z ¹ to ring Z ⁶ . In the dimerized cyanine compound corresponding to the formula (A-II), the main skeleton 1 connects the ring Z ³ and the ring Z ⁴ , and the main skeleton 2 connects the ring Z ⁵ and the ring Z ⁶ .

In the above table, each of ring Z ¹ to ring Z ⁴ means the following substituent. Note that * represents a bond to the main skeleton, and ** in ring Z ³ represents a bond to L ¹ .

<Method for producing cyanine compound>
Compound (A-1) to Compound (A-IV) are salts containing a cation moiety of Formula (A-1) to Formula (A-IV) (hereinafter sometimes referred to as Compound (AV)). , Counter anions X ^b1- , X ^c1- alkali metal salts or proton acids can be mixed.

As the compound (A-V), a salt containing a cation moiety of compound (A-1) to compound (A-IV), halide ion, ClO ₄ ⁻ , OH ⁻ , PO ₄ ³⁻ , SO ₄ ²⁻ And a salt formed from at least one kind of anion selected from organic carboxylate anions, organic sulfonate anions, Lewis acid anions and dye-derived anions.

Examples of the halide ion include Cl ⁻ , Br ⁻ , I ^{− and the} like.
Examples of the organic carboxylate anion include benzoate ion, alkanoic acid ion, trihaloalkanoic acid ion, and nicotinic acid ion.
Examples of the organic sulfonate anion include benzene sulfonate ion, naphthalene sulfonate ion, p-toluene sulfonate ion, and alkane sulfonate ion.
Examples of the Lewis acid anion include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{− and the} like.
Examples of the dye-derived anion include an anion derived from a phthalocyanine compound, an anion derived from an azo compound, and the like, preferably an anion derived from a phthalocyanine compound.

^Examples of the alkali metal that forms a salt with ^Xb1- and ^Xc1- include lithium, sodium, and potassium.

The amount of ^Xb1- , ^Xc1- alkali metal salt or protonic acid used for compound (A-V) is such that the cation of compound ( ^AV ) and the charges of ^Xb1- , ^Xc1- are balanced. It is good to add in stoichiometric ratio.

  Mixing with the compound (A-V), the alkali metal salt or the protonic acid may be carried out by dissolving both in a solvent or not.

Solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, water and chloroform. Is mentioned.
Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol and water are preferable. When these solvents are used, the solubility of the compound (A-V) and the alkali metal salt tends to be high.
When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added.

  The mixing temperature with the compound (A-V), the alkali metal salt or the protonic acid is preferably 0 to 150 ° C, more preferably 10 to 120 ° C, and further preferably 20 to 100 ° C. The mixing time is preferably 1 to 72 hours, more preferably 2 to 24 hours, and further preferably 3 to 18 hours.

  When a solvent that is compatible with water is used, the solution is mixed, and further stirred for 1 to 3 hours as necessary. Thereafter, the precipitate is obtained by solid-liquid separation such as filtration, whereby the compound ( AI) to compound (A-IV) can be obtained. If necessary, the obtained compound (AI) to compound (A-IV) may be washed with ion-exchanged water or the above solvent.

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

<Colored dispersion>
The cyanine compound of the present invention can be used as a colorant. Two or more cyanine compounds may be used.
In the present invention, a cyanine compound may be mixed with a solvent to form a colored dispersion containing the cyanine compound and the solvent. When a colored curable resin composition is formed by mixing with a resin (B), a polymerizable compound (C), a polymerization initiator (D), etc. after making a colored dispersion, the heat resistance when it is made into a color filter is further increased. It can be expected to increase.

Any solvent can be used as long as it can be used as the solvent (E) of the colored curable resin composition. Particularly excellent solvents for the purpose of dispersing the cyanine compound are, for example, amide solvents and ether ester solvents, and more preferably N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, alkylene glycol or Solvents in which one hydroxy group of polyalkylene glycol is etherified and the remaining hydroxy groups are esterified, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate, dipropylene glycol methyl ether acetate and the like. You may use these individually or in mixture of multiple types.
The amount of the solvent is usually 1 to 50 parts by mass, preferably 2 to 30 parts by mass, more preferably 3 to 10 parts by mass with respect to 1 part by mass of the cyanine compound.

  The colored dispersion preferably contains a dispersant. As the dispersant, for example, known dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic can be used. These dispersants may be used alone or in combination of two or more. As the 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 Corporation), Ajispur (Ajinomoto Fine Techno) (Manufactured by Co., Ltd.), Disperbyk (manufactured by Big Chemie), etc.

  The amount of the dispersant is, for example, 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the cyanine compound. .

  The colored dispersion may contain a part or all of the resin (B) used in the colored curable resin composition, preferably a part thereof, if necessary. By including the resin (B) in advance, the dispersibility of the colored curable resin composition can be further improved. The solid equivalent of the resin (B) in the colored dispersion is usually 1 to 300 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the cyanine compound. .

  In preparing the dispersion, it is preferable to finely disperse using a dispersion apparatus after appropriately adding necessary components. A bead mill device can be used as the dispersing device. The beads used are generally hard beads such as zirconia beads, and the particle size thereof is selected from the range of 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, more preferably. 0.1 to 0.5 mm.

<Colored curable resin composition>
The colored curable resin composition refers to a composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) includes cyanine. It is preferable to use a colored dispersion liquid containing a compound and / or a cyanine compound and a solvent.
The colored curable resin composition can appropriately include a polymerization initiation assistant (D1), a solvent (E), a leveling agent (F), and the like. Hereinafter, each component will be described.

<Colorant (A)>
As the colorant (A), a cyanine compound may be contained alone, but for the purpose of toning, that is, to adjust the spectral characteristics, it further contains other dye (A1) and pigment (P). May be.

  Examples of the dye (A1) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, sulfonamides of acid dyes, and the like, for example, Color Index (The Society). of Dyers and Colorists) and known dyes described in Dyeing Notes (Color Dyeing). Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And 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. of Basic Green 1 etc. I. Basic dyes;
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. C. of Reactive Red 36, etc. 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 dyes;
Etc.
Two or more of these dyes may be used in combination.

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;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
Etc.

  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.

The content of the cyanine compound is, for example, 0.1% by mass or more, preferably 10% by mass or more, more preferably 10% by mass or more, and further preferably 30% by mass in the total amount of the colorant (A). % Or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the content rate of a compound (AI) is 100 mass% in the total amount of a coloring agent (A).
When the dye (A1) is contained, the content of the dye (A1) is preferably 0.5% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 80% by mass in the total amount of the colorant (A). % Or less.
When the pigment (P) is contained, the content of the pigment (P) 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, in 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 0.1% by mass or more and 70% by mass or less, more preferably 0.2% by mass or more and 60% by mass in the total solid content of the colored curable resin composition. Or less, more preferably 0.35 mass% or more and 50 mass% or less. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.
In addition, in this specification, "the total amount of solid content" means the total amount of the component remove | excluding the solvent (E) from the colored curable resin composition of this 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. The alkali-soluble resin is a copolymer containing a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

  The monomer (a) includes at least a monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond, and a monomer (c) copolymerizable with (a). It is preferable to copolymerize with one to make resin (B). When copolymerized with both monomer (b) and monomer (c), a carboxylic acid anhydride may be further reacted. .

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Unsaturated dicarboxylic acids such as maleic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds containing a carboxy group of
Unsaturated dicarboxylic acid anhydrides such as maleic anhydride;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) 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.
(B) is preferably a monomer having a C2-C4 cyclic ether 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 (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned. Preferred (b) is a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond.

  As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”). (B1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (II), and Formula (III) The compound etc. which are represented by these are mentioned.

[In Formula (II) and Formula (III), R ^a and R ^b 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 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 formula (III-1) to the formula (III-15), among which the formula (III-1) and the formula are preferable. And compounds represented by formula (III-3), formula (III-5), formula (III-7), formula (III-9), and formula (III-11) to formula (III-15). Preferable examples include 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: It is 90-90: 10, More preferably, it is 20: 80-80: 20.

Examples of (c) 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”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [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 esters 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, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N from the viewpoint of copolymerization reactivity and heat resistance. -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene are preferred.

  Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Resins such as decyl (meth) acrylate / (meth) acrylic acid copolymer; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4- epoxytricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) Resins such as rylloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) Resin such as acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, tri Resin with glycidyl (meth) acrylate added to cyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer A resin such as a resin obtained by adding glycidyl (meth) acrylate to the coalescence; Resin in which (meth) acrylic acid is reacted with a copolymer of licyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate (meth) Resin such as resin reacted with acrylic acid; tetrahydrophthalic anhydride was further reacted with a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Examples thereof include resins such as resins.

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

  The acid value in terms of solid content of the resin (B) is preferably 30 to 170 mg-KOH / g, more preferably 40 to 150 mg-KOH / g, and still more preferably 50 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 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass in 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.

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

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

  Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (Meth) acrylate, 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 in 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 35:65 to 65:35, more preferably 40:60 to 60:40.
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, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9 Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

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

  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 (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is 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-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) Thenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

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

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

  The content of the polymerization initiator (D) is preferably 0.1 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 a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is 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 amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

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

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. As the solvent (E), an ester solvent (including -COO- in the molecule and -O- is included). No solvent), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (intramolecular -CO- and -COO--free solvent), alcohol solvent (including OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvent, amide A solvent, dimethyl sulfoxide, etc. are mentioned.
These solvents may be used alone or in combination of two or more.

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

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

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

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

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

  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 Chill acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, more preferably N- methylpyrrolidone, even more preferably N- methylpyrrolidone.

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

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

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

  When the leveling agent (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% by mass in the total amount of the colored curable resin composition. The content is 0.1% by mass or less, more preferably 0.005% by mass or more and 0.07% by mass or less. 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 cyanine compound and / or a colored dispersion, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a cyanine used as necessary. It can be prepared by mixing the colorant (A) other than the compound, the solvent (E), the leveling agent (F), the polymerization initiation assistant (D1) and other components.
When the colorant (A) other than the cyanine compound contains the pigment (P), the pigment (P) is previously mixed with part or all of the solvent (E), and the average particle diameter of the pigment is about 0.2 μm or less. Until it becomes, it is preferable to disperse | distribute using a bead mill etc. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

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

  As the substrate, a glass plate, a resin plate, silicon, or an aluminum, silver, silver / copper / palladium alloy thin film formed on the substrate 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.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern.
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 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.

  With the colored curable resin composition using the cyanine compound according to the present invention, a color filter particularly excellent in heat resistance can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

[Synthesis Example 1]
400 parts of methanol was added to 5.6 parts of the compound represented by the formula (2c-1), and the mixture was stirred at 20 to 30 ° C. for 1 hour to obtain a solution. To this solution, 400 parts of ion exchange water was added and stirred for 2 hours to obtain a solution (2c-1A). On the other hand, 28.8 parts of ion-exchanged water was added to 9.6 parts of phospho12 tungstic acid 3 hydrogen, and the mixture was stirred at 20 ° C. to 30 ° C. for 1 hour, and then 28.8 parts of methanol was added and stirred for 2 hours. (2c-1B) was obtained. The solution (2c-1B) was added to the solution (2c-1A), and the mixture was stirred at 20 ° C to 30 ° C for 12 hours. The resulting precipitate was collected by filtration, washed twice with 200 parts of ion-exchanged water, and then washed twice with 200 parts of methanol. The crystal collected by filtration was dried at 60 ° C. for 24 hours to obtain 10.3 parts of a compound represented by the formula (2c-1P).

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

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

(Preparation of colored curable resin composition)
Example 1
Colorant (A1): 0.5 part of a colorant represented by formula (2c-1P);
Alkali-soluble resin (B): 50 parts of resin (B-1) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 10 parts;
Solvent (E): 700 parts of N-methylpyrrolidone;
In addition, 0.1 part of leveling agent (F): Megafac (registered trademark) F554 (manufactured by DIC Corporation) was mixed to obtain a colored curable resin composition.

Comparative Example 1
Colorant (A1): 0.3 part of a colorant represented by formula (2c-1);
Alkali-soluble resin (B): 50 parts of resin (B-1) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 10 parts;
Solvent (E): 700 parts of propylene glycol monomethyl ether acetate;
In addition, 0.1 part of leveling agent (F): Megafac (registered trademark) F554 (manufactured by DIC Corporation) was mixed to obtain a colored curable resin composition.

[Formation of pattern]
A colored curable composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer is formed and the photomask made of quartz glass is set to 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), 150 mJ / cm ^{2 in} an air atmosphere. Is irradiated with light at an exposure amount (365 nm reference). A photomask having a 100 μm line and space pattern is used. After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and 220 ° C. in an oven. Was post-baked for 20 minutes to obtain a pattern having a thickness of 2.5 μm.

[Heat resistance evaluation]
The coating film of the colored curable resin composition was heated at 230 ° C. for 20 minutes, and the color difference (ΔEab *) before and after the heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). As a result of carrying out heat resistance evaluation about the coating film obtained in Example 1, color difference ((DELTA) Eab *) was 2.5. Moreover, as a result of carrying out heat resistance evaluation similarly about the comparative example 1, color difference ((DELTA) Eab *) was 5.4 and it turned out that this-application compound is excellent in heat resistance.

  When a colored curable resin composition containing a cyanine compound is used, a color filter having excellent heat resistance can be provided. 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.

Claims (9)

A cyanine compound represented by formula (AI) or formula (A-II).


[In the formula (AI),
Ring Z ¹ and ring Z ² each independently represent an optionally substituted heterocyclic ring.
Ring Z ¹ and ring Z ² have a structure in which a nitrogen atom is onium-ized independently of each other.
R ^a1 , R ^a2 and R ^a3 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an optionally substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms or a substituent. It represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have, and two selected from R ^a1 , R ^a2 and R ^a3 may be bonded to each other to form a ring.
u represents an integer of 1 to 3.
R ^a10 and R ^a11 each independently represent a hydrogen atom, an ^optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic carbon atom having 6 to 12 carbon atoms. It represents a hydrogen group or an optionally substituted aralkyl group having 7 to 10 carbon atoms.
R ^a12 and R ^a13 each independently represent a hydrogen atom, a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.
p1 and p2 represent the integer of 0-2 independently of each other.
A ¹ , A ² , A ³ , and A ⁴ each independently represent —C (H) — or a nitrogen atom.
^Xb1- represents an anion containing a boron atom, an anion containing an aluminum atom, and an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, b1 The integer of 1-20 is represented.
n is determined to be equal to the positive charge resulting from the onium nitrogen atom of ring Z ¹ and / or ring Z ² .
In formula (A-II),
Ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ each independently represent an optionally substituted heterocyclic ring.
At least two or more of the ring Z ³ , the ring Z ⁴ , the ring Z ^5, and the ring Z ⁶ have a structure in which a nitrogen atom is oniumated.
R ^a4 , R ^a5 , R ^a6 , R ^a7 , R ^a8 and R ^a9 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a C 1-8 which may have a substituent. Represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, and two selected from R ^{a4 to} R ^a6 _and R ^{a7 to} R ^a9 are bonded to each other; To form a ring.
L ¹ represents an optionally substituted divalent hydrocarbon group having 1 to 16 carbon atoms.
v and w each independently represent an integer of 1 to 3.
R ^a14 , R ^a15 , R ^a18 and R ^a19 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or may be substituted. A C6-C12 aromatic hydrocarbon group or the C7-C10 aralkyl group which may be substituted is represented.
R ^a16 , R ^a17 , R ^a20 and R ^a21 each independently represent a hydrogen atom, a halogen atom, or an ^optionally substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms.
p3 to p6 each independently represent an integer of 0 to 2.
A ^{5 to} A ¹² each independently represent —C (H) — or a nitrogen atom.
X ^c1- represents an anion containing a boron atom, an anion containing an aluminum atom, and an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, c1 Represents an integer of 1-20.
m is determined so as to be equal to a positive charge caused by the onium nitrogen atom in the ring Z ³ to the ring Z ⁶ . ] ^2. The cyanine compound according to claim 1, wherein ^Xb1- and ^Xc1- are ^{anions containing} , independently of each other, at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements. . The cyanine compound according to claim 1 or 2, wherein ^Xb1- and ^Xc1- are anions of heteropolyacid or isopolyacid containing tungsten as an essential element, independently of each other. The cyanine compound according to any one of claims 1 to 3, wherein the compound represented by the formula (AI) is a compound represented by the formula (A-III).

[Formula (A-III),
Ring Z ⁷ and ring Z ⁸ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
R ^{a1 to} R ^a3 , R ^{a10 to} R ^a13 u, p1, p2, ^Xb1− , b1 and n represent the same meaning as described above. ] In formula (A-III):
Ring Z ⁷ and Ring Z ⁸ each independently represent a benzene ring or a naphthalene ring which may be substituted with a methyl group, an ethyl group, a chlorine atom or a trifluoromethyl group,
R ^a10 and R ^a11 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom,
R ^a12 and R ^a13 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom;
The cyanine compound according to claim 4, wherein p1 and p2 represent 2. R ^{a1 to} R ^a3 in formulas (A-I) to (A-III) are each independently a hydrogen atom, a cyano group, a halogen atom, or a C 1-8 fatty acid that may have a substituent. The cyanine compound according to any one of claims 1 to 5, which represents a group hydrocarbon group, or two selected from R ^{a1 to} R ^a3 are bonded to each other to form a ring.   The colored curable resin composition containing the cyanine compound in any one of Claims 1-6, resin (B), polymeric compound (C), and a polymerization initiator (D).   A color filter formed using the colored curable resin composition according to claim 7.   A display device comprising the color filter according to claim 8.