JP6951929B2 - Color curable resin composition - Google Patents

Description

The present invention relates to a colored curable resin composition.

As a color-curable resin composition for forming a color filter contained in a liquid crystal display device or the like, a solid-state imaging device, etc., Patent Document 1 contains a triarylmethane dye and a xanthene dye as a colorant. The resin composition is described.

Japanese Unexamined Patent Publication No. 2015-199912

In the above-mentioned color-curable resin composition, the contrast of the color filter was not always sufficiently satisfactory. An object of the present invention is to provide a color curable resin composition capable of producing a high-contrast color filter, a color filter formed from the color curable resin composition, and a display device including the color filter. ..

The present invention provides the following [1] to [5].
[1] Contains a colorant, a resin, a polymerizable compound and a polymerization initiator.
The colorant is a color curable resin composition containing a triarylmethane colorant, a xanthene dye, and a tetraazaporphyrin dye.

[2] The color curable resin composition according to [1], wherein the content of the tetraazaporphyrin dye in the colorant is 0.5 to 50 parts by mass with respect to 100 parts by mass of the triarylmethane colorant. thing.

[3] The color curability according to [2], wherein the content of the tetraazaporphyrin dye in the colorant is 1.0 to 9.0 parts by mass with respect to 100 parts by mass of the triarylmethane colorant. Resin composition.

[4] A color filter formed from the colored curable resin composition according to [1] to [3].

[5] A display device including the color filter according to [4].

According to the color curable resin composition of the present invention, a high-contrast color filter can be obtained.

The color-curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The color curable resin composition of the present invention preferably contains a solvent (E) and / or a leveling agent (F), and may further contain an antioxidant (H) and other components. The colorant (A) includes a triarylmethane colorant (Aa1), a xanthene dye (Aa2), and a tetraazaporphyrin dye (Aa3). According to the present invention, a high-contrast color filter can be manufactured.

<Colorant (A)>
The colorant (A) includes a triarylmethane colorant (Aa1), a xanthene dye (Aa2), and a tetraazaporphyrin dye (Aa3). Further, a dye different from the triarylmethane colorant (Aa1), the xanthene dye (Aa2), and the tetraazaporphyrin dye (Aa3) (hereinafter, may be referred to as “dye (Aa4)”) may be contained.

(Triarylmethane colorant (Aa1))
The triarylmethane colorant (Aa1) is a colorant containing a compound having a triarylmethane skeleton in the molecule, and examples thereof include dyes and pigments, and may be lake pigments. As the triarylmethane colorant (Aa1), the compound represented by the formula (AI) and its tautomer (hereinafter, the compound represented by the formula (AI) and its tautomer) are referred to as " A dye containing "Compound (AI)" is preferable.
When compound (AI) is used, the content of compound (AI) in the triarylmethane colorant (Aa1) is preferably 50% by mass or more, more preferably 70% by mass or more. , More preferably 90% by mass or more. In particular, it is preferable to use only the compound (AI) as the triarylmethane colorant (Aa1).

[In formula (AI), [Y ² ] ^m- represents an m-valent anion.
In R ^{41 to} R ⁴⁴ , hydrogen atoms, saturated hydrocarbon groups having 1 to 20 carbon atoms which may be substituted, and oxygen atoms are inserted between carbon atoms constituting the alkyl groups having 2 to 20 carbon atoms independently of each other. Represents a substituted group, an optionally substituted aryl group, or an optionally substituted aralkyl group. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{45 to} R ⁵² are independently located between carbon atoms constituting a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. It may represent a group in which an oxygen atom is inserted, or R ⁴⁶ and R ⁵⁰ may be bonded to each other to form -O-, -NH-, -S- or -SO _2- .
Y ¹ represents an aryl group which may be substituted or a heteroaryl group which may be substituted.
When the compound represented by the formula (AI) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other.
m represents an arbitrary natural number. ]

[Y ² ] ^m- represents an m-valent anion. The anion represented by [Y ² ] ^m- is not particularly limited as long as it is an anion capable of forming a counterion with the cation, and is preferably a halogen such as a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, and a chlorine anion. Examples thereof include anions and anions having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom.

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

[In formula (4), W ¹ and W ² represent groups in which protons are released from a compound having two monovalent proton donating substituents independently of each other. M represents boron or aluminum. ]

Examples of the compound having two monovalent proton donating substituents include compounds having two monovalent proton donating substituents (for example, hydroxy group, carboxy group, etc.), for example, dihydroxynaphthalene and substituents. 2,2'-biphenol which may have, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, substitution 1-Hydroxy-2-naphthoic acid which may have a group, binaphthol which may have a substituent, salicylic acid which may have a substituent, and benzylic acid which may have a substituent. Alternatively, mandelic acid which may have a substituent may be mentioned.
The group in which protons are released from the compound is a group in which all protons are dissociated from a plurality of proton-donating substituents in the compound, and means, for example, a group having ^{O −} and COO ^−.

Examples of the substituent in each of the compounds exemplified as the compound having at least two monovalent proton-donating substituents include a saturated hydrocarbon group (alkyl group, cycloalkyl group, etc.), halogen atom, hydroxy group, amino group, and nitro. Examples include groups and alkoxy groups.

Examples of salicylic acid that may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, and 3,5-di-. Monoaminosalicylic acids such as tert-butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid and 6-aminosalicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2) , 4-Dihydroxysalicylic acid), 5-hydroxysalicylic acid (2,5-dihydroxysalicylic acid) and 6-hydroxysalicylic acid (2,6-dihydroxysalicylic acid) and other monohydroxysalicylic acids; 4,5-dihydroxysalicylic acid and 6 Dihydroxysalicylic acid such as −dihydroxysalicylic acid; mono such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid and 6-bromosalicylic acid. Halo-salicylic acid; dihalosalicylic acid such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid and 3,5-diiodosalicylic acid; trihalosalicylic acid such as 3,5,6-trichlorosalicylic acid; and the like.

Examples of the benzylic acid which may have a substituent include the following compounds.

Examples of mandelic acid that may have a substituent include the following compounds.

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

［Ｍは、ホウ素又はアルミニウムを表す。］

[M represents boron or aluminum. ]

［式（ＢＣ−２５）〜式（ＢＣ−２８）中、Ｍは、ホウ素又はアルミニウムを表す。］

[In formulas (BC-25) to (BC-28), M represents boron or aluminum. ]

Examples of the anion represented by the formula (4) include anion (BC-1), anion (BC-2), anion (BC-3), anion (BC-25), anion (BC-26), and anion (BC). -27) is preferable, anion (BC-1), anion (BC-2) and anion (BC-25) are more preferable, and anion (BC-1) and anion (BC-2) are further preferable. The compound represented by the formula (AI) having any of these anions tends to have excellent solubility in an organic solvent.

Examples of the fluorine-containing anion include groups represented by the formulas (6) to (9).

[In formula (6), W ³ and W ⁴ represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms independently of each other, or W ³ and W ⁴ together have a carbon number of carbons. Represents 1 to 4 fluorinated alkanediyl groups. ]

[In formula (7), W ⁵ , W ⁶ and W ⁷ represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms independently of each other. ]

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

[In formula (9), Y ^b represents an alkyl fluoride group having 1 to 4 carbon atoms. ]

In the formulas (6), (7) and (9), the perfluoroalkyl group having 1 to 4 carbon atoms is preferable as the fluorinated alkyl group having 1 to 4 carbon atoms. Examples of the perfluoroalkyl group having 1 to 4 carbon atoms include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , and-. CF ₂ CF (CF ₃ ) ₂ or -C (CF ₃ ) ₃ can be mentioned.
In the formulas (6) and (8), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and more preferably −CF ₂ −, _{−CF 2} CF ₂ −, −. CF ₂ CF ₂ CF ₂ −, −C (CF ₃ ) ₂ − and −CF ₂ CF ₂ CF ₂ CF ₂ − and the like can be mentioned.

Examples of the anion represented by the formula (6) (hereinafter sometimes referred to as “anion (6)”) include anions represented by the formulas (6-1) to (6-6) (hereinafter, “anion (6)”). -1) ”to“ anion (6-6) ”).

As the anion represented by the formula (7) (hereinafter sometimes referred to as "anion (7)"), the anion represented by the formula (7-1) (hereinafter referred to as "anion (7-1)") may be used. There is).

Examples of the anion represented by the formula (8) (hereinafter sometimes referred to as "anion (8)") include anions represented by the formulas (8-1) to (8-4) (hereinafter "anion (8-)". 1) ”to“ anion (8-4) ”).

Examples of the anion represented by the formula (9) (hereinafter sometimes referred to as "anion (9)") include anions represented by the formulas (9-1) to (9-4) (hereinafter "anion (9-)". 1) ”to“ anion (9-4) ”).

As [Y ² ] ^m- , a fluorine-containing anion and a polyacid anion are preferable, and the anions represented by the formula (6), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [ SiW ₁₂ O ₄₀ ] ^4- and [W ₁₀ O ₃₂ ] ^4- are more preferable, and the anions represented by the formulas (6-1) to (6-5), [PW ₁₂ O ₄₀ ] ^3- , [P. ₂ W ₁₈ O ₆₂ ] ^6- is more preferable, and the anion represented by the formula (6-2), [PW ₁₂ O ₄₀ ] ^3-, is particularly preferable.

m represents an arbitrary natural number and is equal to the negative charge of ^{the anion [Y 2} ] ^m-. The m on the cation side is ^{defined so that the charge of the anion [Y 2} ] ^m- and the cation are equal. m is preferably a natural number from 1 to 10.

The saturated hydrocarbon groups having 1 to 20 carbon atoms in R ^{41 to} R ^{44 may be linear, branched or cyclic.} The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
The linear or branched saturated hydrocarbon group includes a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group and a decyl group. Examples include branched chain alkyl groups such as isopropyl group, isobutyl group and 2-ethylhexyl group. The linear or branched saturated hydrocarbon has preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms.
Further, the cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

The hydrogen atom of the saturated hydrocarbon group in R ^{41 to} R ^{44 may be substituted with a substituent.} Examples of the substituent include a substituted or unsubstituted amino group and a halogen atom. Examples of the substituted amino group include a dialkylamino group such as a dimethylamino group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the saturated hydrocarbon group in which the hydrogen atom is substituted with a substituted or unsubstituted amino group or a halogen atom include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

Examples of the group in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms in R ^{41 to} R ^{44 include a group represented by the following formula.} In the following formula, * represents a bond with a nitrogen atom. Among them, as the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group, a group having 2 to 10 carbon atoms is preferable, and a group having 2 to 6 carbon atoms is more preferable. The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group. The number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

In R ^{41 to} R ⁴⁴ , the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and the aralkyl group has preferably 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. Is.
Examples of the aryl group of R ^{41 to R 44} include a phenyl group, a naphthyl group and a toluyl group.
Examples of the aryl group in the aralkyl groups of R ^{41 to} R ⁴⁴ include a phenyl group and a naphthyl group, and examples of the aralkyl group include a group in which the bond of these aryl groups and an alkandyl group are bonded. The alkanediyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is preferably a linear alkanediyl group. Specific examples of the alkandiyl group include a methylene group, an ethylene group, a propylene group, a butanjiyl group and a pentandiyl group, and examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group and a naphthylethyl group. And so on.
The ^{substituents that the aryl group and the aralkyl group in R 41 to} R ⁴⁴ may have are halogen atoms such as fluorine atom, chlorine atom and iodine atom; alkoxy having 1 to 6 carbon atoms such as methoxy group and ethoxy group. Groups; hydroxy groups; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl groups; alkoxycarbonyl groups having 2 to 6 carbon atoms such as methoxycarbonyl groups and ethoxycarbonyl groups; and the like.
Specific examples of the aryl group which may be substituted include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

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

The ^{ring formed by combining R 41} and R ⁴² together with the nitrogen atom to which they are bonded, and the ring formed by combining R ⁴³ and R ⁴⁴ together with the nitrogen atom to which they are bonded are 5 such as a pyrrolidine ring and the like. Memberd rings; 6-membered rings such as morpholine ring, piperidine ring and piperazine ring; and the like.

From ^{the viewpoint of ease of synthesis, R 41 to} R ⁴⁴ are independently substituted saturated hydrocarbon groups having 1 to 20 carbon atoms, optionally substituted aryl groups, or substituted. It is preferably an aralkyl group, and more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula, independently of each other. In the following formula, * represents a bond with a nitrogen atom.

The saturated hydrocarbon groups in R ^{45 to} R ⁵² may be linear, branched or cyclic, and are preferably chain. Examples of the saturated hydrocarbon group represented by R ^{45 to} R ⁵² include a group having 1 to 8 carbon atoms among the groups exemplified as the saturated hydrocarbon group in ^{R 41 to} R ^44. As a group in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting the alkyl group, an alkyl group having 2 to 8 carbon atoms is more preferable. As the alkyl group into which the oxygen atom is inserted, a linear alkyl group is preferable, and the number of carbon atoms between the oxygen atoms is preferably 1 to 4, more preferably 2 to 3. For example, a group represented by the following formula can be mentioned. In the following formula, * represents a bond with a carbon atom.

From ^{the viewpoint of ease of synthesis, R 45 to} R ⁵² are preferably hydrogen atoms, halogen atoms or saturated hydrocarbon groups having 1 to 8 carbon atoms independently of each other, and independent of each other, hydrogen atoms and methyl groups. , Fluorine atom or chlorine atom is more preferable.

R ⁴⁶ and R ⁵⁰ may be combined with each other to form -O-, -NH-, -S- or -SO _2- .

Y ¹ represents an aryl group which may be substituted or a heteroaryl group which may be substituted.
The aryl group may be either a monocyclic ring or a fused ring, and has 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group. Aromatic hydrocarbon groups can be mentioned.
Heteroaryl groups are substituents derived from aromatic heterocycles. The aromatic heterocycle may be either a monocyclic ring or a condensed ring, preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring.
Examples of the monocyclic aromatic heterocycle include a 5-membered ring having a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a sol ring;
A 5-membered ring having an oxygen atom or a sulfur atom such as a furan ring and a thiophene ring;
6-membered rings having nitrogen atoms such as pyridine ring, pyrimidine ring, pyridazine ring and pyrazine ring; and the like. As the aromatic heterocycle of the fused ring, a fused ring having a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring and a quinoline ring;
A ring having an oxygen atom such as a benzofuran ring or a sulfur atom; and the like. As the heteroaryl group which may be substituted, the group represented by the formula (Ab2-x1) is more preferable.

[Ring T ² represents an aromatic heterocycle.
In R ⁵³ and R ⁵⁴ , an oxygen atom is inserted between carbon atoms constituting a saturated hydrocarbon group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may be substituted independently of each other. Represents a group, an optionally substituted aryl group, an optionally substituted aralkyl group, or a hydrogen atom.
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.
k1 represents 0 or 1.
* Represents a bond with a carbocation. ]
Ring T ² represents an aromatic heterocycle, preferably an aromatic heterocycle having 2 to 9 carbon atoms.
The details of R ^{53 to} R ⁵⁵ will be described later.

As the compound (AI), the compound represented by the formula (A-II) is more preferable.

[In formula (A-II), [Y ² ] ^m- , R ^{41 to} R ⁵² , and m have the same meanings as described above.
In R ⁵³ and R ⁵⁴ , an oxygen atom is inserted between carbon atoms constituting a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, and an alkyl group having 2 to 20 carbon atoms independently of each other. Represents a substituted group, an optionally substituted aryl group, or an optionally substituted aralkyl group.
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.
X represents an oxygen atom, -NR ⁵⁷ - shows a or a sulfur atom.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
When the compound represented by the formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other. ]

Examples of R ⁵³ and R ⁵⁴ include groups similar to the groups exemplified in ^{R 41 to} R ^44.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{55 include the same groups as those exemplified as the saturated hydrocarbon group having R 41 to} R ⁴⁴ , and preferably an alkyl group having 1 to 10 carbon atoms. , More preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the group in R ⁵⁵ in which an oxygen atom is inserted between the carbon atoms constituting the alkyl group include groups similar to the groups exemplified in ^{R 41 to} R ^44. As the alkyl group into which the oxygen atom is inserted, a linear alkyl group is preferable. The number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

In R ⁵⁵ , the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
Examples of the aryl group include ^{groups similar to those exemplified for R 41 to} R ⁴⁴ , and a phenyl group is preferable.
In R ⁵⁵ , the substituent of the aryl group includes a halogen atom such as a fluorine atom, a chlorine atom and an iodine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; a sulfamoyl group; a methylsulfonyl group. Examples thereof include an alkylsulfonyl group having 1 to 6 carbon atoms such as a group; an alkoxycarbonyl group having 2 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like.

From ^{the viewpoint of ease of synthesis, R 55} is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an optionally substituted aryl group, and more preferably an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. It is an aryl group that may be substituted with a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, or a methylsulfonyl group, and more preferably a group represented by the following formula. In the following formula, * represents a bond with a carbon atom.

^R57 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
X represents an oxygen atom, -NR ⁵⁷ - represents a or sulfur atom. Examples of the cyclic structure containing X include a group represented by the following formula. In the formula, R ^{53 to} R ⁵⁵ are synonymous with the above, and * represents a bond with a carbocation. Among them, as X, an oxygen atom and a sulfur atom are preferable, and a sulfur atom is more preferable.

Examples of the cation contained in the formula (AI) include cations 1 to 27 represented by the formula (AI-1) and having a substituent shown in Table 2 below.

In Table 2, Ph1 to Ph12 mean a group represented by the following formula.

As the cations in the formula (AI), cations 1 to 6, cations 11 and 12 are preferable, and cations 1, cation 2 and cation 12 are more preferable.

When the compound represented by the formula (A-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other.

(Xanthene dye (Aa2))
The xanthene dye (Aa2) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (Aa2) include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. The same applies to the others), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic Violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modant Red 27, C.I. I. Examples thereof include reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP-A-2010-32999, and xanthene dyes described in Japanese Patent No. 4492760. Those that dissolve in an organic solvent are preferable.

Among these, as the xanthene dye (Aa2), the compound represented by the formula (1a) and its tautomer (hereinafter, the compound represented by the formula (1a) and its tautomer are referred to as "compound (1a)". ) ”Is included.) Is preferable. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (Aa2) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (Aa2).

［式（１ａ）中、Ｒ¹〜Ｒ⁴は、互いに独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、炭素数６〜１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。Ｒ¹及びＲ^２は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^３及びＲ^４は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上の整数である場合、複数のＲ⁵は同一でも異なってもよい。
ａは、０又は１の整数を表す。
Ｘ０は、ハロゲン原子を表す。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、互いに独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^８−で置き換っていてもよく、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
⁺Ｎ（Ｒ¹¹）₄における４つのＲ¹¹は、互いに独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］

[In the formula (1a), R ^{1 to} R ⁴ may have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent having 6 to 10 carbon atoms independently of each other. Representing a monovalent aromatic hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the aromatic hydrocarbon may be substituted. hydrogen atoms contained in the group, _-CH 2 may be substituted with an alkoxy group having 1 to 3 carbon atoms, contained in the saturated hydrocarbon group - is, -O -, - CO- or ^{-NR 11} - It may be replaced with. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ Represents NR ⁹ R ^10.
R ⁶ and R ⁷ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms independently of each other.
m represents an integer from 0 to 5. when m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X0 represents a halogen atom.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ represent monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and are contained in the saturated hydrocarbon groups -CH _2. - it is -O -, - CO -, - NH- or -NR ⁸ - in place may have I conversion, R ⁹ and R ^10, 3-10 membered ring containing a nitrogen atom bonded to each other It may form a heterocycle.
⁺ N (R ¹¹⁾ ₄ in the four R ¹¹ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group or an aralkyl group having 7 to 10 carbon atoms having 1 to 20 carbon atoms. ]

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

The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - ^{_{CO 2 H, -CO 2 R 8}} , -SR 8, -SO 2 R 8, -SO 3 R 8 and -SO ₂ NR ⁹ R ¹⁰ can be mentioned, preferably _{^{-SO 3 -, -SO 3 H,}} - SO ₃ ^- Z ⁺ and −SO ₂ NR ⁹ R ¹⁰ are mentioned, and more preferably −SO ₃ ^- Z ⁺ and −SO ₂ NR ⁹ R ¹⁰ are mentioned. In this case, as −SO ₃ ⁻ Z ⁺ , −SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable. When R ^{1 to} R ⁴ are these groups, a color filter containing less foreign matter and excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1a).

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ^{4 together include the following.}

The ^{monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 8 to} R ¹¹ includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. A linear alkyl group having 1 to 20 carbon atoms such as a group, a dodecyl group, a hexadecyl group and an icosyl group; a branched chain having 3 to 20 carbon atoms such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group. Alkyl group: Examples thereof include an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group.

Examples of −OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group.

Examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, an icosyloxycarbonyl group and the like.

Examples of −SR ⁸ include methylsulfanil group, ethylsulfanil group, butylsulfanil group, hexylsulfanil group, decylsulfanil group and icosylsulfanil group.
Examples of −SO ₂ R ⁸ include a methyl sulfonyl group, an ethyl sulfonyl group, a butyl sulfonyl group, a hexyl sulfonyl group, a decyl sulfonyl group and an icosyl sulfonyl group.
Examples of −SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.

-SO ₂ NR ⁹ R ¹⁰ is a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3) -Methylbutyl) sulfamoyl group, N-cyclopentyl sulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N- Heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- N-1-substituted sulfamoyl groups such as (1,5-dimethyl) hexyl sulfamoyl group and N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group and N, N-heptylmethylsulfamoyl Examples thereof include N, N-2 substituted sulfamoyl groups such as groups.

Examples of the substituent that the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ^{10 may have include a hydroxy group and a halogen atom.}

The _{^{R 5, -CO 2 H, -CO}} 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H and _SO 2 NHR ⁹ are preferred, SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H and SO ₂ NHR ⁹ are more preferred.
As m, 1 to 4 is preferable, and 1 or 2 is more preferable.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ may be a linear group or a branched chain, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

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

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
The ⁺ a N (R ¹¹⁾ _4, of the four R ^11, it is preferred that at least two of a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. It is preferable that the total number of carbon atoms of the four R ¹¹ is 20 to 80, and more preferably from 20 to 60. ^{When +} N (R ¹¹ ) ₄ is present in the compound (1a), ^{if R 11} is these groups, the color filter containing the compound (1a) and having less foreign matter can be obtained from the colored curable resin composition of the present invention. Can be formed.

As a preferable example of the compound (1a), the compound represented by the formula (2a) and its tautomer (hereinafter, the compound represented by the formula (2a) and its tautomer are referred to as "compound (2a)". In some cases). When the compound (2a) is used, the content of the compound (2a) in the xanthene dye (Aa2) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more.

［式（２ａ）中、Ｒ²¹〜Ｒ²⁴は、互いに独立に、水素原子、−Ｒ²⁶又は置換基を有していてもよい炭素数６〜１０の１価の置換基を有していてもよい芳香族炭化水素基を表す。Ｒ²¹及びＲ²²は、一緒になって窒素原子を含む環を形成してもよく、Ｒ²³及びＲ²⁴は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ²⁵は、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ１⁺又は−ＳＯ₂ＮＨＲ²⁶を表す。
ｍ１は、０〜５の整数を表す。ｍ１が２以上の整数である場合、複数のＲ²⁵は同一であっても、異なってもよい。
ａ１は、０又は１の整数を表す。
Ｘ１は、ハロゲン原子を表す。
Ｒ²⁶は、炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｚ１⁺は、⁺Ｎ（Ｒ²⁷）₄、Ｎａ⁺又はＫ⁺を表す。
⁺Ｎ（Ｒ²⁷）₄における複数のＲ²⁷は、互い独立に、炭素数１〜２０の１価の飽和炭化水素基又はベンジル基を表す。］

[In formula (2a), R ^{21 to} R ²⁴ have a hydrogen atom, −R ^26, or a monovalent substituent having 6 to 10 carbon atoms, which may have a substituent, independently of each other. Represents a good aromatic hydrocarbon group. R ²¹ and R ²² may be combined to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may be combined to form a ring containing a nitrogen atom.
R ²⁵ is, -SO ₃ ^- represents a Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents an integer from 0 to 5. When m1 is an integer of 2 or more, the plurality of R ^25s may be the same or different.
a1 represents an integer of 0 or 1.
X1 represents a halogen atom.
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
The plurality of R ^{27s in +} N (R ²⁷ ) ₄ independently represent monovalent saturated hydrocarbon groups or benzyl groups having 1 to 20 carbon atoms. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{21 to} R ²⁴ include the same groups as those listed as the aromatic hydrocarbon group in ^{R 1 to} R ^4. Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, it may be substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26.
As a combination of ^{R 21 to} R ^{24 , R 21} and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbons. hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, those substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ preferred. A more preferable combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and hydrogen contained in the aromatic hydrocarbon groups. Atoms are substituted with _{-SO 3} ^- Z1 ⁺ or -SO ₂ NHR ^26.
When R ^{21 to} R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

As ^{a ring containing a nitrogen atom formed by R 21} and R ²² together, and a ring containing a nitrogen atom formed by R ²³ and R ²⁴ together, R ¹ and R ² are combined. Examples thereof include rings similar to the ring to be formed. Of these, an aliphatic heterocycle is preferable. Examples of the aliphatic heterocycle include the following rings.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same group as the group mentioned as ^{the saturated hydrocarbon group in R 8 to} R ^11.
When R ^{21 to} R ²⁴ are -R ²⁶ , the plurality of -R ^26s are preferably methyl or ethyl groups independently of each other. As the R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, 2-Ethylhexyl groups are more preferred. When R ²⁶ is these groups, a color filter containing less foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
The ⁺ a N (R ²⁷⁾ _4, among the four R ^27, it is preferred that at least two of a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. It is preferable that the total number of carbon atoms of the four R ²⁷ is 20 to 80, and more preferably from 20 to 60. When compound (2a) has ⁺ N (R ²⁷ ) ₄ , a color filter with less foreign matter is formed from the colored curable resin composition of the present invention in which ^{R 27 contains the compound (2a) which is a group thereof.} can.

As m1, 1 to 4 is preferable, and 1 or 2 is more preferable.

As a preferable example of the compound (1a), the compound represented by the formula (3a) and its tautomer (hereinafter, the compound represented by the formula (3a) and its tautomer are referred to as "compound (3a)". In some cases). When the compound (3a) is used, the content of the compound (3a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more.

［式（３ａ）中、Ｒ³¹及びＲ³²は、互いに独立に、炭素数１〜１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、炭素数６〜１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ³³及びＲ³⁴は、互いに独立に、炭素数１〜４のアルキル基、炭素数１〜４のアルキルスルファニル基又は炭素数１〜４のアルキルスルホニル基を表す。
Ｒ³¹及びＲ³³は、一緒になって窒素原子を含む環を形成してもよく、Ｒ³²及びＲ³⁴は、一緒になって窒素原子を含む環を形成してもよい。
ｐ及びｑは、互いに独立に、０〜５の整数を表す。ｐが２以上である場合、複数のＲ³³は同一であっても異なってもよく、ｑが２以上である場合、複数のＲ³⁴は同一であっても異なってもよい。
Ｒ^１１は、上記と同じ意味を表す。］

[In the formula (3a), R ³¹ and R ³² represent monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms independently of each other, and the hydrogen atoms contained in the saturated hydrocarbon groups have 6 to 10 carbon atoms. It may be substituted with 10 aromatic hydrocarbon groups or halogen atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and the saturated hydrocarbon may be substituted. it is, -O - - _-CH 2 contained in the hydrogen radical, - CO- or ^{-NR 11} - may be replaced by.
R ³³ and R ³⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl sulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ³¹ and R ³³ may be combined to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be combined to form a ring containing a nitrogen atom.
p and q represent integers 0 to 5 independently of each other. When p is 2 or more, the plurality of R ^33s may be the same or different, and when q is 2 or more, the plurality of R ^34s may be the same or different.
R ¹¹ has the same meaning as described above. ]

The ^{monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms in R 31} and R ³² include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl. A linear alkyl group having 1 to 10 carbon atoms such as a group; a branched chain alkyl group having 3 to 10 carbon atoms such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group; a cyclopropyl group and a cyclopentyl group. Examples thereof include an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms such as a group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group.
The aromatic hydrocarbon group which may have a substituent include the same groups as aromatic hydrocarbon group in R ^1.
Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group and a propoxy group.
R ³¹ and R ³² are preferably monovalent saturated hydrocarbon groups having 1 to 3 carbon atoms independently of each other.

Examples of the alkyl group having 1 to 4 carbon atoms representing R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl sulfanyl group, an ethyl sulfanyl group, a propyl sulfanyl group, a butyl sulfanyl group, an isopropyl sulfanyl group and the like.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl sulfonyl group, an ethyl sulfonyl group, a propyl sulfonyl group, a butyl sulfonyl group and an isopropyl sulfonyl group.
R ³³ and R ³⁴ are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups.

As p and q, an integer of 0 to 2 is preferable, and 0 or 1 is more preferable.

Examples of the compound (1a) include compounds represented by formulas (1-1) to (1-42) and formulas (1-21'). In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. The compounds represented by the formulas (1-1) to (1-29) and (1-21') correspond to the compound (2a), and are represented by the formulas (1-30) to (1-42). The compound to be added corresponds to compound (3a).

Among these, C.I. I. Sulfonamides of Acid Red 289, C.I. I. Acid Red 289 Quaternary Ammonium Salt, C.I. I. Sulfonamides of acid violet 102 or C.I. I. A quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such compounds include compounds represented by formulas (1-1) to (1-8), formulas (1-11) and formulas (1-12).
Further, compounds represented by formulas (1-30) to (1-39) are preferably mentioned because they are excellent in solubility in an organic solvent.

As the xanthene dye (Aa2), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugai Pharmaceutical Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) can be used. can. Further, it is also possible to synthesize using a commercially available xanthene dye as a starting material with reference to Japanese Patent Application Laid-Open No. 2010-32999.

(Tetraazaporphyrin dye (Aa3))
The tetraazaporphyrin dye (Aa3) is a compound having a tetraazaporphyrin skeleton in the molecule. When the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.

Among these, as the tetraazaporphyrin dye (Aa3), a dye containing a compound represented by the formula (1c) (hereinafter, may be referred to as a compound (1c)) is preferable.

[In formula (1c), R ^{71 to} R ⁷⁸ are independently substituted with a hydrogen atom, a halogen atom, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, and substituted. It represents an aryl group which may be substituted, an aryloxy group which may be substituted, an aralkyloxy group which may be substituted, and an amino group which may be substituted.
x represents 1 or 2.
When x represents 1, M1 represents a divalent metal atom, a trivalent substituted metal atom, or a metal oxide atom.
When x represents 2, M1 represents a hydrogen atom or a monovalent metal atom. ]

Examples of the monovalent metal atom include alkali metal atoms such as Na, K and Li.
Examples of the divalent metal atom include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb and Sn.
Examples of the trivalent substituted metal atom, Al-Cl, Ga-Br , Ga-I, In-Cl, Al-C 6 H 5, In-C 6 H 5, Mn (OH), Mn [OSi (CH 3 ) ₃ ] and Fe-Cl and the like.
Examples of the metal oxide atom include V (= O), Mn (= O) and Ti (= O).
M1 is preferably a divalent metal atom or a metal oxide atom, more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, V (= O) or Ti (= O). It is more preferably Cu, Ni, Pd or V (= O), and particularly preferably Cu, Pd or V (= O).

In the compound (1c), a compound in which x is 1 and M1 is a divalent metal atom or a metal oxide atom, or x is 2 and M1 is a hydrogen atom is preferable, and x is 1. , M1 is a divalent metal atom or a metal oxide atom, more preferably.

R ^{71 to} R ⁷⁸ may be independently substituted with a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 24 carbon atoms, or an alkyl group having 1 to 24 carbon atoms. An alkoxy group, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted aryloxy group having 6 to 30 carbon atoms, an optionally substituted aralkyloxy group having 7 to 30 carbon atoms, or Represents a substituted amino group having 1 to 30 carbon atoms, and more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, an alkyl group having 1 to 16 carbon atoms which may be substituted, and carbon. Substituent alkoxy groups of numbers 1 to 16, optionally substituted aryl groups of 6 to 24 carbon atoms, optionally substituted aryloxy groups of 6 to 24 carbon atoms, 7 to 24 carbon atoms Represents an optionally substituted aralkyloxy group or a substituted amino group having 1 to 16 carbon atoms, and is substituted independently of each other, more preferably a hydrogen atom, a fluorine atom, a bromine atom, a cyano group, or a substituted amino group having 1 to 10 carbon atoms. An alkyl group which may be present, an alkoxy group which may be substituted with 1 to 10 carbon atoms, an aryl group which may be substituted with 6 to 16 carbon atoms, and an aryl group which may be substituted with 6 to 16 carbon atoms. It represents an oxy group, an optionally substituted arylyloxy group having 7 to 16 carbon atoms, or a substituted amino group having 1 to 12 carbon atoms.

^{Specific examples of R 71 to} R ^{78 in} the formula (1c) are shown below.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and sec-. Butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n -Heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl -4-Heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexyl Heptyl group, n-tetradecyl group, n-pentadecyl group, 1-heptyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octylnonyl group, n-octadecyl group, 1-nonyldecyl group, 1-decylundecyl group, Examples thereof include linear, branched or cyclic alkyl groups consisting only of carbon atoms and hydrogen atoms such as n-eicosyl group, n-docosyl group, n-tetracosyl group, 1-adamantyl group, cyclopentyl group and cyclohexyl group and norbornyl group. ..

Examples of the substituent in the alkyl group include an alkyloxy group having 1 to 16 carbon atoms, an alkyloxyalkyloxy group having 2 to 16 carbon atoms, an aralkyloxy group having 7 to 16 carbon atoms, and an aryloxy group having 6 to 16 carbon atoms. Examples thereof include an alkylthio group having 1 to 16 carbon atoms, a halogen atom, a halogenoalkyloxy group having 1 to 16 carbon atoms, and an aryloxy group having 6 to 16 carbon atoms.
Specific examples of the alkyl group having a substituent include a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, an n-hexyloxymethyl group, a (2-ethylbutyloxy) methyl group, and an n-octyloxymethyl group. n-decyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group , 2-n-hexyloxyethyl group, 2- (2'-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2'-ethylhexyloxy) Ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-Ethylpropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyloxy) Propyl group, 3- (2'-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2'-ethylhexyloxy) propyl group, 3- (n-decyloxy) propyl group, 3- (N-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4- Isopropoxybutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5 -Methylpentyl group, 5-ethoxypentyl group, 5-n-propoxypentyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6 -N-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxy An alkyl group having an alkyloxy group, such as a dodecyl group, a 12-isopropoxidedecyl group and a tetrahydrofurfuryl group;
(2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) methyl group, (2-n-hexyloxyethoxy) methyl group, (3-methoxypropyloxy) methyl Group, (3-ethoxypropyloxy) methyl group, (3-n-butyloxypropyloxy) methyl group, (3-n-pentyloxypropyloxy) methyl group, (4-methoxybutyloxy) methyl group, (6 -Methyloxyloxy) methyl group, (10-ethoxydecyloxy) methyl group, 2- (2'-methoxyethoxy) ethyl group, 2- (2'-ethoxyethoxy) ethyl group, 2- (2'-n- Butoxyethoxy) ethyl group, 3- (2'-ethoxyethoxy) propyl group, 3- (2'-methoxypropyloxy) propyl group, 3- (2'-isopropyloxypropyloxy) propyl group, 3- (3') An alkyl group having an alkyloxyalkyloxy group, such as a −methoxypropyloxy) propyl group, a 3- (3'-ethoxypropyloxy) propyl group; for example, a benzyloxymethyl group, a 2-benzyloxyethyl group, a 2-phenethyl group. Oxyethyl group, 2- (4'-methylbenzyloxy) ethyl group, 2- (2'-methylbenzyloxy) ethyl group, 2- (4'-fluorobenzyloxy) ethyl group, 2- (4'-chloro Benzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4'-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 2- (benzyloxymethoxy) ethyl group and 2- (4'-methyl) An alkyl group having an aralkyloxy group, such as a benzyloxymethoxy) ethyl group;
Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyloxymethyl group Group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4'-methylphenyloxy) ethyl group, 2- (4'-ethylphenyloxy) ethyl group, 2- (4'-methoxyphenyl) Oxy) ethyl group, 2- (4'-chlorophenyloxy) ethyl group, 2- (4'-bromophenyloxy) ethyl group, 2- (1'-naphthyloxy) ethyl group, 2- (2'-naphthyloxy) ) Ethyl group, 3-phenyloxypropyl group, 3- (2'-naphthyloxy) propyl group, 4-phenyloxybutyl group, 4- (2'-ethylphenyloxy) butyl group, 5- (4'-tert) -Butylphenyloxy) pentyl group, 6- (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3'-chlorophenyloxy) decyl group, 2- (2) An alkyl group having an aryloxy group, such as an'-phenyloxyethoxy) ethyl group, a 3- (2'-phenyloxyethoxy) propyl group, a 4- (2'-phenyloxyethoxy) butyl group;
n-Butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octyl Thioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group , 4-N-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group and 8-methylthiooctyl group. Alkyl group having;
Fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n-propyl Group, 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 1,1-dihydro- Perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1, 1-dihydro-perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1-dihydro-perfluoro-n-tetradecyl group, 1,1-dihydro-perfluoro-n -Hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 2,2-bis (trifluoromethyl) propyl group, dichloromethyl group, Alkyl groups having halogen atoms such as 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group and 2,2,2-trichloroethyl group;
Fluoromethyloxymethyl group, 3-fluoro-n-propyloxymethyl group, 6-fluoro-n-hexyloxymethyl group, trifluoromethyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1, 1-dihydro-perfluoro-n-propyloxymethyl group, 2-hydro-perfluoro-2-propyloxymethyl group, 1,1-dihydro-perfluoro-n-butyloxymethyl group, 1,1-dihydro- Perfluoro-n-pentyloxymethyl group, 1,1-dihydro-perfluoro-n-hexyloxymethyl group, 1,1-dihydro-perfluoro-n-octyloxymethyl group, 1,1-dihydro-perfluoro -N-decyloxymethyl group, 1,1-dihydro-perfluoro-n-tetradecyloxymethyl group, 2,2-bis (trifluoromethyl) propyloxymethyl group, 3-chloro-n-propyloxymethyl group , 2- (8-fluoro-n-octyloxy) ethyl group, 2- (1,1-dihydro-perfluoroethyloxy) ethyl group, 2- (1,1,3-trihydro-perfluoro-n-propyl) Oxy) ethyl group, 2- (1,1-dihydro-perfluoro-n-pentyloxy) ethyl group, 2- (6-fluoro-n-hexyloxy) ethyl group, 2- (1,1-dihydro-per) Fluoro-n-octyloxy) ethyl group, 3- (4-fluorocyclohexyloxy) propyl group, 3- (1,1-dihydro-perfluoroethyloxy) propyl group, 3- (1,1-dihydro-perfluoro) -N-dodecyloxy) propyl group, 4- (perfluoro-n-hexyloxy) butyl group, 4- (1,1-dihydro-perfluoroethyloxy) butyl group, 6- (2-chloroethyloxy) hexyl An alkyl group having a halogenoalkyloxy group, such as a group and a 6- (1,1-dihydro-perfluoroethyloxy) hexyl group;
Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-ethylphenyloxymethyl group, 4-n-propylphenyloxymethyl group, 4-n -Butylphenyloxymethyl group, 4-tert-butylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-octylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4-methoxy Phenyloxymethyl group, 4-ethoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-n-pentyloxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 3-fluorophenyloxymethyl group, 2- Fluorophenyloxymethyl group, 3,4-difluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-chlorophenyloxymethyl group, 4-phenylphenyloxymethyl group, 1-naphthyloxymethyl group, 2-naphthyloxymethyl group Group, 2-furyloxymethyl group, 1-phenyloxyethyl group, 2-phenyloxyethyl group, 2- (4'-methylphenyloxy) ethyl group, 2- (4'-ethylphenyloxy) ethyl group, 2 -(4'-n-hexylphenyloxy) ethyl group, 2- (4'-methoxyphenyloxy) ethyl group, 2- (4'-n-butoxyphenyloxy) ethyl group, 2- (4'-fluorophenyl) Oxy) ethyl group, 2- (4'-chlorophenyloxy) ethyl group, 2- (4'-bromophenyloxy) ethyl group, 2- (1'-naphthyloxy) ethyl group, 2- (2'-naphthyloxy) ) Ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3- (4'-methylphenyloxy) propyl group, 3- (2'-naphthyloxy) propyl group, 4-phenyloxybutyl group, 4- (2'-Ethylphenyloxy) butyl group, 4-phenyloxypentyl group, 5-phenyloxypentyl group, 5- (4'-tert-butylphenyloxy) pentyl group, 6-phenyloxyhexyl group, 6 Alkyl groups having an aryloxy group such as-(2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group and 10- (3'-methylphenyloxy) decyl group can be mentioned. ..

Examples of the substituent in the alkoxy group include substituents similar to those in the above-mentioned alkyl group, and examples of the alkoxy group having the substituent include the groups described as specific examples of the above-mentioned alkyl group having the substituent. Examples include the group to be induced.
Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthrasenyl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 1-pyrenyl group and a 2-pyrenyl group. Examples thereof include 2-perylenyl group, 3-perylenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 7-fluoranthenyl group and 8-fluoranthenyl group.
Examples of the substituent in the aryl group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a halogen atom. Be done.
Specific examples of the aryl group having a substituent include 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4'-tert-butylcyclohexyl) phenyl group and 3-cyclohexyl. An aryl group having an alkyl group such as a phenyl group, a 2-cyclohexylphenyl group, a 4-ethyl-1-naphthyl group, a 6-n-butyl-2-naphthyl group and a 2,4-dimethylphenyl group;
4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2- Alkoxy such as isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group and 2-phenyloxyphenyl group. An aryl group having a group and an allyloxy group;
4-Phenylphenyl group, 3-Phenylphenyl group, 2-Phenylphenyl group, 2,6-diphenylphenyl group, 4- (2'-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1-phenyl- An aryl group having an aryl group such as a 2-naphthyl group and a 7-phenyl-1-pyrenyl group;
4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2 An aryl group having a halogen atom such as a methyl-3-chlorophenyl group, a 2-methoxy-4-fluorophenyl group and a 2-fluoro-4-methoxyphenyl group;
2-Trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl group, 4- Examples thereof include ethylthiophenyl group, 4-cyanophenyl group and 3-cyanophenyl group.
Examples of the substituent in the aryloxy group include substituents similar to those in the above-mentioned aryl group, and examples of the aryloxy group having a substituent are described as specific examples of the above-mentioned aryl group having a substituent. Examples include groups derived from groups.
The aralkyloxy group which may be substituted includes a benzyloxy group, an α-methylbenzyloxy group, a phenethyloxy group, an α-methylphenetyloxy group, an α, α-dimethylbenzyloxy group, an α, α-dimethylphenethyloxy group. Aralkyloxy groups having an unsubstituted or alkyl group, such as a group, a 4-methylphenethyloxy group, a 4-methylbenzyloxy group and a 4-isopropylbenzyloxy group;
An aralkyloxy group having an allyl group such as a 4-benzylbenzyloxy group, a 4-phenethylbenzyloxy group, a 4-phenylbenzyloxy group or an aralkyl group; a 4-methoxybenzyloxy group, a 4-n-tetradecyloxybenzyl Oxy group, 4-n-heptadecyloxybenzyloxy group, 3,4-dimethoxybenzyloxy group, 4-methoxymethylbenzyloxy group, 4-vinyloxymethylbenzyloxy group, 4-benzyloxybenzyloxy group and 4- An aralkyloxy group having a substituted oxy group such as a phenethyloxybenzyloxy group;
Aralkyloxy group having a hydroxyl group such as 4-hydroxybenzyloxy group, 4-hydroxy-3-methoxybenzyloxy group; such as 4-fluorobenzyloxy group, 3-chlorobenzyloxy group and 3,4-dichlorobenzyloxy group. Aralkyloxy group with halogen atom;
Examples thereof include 2-furfuryloxy group, diphenylmethyloxy group, 1-naphthylmethyloxy group and 2-naphthylmethyloxy group.
Specific examples of the amino group having a substituent include N-methylamino group, N-ethylamino group, Nn-butylamino group, N-cyclohexylamino group, Nn-octylamino group and Nn-. Amino groups with alkyl groups such as decylamino groups;
N-benzylamino group, N-phenylamino group, N- (3-methylphenyl) amino group, N- (4-methylphenyl) amino group, N- (4-n-butylphenyl) amino group, N- ( 4-methoxyphenyl) amino group, N- (3-fluorophenyl) amino group, N- (4-chlorophenyl) amino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group, etc. Amino group with aralkyl or aryl group;
N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-butylamino group, N, N-di-n-hexylamino group, N, N-di-n-octylamino group , N, N-di-n-decylamino group, N, N-di-n-dodecylamino group, N-methyl-N-ethylamino group, N-ethyl-Nn-butylamino group, N-methyl- Alkyl or aralkyl disubstituted amino groups such as N-phenylamino groups, N-ethyl-N-phenylamino groups and Nn-butyl-N-phenylamino groups;
N, N-diphenylamino group, N, N-di (3-methylphenyl) amino group, N, N-di (4-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino group, N, N-di (4-tert-butylphenyl) amino group, N, N-di (4-n-hexylphenyl) amino group, N, N-di (4-methoxyphenyl) amino group, N, N- Di (4-ethoxyphenyl) amino group, N, N-di (4-n-butoxyphenyl) amino group, N, N-di (4-n-hexyloxyphenyl) amino group, N, N-di (1) -Naphthyl) amino group, N, N-di (2-naphthyl) amino group, N-phenyl-N- (3-methylphenyl) amino group, N-phenyl-N- (4-methylphenyl) amino group, N -Phenyl-N- (4-octylphenyl) amino group, N-phenyl-N- (4-methoxyphenyl) amino group, N-phenyl-N- (4-ethoxyphenyl) amino group, N-phenyl-N- (4-n-Hexyloxyphenyl) amino group, N-phenyl-N- (4-fluorophenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-) Examples thereof include amino groups substituted with aryl groups such as naphthyl) amino group, N-phenyl-N- (3-phenylphenyl) amino group and N-phenyl-N- (4-phenylphenyl group) amino group. ..

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

As the tetraazaporphyrin dye, in compound (1c), x is 1, M1 is a divalent metal atom, and R ^{71 to} R ⁷⁸ are substituted with 1 to 24 carbon atoms independently of each other. A good alkyl group, or a compound which is an optionally substituted aryl group having 6 to 30 carbon atoms is preferable, x is 1, M1 is Cu, and R ^{71 to} R ⁷⁸ are carbons independently of each other. Compounds of numbers 1 to 6 which are optionally substituted alkyl groups or optionally substituted phenyl groups are more preferred, and compounds represented by the formula (2-29) are even more preferred.
The composition containing the tetraazaporphyrin dye can form a high-contrast coating film or pattern and generate less foreign matter.

(Dye (Aa4))
The dye (Aa4) is not particularly limited as long as it is a dye different from the triarylmethane colorant (Aa1), the xanthene dye (Aa2), and the tetraazaporphyrin dye (Aa3), and the dye (Aa4) is oil-soluble. Dyes such as dyes, acidic dyes, basic dyes, direct dyes, medium dyes, amine salts of acidic dyes and sulfonamide derivatives of acidic dyes, for example, dyes in the Color Index (published by The Society of Dyers and Colorists), That is, compounds classified other than pigments and known dyes described in dyeing notes (color dyeing company) can be mentioned. Further, according to the chemical structure, azo dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, squarylium dyes, acrydin dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes and the like can be mentioned. .. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C. I. Solvent Red 125, 130;
C. I. Solvent Orange 2, 7, 11, 15, 56;
C. I. Solvent Blue 37, 67, 70, 90;
C. I. Solvent Green 5, 7, 34, 35, etc. I. Solvent dye,
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, 57, 66, 73, 80, 88, 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, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 421, 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 6, 7;
C. I. Acid Blue 18, 29, 59, 60, 70, 72, 74, 82, 87, 92, 102, 113, 117, 120, 126, 130, 131, 142, 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 58, 63, 65, 80, 104, 105, 106, 109 and the like. I. Acid dye,
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 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, 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, 245, 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 and the like. I. Direct dye,
C. I. Basic Blue 3, 9, 19, 24, 25, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 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. Modant 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. Modant Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modant Blue 2, 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. Modant Green 1, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Examples include modern dyes.

(Pigment (Ab))
The color curable resin composition of the present invention may contain a pigment (Ab). As the pigment (Ab), a known pigment can be used without particular limitation, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
Examples of the pigment (Ab) 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. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Examples thereof include black pigments such as Pigment Blacks 1 and 7.

The pigment (Ab) is preferably a blue pigment, more preferably a phthalocyanine pigment and a dioxazine pigment, and even more preferably C.I. I. It is at least one selected from the group consisting of Pigment Blue 15: 6 and Pigment Violet 23.

The pigment (Ab) may be treated with a rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, a sulfuric acid atomization method, etc., if necessary. It may be subjected to atomization treatment by the above, cleaning treatment with an organic solvent, water or the like for removing impurities, removal treatment of ionic impurities by an ion exchange method or the like. It is preferable that the particle size of each pigment is uniform.
The pigment can be made into a pigment dispersion liquid in a state of being uniformly dispersed in the pigment dispersant solution by containing a pigment dispersant and performing a dispersion treatment. The pigments may be individually dispersed 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 pigment dispersants, 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 Co., Ltd.), Azisper (manufactured by BASF Co., Ltd.) Examples thereof include Ajinomoto Fine Techno Co., Ltd. (manufactured by Big Chemie Co., Ltd.) and Disperbyk (manufactured by Big Chemie Co., Ltd.).
When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of types unless otherwise specified.

The content of the colorant (A) in the color curable resin is preferably 5% by mass or more and 70% by mass or less, and more preferably 5% by mass or more and 60% by mass or less, based on the total amount of solids. More preferably, it is 5% by mass or more and 50% by mass or less. When the content of the colorant (A) is within the above range, desired spectroscopy and color density can be obtained.

In the present specification, the "total amount of solid content" means the total amount of the components excluding the solvent (E) from the colored curable resin composition of the present invention. The total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

In the colorant (A), the content of each dye can be appropriately selected according to the desired spectroscopy, but the following range is preferable from the viewpoint of forming a high-contrast coating film or pattern.

The content of the triarylmethane colorant (Aa1) in the colorant (A) is preferably 0.5% by mass or more and 98% by mass or less, more preferably 61% by mass or more and 97% by mass or less, and further preferably. Is 81% by mass or more and 96% by mass or less.

The content of the xanthene dye (Aa2) in the colorant (A) is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.5% by mass or more and 40% by mass or less, and further preferably. It is 1% by mass or more and 20% by mass or less.

The content of the tetraazaporphyrin dye (Aa3) in the colorant (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more. Is. The content of the tetraazaporphyrin dye (Aa3) in the colorant (A) is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 10% by mass or less.

In the colorant (A), the content of the tetraazaporphyrin dye (Aa3) is preferably 0.5 to 50 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the triarylmethane colorant (Aa1). It is .0 to 20 parts by mass, more preferably 1.0 to 9.0 parts by mass, and even more preferably 1.2 to 8.8 parts by mass. When the content of the tetraazaporphyrin dye (Aa3) is within the above range, a higher contrast coating film or pattern can be formed.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as "resin (B)") is derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. It is a copolymer containing a structural unit.
Examples of such a resin (B) include the following resins [K1] to [K6].
Resin [K1] At least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)") and 2 to 4 carbon atoms. A copolymer with a monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)");
Resins [K2] (a) and (b) and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as "(c)" Copolymer with);
Copolymer of resin [K3] (a) and (c);
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.

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

(B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. say.
In (b), a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group is preferable.
In addition, in this specification, "(meth) acrylic acid" represents at least one kind 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 oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a simple monomer having an oxetanyl group and an ethylenically unsaturated bond. A metric (b2) (hereinafter sometimes referred to as "(b2)"), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)"), etc. Can be mentioned.

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)”). There is), and a monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter, may be referred to as “(b1-2)”) can be mentioned.

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and 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-tris (Glysidyloxymethyl) styrene and the like can be mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel Co., Ltd.), and 3,4-epoxycyclohexylmethyl (meth) acrylate (for example,). Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (II) and a compound represented by the formula (III). Examples thereof include compounds represented by.

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

Examples of the alkyl group having 1 to 4 carbon atoms 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.
Alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.
Examples of R ^a and R ^b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group having 1 to 6 carbon atoms includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Diyl group and hexane-1,6-diyl group and the like can be mentioned.
Examples of X ^a and X ^b are independent of each other, preferably a single bond, a methylene group, an ethylene group, * -CH _2- O- and * -CH ₂ CH _2- O-, and more preferably a single bond. * -CH ₂ CH _2- O- can be mentioned (* represents a bond with O).

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

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

The compound represented by the formula (II) and the compound represented by the formula (III) may be used alone, or the compound represented by the formula (II) and the compound represented by the formula (III) may be used in combination. You may. 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 on a molar basis, preferably 5:95 to 95: 5, and more preferably 10:90 to. It is 90:10, more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyloxymethyloxetane. , 3-Methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.

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

As (b), (b1) is preferable in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further improved. Further, (b1-2) is more preferable in that the color-curable resin composition is excellent in storage stability.

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 ] Decane-8-yl (meth) acrylate (In the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate", and when it is referred to as "tricyclodecyl (meth) acrylate". ), Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate". ), Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl. (Meta) acrylic acid esters such as (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;
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 and 5,6-bis (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylnitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene and 2,3-dimethyl-1,3-butadiene and the like.
Of these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N. -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

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

Resin [K1] can be used, for example, in the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972). It can be manufactured with reference to the cited references described in.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples thereof include a method of heating and keeping warm. The polymerization initiator, solvent and the like are not particularly limited, and those usually used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). As the solvent, any solvent may be used as long as it dissolves each monomer, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later.

As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the copolymer is taken out as a solid (powder) by a method such as reprecipitation. You may use the one. In particular, by using the solvent contained in the color curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the color curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each is determined in the total structural units constituting the resin [K2].
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2-95 mol%
Structural unit derived from (c); 1-65 mol%
Is preferable,
Structural unit derived from (a); 5-40 mol%
Structural unit derived from (b); 5-80 mol%
Structural unit derived from (c); 5-60 mol%
Is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the color-curable resin composition, the developability when forming a color pattern, and the solvent resistance of the obtained color filter, It tends to have excellent heat resistance and mechanical strength.

The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

In the resin [K3], the ratio of the structural units derived from each is determined among all the structural units constituting the resin [K3].
Structural unit derived from (a); 2-60 mol%
Structural unit derived from (c); 40-98 mol%
Is preferable,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50-90 mol%
Is more preferable.
The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

The resin [K4] is a carboxylic acid and / or a carboxylic acid anhydride having the cyclic ether having 2 to 4 carbon atoms of (b) obtained by obtaining a copolymer of (a) and (c). It can be manufactured by adding to.
First, the copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that mentioned in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms of (b) is reacted with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.
Following the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen, and (b), a reaction catalyst of carboxylic acid or carboxylic acid anhydride and cyclic ether (for example, Tris (for example, Tris). Resin [K4] can be produced by putting (dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours, for example. can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, based on 100 mol of (a). Within this range, the storage stability of the color-curable resin composition, the developability when forming a pattern, and the balance between the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are improved. Tend. Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value of the polymerization, and the like.

As the first step, the resin [K5] obtains a copolymer of (b) and (c) in the same manner as in the above-mentioned production method of the resin [K1]. In the same manner as above, the obtained copolymer may be a solution after the reaction as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. You may use the one taken out as.
The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
Is preferable,
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c); 10-90 mol%
Is more preferable.

Further, under the same conditions as the method for producing the resin [K4], the carboxylic acid or carboxylic acid anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c). The resin [K5] can be obtained by reacting an object.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K5], and (b1-1) is more preferable.

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

The resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymers, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] Resins such as decyl (meth) acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymers, 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) acryloyl oxymethyl-oxetane / Resin such as (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / Resins such as tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer, etc. [K3]; Resins obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, etc. A resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, both tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid Resin such as resin to which glycidyl (meth) acrylate is added to the polymer [K4]; resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, tri Resin [K5] such as a resin obtained by reacting a copolymer of cyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate with (meth) acrylic acid; tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Examples thereof include a resin [K6] such as a resin obtained by reacting a copolymer with (meth) acrylic acid and further reacting with tetrahydrophthalic acid anhydride.

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

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30, It is 000. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the coloring pattern tends to be improved.
The dispersity [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 of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and even more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

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 with respect to the total amount of solids. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual 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). Examples of the polymerizable compound (C) include compounds having a polymerizable ethylenically unsaturated bond, and a (meth) acrylic acid ester compound is preferable.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. In addition, the above-mentioned (a), (b) and (c) can be mentioned.

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

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth). Acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocia Nurate, 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 Examples thereof include pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, and more preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of solids. be.
The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 35: 65-80: 20.
When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the coloring 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 that can initiate polymerization by generating active radicals, acids, etc. by the action of light or heat, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include an O-acyloxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, an acylphosphine oxide compound and the like.

前記Ｏ−アシルオキシム化合物としては、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン及びＮ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュアＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ（株）製）、Ｎ−１９１９（（株）ＡＤＥＫＡ製）等の市販品を用いてもよい。中でも、Ｏ−アシルオキシム化合物は、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン及びＮ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミンからなる群から選ばれる少なくとも１種が好ましく、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミンがより好ましい。これらのＯ−アシルオキシム化合物であると、高明度なカラーフィルタが得られる傾向にある。 The O-acyloxime compound is a compound having a structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1. −On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2) -Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-) Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Il] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1- On-2-imine and the like can be mentioned. Commercially available products such as Irgacure OXE01 and OXE02 (all manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used. Among them, the O-acyloxym compounds are N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and 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-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy is preferable. -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. With these O-acyloxime compounds, a high-brightness color filter tends to be obtained.

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

Examples of the compound having a structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl). ) -2-Benzylbutane-1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. Be done. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF Limited) may be used.
Examples of the compound having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy). ) Phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone and benzyl Dimethylketal and the like can be mentioned.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d2).

［式（ｄ５）中、Ｒ^１３〜Ｒ^１８は、互いに独立に、置換基を有していてもよい炭素数６〜１０のアリール基を表す。］ The biimidazole compound is, for example, a compound represented by the formula (d5).

[In formula (d5), R ^{13 to} R ¹⁸ represent aryl groups having 6 to 10 carbon atoms which may have substituents independently of each other. ]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xsilyl group, an ethylphenyl group and a naphthyl group, and a phenyl group is preferable.
Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, and a methoxy group is preferable.

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 JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4', 5 , 5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis ( 2-Chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole (see JP-A-48-38403, JP-A-62-174204, etc.) and 4,4', Examples thereof include an imidazole compound in which the phenyl group at the 5,5'-position is substituted with a carboalkoxy group (see JP-A-7-10913, etc.). Of these, compounds represented by the following formulas and mixtures thereof are preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-) Methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like. Be done.

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

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoin compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrene quinone, Kinone compounds such as 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate and titanosen compounds.
These are preferably used in combination with the polymerization initiation aid (D1) (particularly an amine compound) described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound, and more preferably. 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 by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part.

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4 -Dimethylaminobenzoate 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4,4'-bis Examples thereof include (ethylmethylamino) benzophenone, and preferably 4,4'-bis (diethylamino) benzophenone. Commercially available products such as EAB-F (manufactured by 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-di. Butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

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

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, and dichlorophenylsulfanyl acetic acid. Examples thereof include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When these polymerization initiators (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). , More preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a coloring 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. Examples of the solvent (E) include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), and ether. Ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , Propropylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol, methyl anisole and the like.

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

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. And so on.

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

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

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the color-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 within the above range, the flatness at the time of application of the color curable resin composition becomes good, and the display characteristics are not insufficient when the color filter is formed, so that the display characteristics are improved. Tends to be good.

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

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

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

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, and more preferably 0.002, based on the total amount of the colored curable resin composition. It is by mass% or more and 0.1% by mass or less, and 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.

<Antioxidant (H)>
From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use the antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an antioxidant generally used in the industry, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and the like can be used.

Examples of the phenolic antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Co., Ltd.), and Irganox. 1076 (Irganox 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Co., Ltd.), Irganox 1330 (Irganox 1330: 3,3', 3'', 5,5', 5''-Hexa-tert-butyl-a, a', a''-(methicylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Co., Ltd., Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- Trion, manufactured by BASF Co., Ltd., Irganox 3790: 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5- Triazine-2,4,6 (1H, 3H, 5H) -trion, manufactured by BASF Co., Ltd., Irganox 1035: thiodiethylenebis [3- (3,5-di-tert-butyl-4-) Hydroxyphenyl) propionate], BASF Co., Ltd.), Irganox 1135 (Irganox 1135: benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, BASF Co., Ltd., Irganox 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, BASF Co., Ltd.), Irganox 3125 (Irganox 3125, BASF Co., Ltd.), Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy 3', 5'-di-tert-butylanilino) -1,3,5-triazine, manufactured by BASF Co., Ltd. ), Adecastab AO-80 (Adecastab AO-80: 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-Tetraoxaspiro (5,5) Eun Decan, ADEKA Corporation, Sumitomo BHT (Sumilizer BHT, Sumitomo Chemical Co., Ltd.), Sumitomo GA-80 (Sumilizer GA-80, Sumitomo Chemical Co., Ltd.), Sumitomo GS (Sumilizer GS, Sumitomo Chemical Co., Ltd.) (Manufactured by Co., Ltd.), Cyanox 1790 (manufactured by Cyanox 1790, manufactured by Cytec Co., Ltd.), Vitamin E (manufactured by Eisai Corporation), and the like.

Examples of the phosphorus-based antioxidant include Irgafos 168 (Irgafos 168: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Co., Ltd.), Irgafos 12 (Irgafos 12: Tris [2-[[ 2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, manufactured by BASF Co., Ltd., Ilgaphos 38 (Irgafos 38: Bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphite, manufactured by BASF Co., Ltd.), Adecastab 329K (manufactured by ADEKA Co., Ltd.), Adecastab PEP36 (Made by ADEKA Co., Ltd.), Adecaster PEP-8 (Made by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (manufactured by Weston 618, GE), Weston 619G (manufactured by Weston 619G, GE) ), Ultranox 626 (Ultranox 626, manufactured by GE) and Sumilizer GP: 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8, Examples thereof include 10-tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the sulfur-based antioxidant include β-alkyl mercaptopropionic acid esters of dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. Examples include compounds.

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

<Manufacturing method of colored curable resin composition>
The color curable resin composition of the present invention is a leveling agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), which are used as necessary. It can be prepared by mixing the agent (F), the polymerization initiator (D1), the antioxidant (H), and other components.
When the pigment (Ab) is contained, the pigment is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size of the pigment becomes about 0.2 μm or less. .. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. The desired color-curable resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.
With respect to the colorant (A), it is preferable that the dye is previously dissolved in a part or all of the solvent (E) to prepare a solution. It is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 μm.
It is preferable to filter the colored curable resin composition after mixing with a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter>
A coloring pattern can be formed from the coloring curable resin composition of the present invention. Examples of the method for producing the colored pattern include a photolithography method, an inkjet method, a printing method, and the like, and a photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and 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 which is a cured product of the coloring composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the purpose, application and the like. For example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5. It is ~ 6 μm.

The substrate includes a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or on the substrate. Aluminum, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit, or the like may be formed on these substrates.

The formation of each color pixel by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows.
First, a color curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and / or vacuum drying to obtain a smooth color composition layer.
Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature for heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

The coloring composition layer is then exposed via a photomask to form the desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, and the like.
An exposure device such as a mask aligner and a stepper is used because it is possible to uniformly irradiate the entire exposed surface with parallel rays and accurately align the photomask with the substrate on which the coloring composition layer is formed. Is preferable.

A coloring pattern is formed on the substrate by developing the coloring composition layer after exposure by bringing it into contact with a developing solution. By development, the unexposed portion of the coloring composition layer is dissolved in a developing solution and removed.
As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method, a 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.

Further, it is preferable to post-bake the obtained coloring pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

The color curable resin composition of the present invention can produce a high-contrast color filter. The color filter is useful as a color filter used in a display device (liquid crystal display device, organic EL device, electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.
Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.

[Synthesis Example 1: Synthesis of Triarylmethane Colorant (AI-18)]
The following reaction was carried out in a nitrogen atmosphere. After adding 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide to a flask equipped with a cooling tube and a stirrer, the mixed solution was ice-cooled. After adding 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) little by little over 30 minutes under ice-cooling, the mixture was stirred for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the reaction solution, and the mixture was stirred at room temperature for 24 hours. After adding the reaction solution to 200 parts of ice water little by little, the mixture was allowed to stand at room temperature for 15 hours, and the water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to this viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was filtered off and then purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C. to obtain 9.8 parts of the compound represented by the formula (CI-18).

The following reaction was carried out in a nitrogen atmosphere. To a flask equipped with a cooling tube and a stirrer, 8.2 parts of the compound represented by the formula (BI-7), 10 parts of the compound represented by the formula (CI-18) and 20 parts of toluene were added. After that, 12.2 parts of phosphorus oxychloride was added, and the mixture was stirred at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then diluted with 170 parts isopropanol. Then, the diluted reaction solution was poured into 300 parts of saturated brine, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and when the mixture was allowed to stand for 30 minutes, it was separated into an organic layer and an aqueous layer. After discarding the aqueous layer by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, and the mixture was stirred for 30 minutes and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with an evaporator to obtain a bluish-purple solid. Further, the bluish purple solid was dried under reduced pressure at 60 ° C. to obtain 18.4 parts of the compound represented by the formula (A-II-18).

The following reaction was carried out in a nitrogen atmosphere. To a flask equipped with a cooling tube and a stirrer, 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol were added, and then the mixture was stirred at room temperature for 30 minutes to prepare a blue solution. Then, after adding 396 parts of water to the blue solution, the mixture was further stirred at room temperature for 30 minutes to obtain a reaction solution.
53 parts of water was added to the beaker, and 11.8 parts of kegin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were added to the water and mixed at room temperature to prepare a phosphotungstic acid solution.
The obtained phosphotungstic acid solution was added dropwise to the previously prepared reaction solution over 1 hour. After further stirring at room temperature for 30 minutes, the mixture was filtered to obtain a blue solid. The obtained blue solid was added to 200 parts of methanol, dispersed for 1 hour, and then filtered, and the operation was repeated twice. The blue solid obtained by the operation was added to 200 parts of water, dispersed for 1 hour, and then filtered, and the operation was repeated twice. The blue solid obtained by the operation was dried under reduced pressure at 60 ° C. to obtain 17.1 parts of the triarylmethane colorant (AI-18) represented by the formula (AI-18).

[Synthesis Example 2: Synthesis of Xanthene Dye (1-38)]
20 parts of the compound represented by the formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the obtained solution was mixed at 110 ° C. The mixture was stirred for 6 hours. The obtained reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35% by mass hydrochloric acid, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were obtained as a residue of suction filtration and then dried to obtain a xanthene dye (1-38) represented by the formula (1-38).

[Synthesis Example 3: Synthesis of Tetraazaporphyrin Dye (Aa3-1)]
In the synthetic method described in Japanese Patent No. 3961078, the tetraazaporphyrin dye (Aa3-1) (formula (2-29), formula (2-39), formula (2-40), and formula (2-41)). A mixture of the compounds represented) was obtained.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部を乳酸エチル２２５部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量（Ｍｗ）が９．１×１０^３、分散度が２．１、固形分が２６質量％、固形分酸価が１２０ｍｇ−ＫＯＨ／ｇの樹脂Ｂ１溶液を得た。樹脂Ｂ１は下記に示す構造単位を有する。

[Synthesis Example 4: Synthesis of Resin B1]
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. and kept warm while stirring. Then, Table 46 parts of acrylic acid, and 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl acrylate (Formula (compounds and the formula represented by I-1) (II-1 ) The compound to be compounded is mixed at a molar ratio of 50:50.) A flask prepared by dissolving 240 parts in 185 parts of ethyl lactate and keeping the solution at 70 ° C. for 4 hours using a dropping funnel. Dropped inside.

On the other hand, a solution prepared by dissolving 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was added dropwise into the flask over 4 hours using another dropping funnel. After the addition of the solution of the polymerization initiator is completed, 4 hours, kept at 70 ° C., then cooled to room temperature, and the weight average molecular weight (Mw) of 9.1 × 10 ^3, the degree of dispersion of 2.1, a solid A resin B1 solution having a molecular weight of 26% by mass and a solid acid value of 120 mg-KOH / g was obtained. Resin B1 has the structural units shown below.

[Synthesis Example 5: Synthesis of Resin B2]
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was placed therein, and the mixture was heated to 85 ° C. with stirring. Then, represented by 54 parts of acrylic acid, a compound represented by 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl acrylate (formula (I-1) and formula (II-1) The compound was mixed at a molar ratio of 50:50.) A mixed solution of 225 parts of vinyl toluene (isomer mixture) and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours.

On the other hand, a mixed solution prepared by dissolving 30 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropping, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin B2) having a B-type viscosity (23 ° C.) of 246 mPas, a solid content of 37.5%, and a solution acid value of 43 mg-KOH / g. ) Was obtained. The weight average molecular weight of the resin B2 (Mw) is 1.1 × 10 ^4, the degree of dispersion was 2.01. Resin B2 has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins obtained in Synthesis Examples 4 and 5 were measured by using the GPC method under the following conditions.
Equipment: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shima-pack GPC-80M
Column temperature; 40 ° C
Solvent; THF (tetrahydrofuran)
Flow velocity; 1.0 mL / min
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained above was defined as the degree of dispersion.

[Preparation Example 1: Preparation of dispersion liquid (1)]
10 parts of the triarylmethane colorant (AI-18) obtained in Synthesis Example 1, 2 parts of a dispersant (BYK (registered trademark) -LPN6919 (manufactured by Big Chemie Japan)), and 5 parts of Synthesis Example 5 were obtained. A dispersion liquid was obtained by mixing 4 parts of the obtained resin B2 (in terms of solid content) and 84 parts of propylene glycol monomethyl ether acetate, and sufficiently dispersing the triarylmethane colorant (AI-18) using a bead mill. (1) was obtained.

[Preparation Example 2: Preparation of Dispersion Liquid (2)]
By mixing 12 parts of a pigment (CI Pigment Blue 15: 6), 2 parts of an acrylic pigment dispersant and 80.5 parts of propylene glycol monomethyl ether acetate, and sufficiently dispersing the pigment using a bead mill. , The dispersion liquid (2) was obtained.

[Examples 1 to 7, Comparative Examples 1 to 3]
(Preparation of Color Curable Resin Composition)
Dispersion liquid (1) (containing 10% by mass of the triarylmethane colorant (AI-18) obtained in Synthesis Example 1),
-Xanthene dye (1-38) obtained in Synthesis Example 2,
-Tetraazaporphyrin dye (Aa3-1) obtained in Synthesis Example 3,
・ Dispersion liquid (2),
(B) Resin: Resin B1 obtained in Synthesis Example 4,
(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.),
(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Ltd.)
(F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.),
-(E) Solvent: Ethyl lactate (EL),
(E) Solvent: Propylene glycol monomethyl ether acetate (PGMEA) was mixed in the number of parts shown in Table 3 to obtain a colored curable resin composition.

<Making a colored pattern>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to obtain a colored composition layer. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere at 150 mJ / cm. Light was irradiated with an exposure amount of ^{2 (based on 365 nm).} As the photomask, a photomask having a 100 μm line-and-space pattern formed was used. The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and then in an oven at 230. Post-baking was performed at ° C. for 30 minutes to obtain a coloring pattern.

<Film thickness measurement>
The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 4. In Table 4, the colorants (A) contained in the color-curable resin composition obtained by mixing in the number of copies shown in Table 3 were converted so that the total amount of the colorants (A) was 100. The content of each component is shown.

<Saturation evaluation>
The obtained coloring pattern is spectrally measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates in the XYZ color system of CIE using the characteristic function of the C light source. (X, y) and the tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 4.

<Contrast evaluation>
A colored coating film was prepared by performing the same operation as the production of the colored pattern except that a photomask was not used at the time of exposure. Contrast meter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5A; manufactured by Topcon Co., Ltd., light source; F-10, polarizing film; manufactured by Tsubosaka Electric Co., Ltd.) was used for the obtained colored coating film. The contrast was measured with a blank value of 30,000. If the contrast in the colored coating film is high, it can be said that the contrast in the colored pattern is also high. The results are shown in Table 4.

The colored curable resin compositions of Examples 1 and 2 and Comparative Example 2 have a chromaticity coordinate of y of 0.095 and a chromaticity coordinate of x of 0.135 to 0.138, which are close in chromaticity. A colored pattern was obtained. In Examples 1 and 2, a coloring pattern having a higher brightness was obtained as compared with Comparative Example 2, and a colored coating film showing high contrast was obtained.
The colored curable resin compositions of Examples 3 to 7 and Comparative Examples 1 and 3 have a chromaticity coordinate of y of 0.095 and a chromaticity coordinate of x of 0.150 to 0.151, which are close colors. A degree coloring pattern was obtained. In Examples 3 to 7, a coloring pattern having a higher brightness was obtained as compared with Comparative Examples 1 and 3, and a colored coating film showing a high contrast was obtained.

As described above, it can be seen that the coloring curable resin composition of the present invention can produce a highly contrasting coloring pattern. Further, the color filter obtained from the colored curable resin composition of the present invention has excellent display characteristics and is useful as a material for a liquid crystal display device.

Claims (3)

Contains colorants, resins, polymerizable compounds and polymerization initiators
The colorant, seen containing a triarylmethane colorants, and xanthene dyes, and a tetraazaporphyrin dye,
In the colorant, the content of the tetraazaporphyrin dye is 1.0 to 9.0 parts by mass with respect to 100 parts by mass of the triarylmethane colorant.
A color curable resin composition except when the colorant contains a compound represented by the following formula (13), a compound represented by the following formula (14), and a combination of the following formula (12).

A color filter formed from the colored curable resin composition according to claim 1. A display device including the color filter according to claim 2.