JP2018127596A - Compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having excellent heat resistance and a compound capable of providing a color filter having excellent heat resistance and light resistance. A compound represented by the formula (AI). [R1A to R8A are independent H, SO3- or alkyl groups; R9A and R10A are independent, alkyl groups, substituted / unsubstituted aromatic hydrocarbon groups or substituted / unsubstituted aralkyl groups; R11A to R20A are independent. SO3-, H, alkyl group or halogen, respectively; R45 and R46 are independently H, alkyl group, aromatic hydrocarbon group, etc .; R55 is H, alkyl group or substituted / unsubstituted aromatic hydrocarbon group Mr + Is r-valent metal ion; k is the number of SO3-] [selection diagram] None

Description

  The present invention relates to a compound and a coloring composition containing the compound.

  Coloring compositions are used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a colored composition, a colored composition containing a colorant represented by the following formula is known (Patent Document 1).

International Publication No. 2016/068203

  A color filter formed from a conventionally known colored composition containing the above compound has not been sufficiently satisfactory in terms of heat resistance and light resistance. The objective of this invention is providing the compound which can provide the color filter excellent in the compound excellent in heat resistance, and heat resistance and light resistance.

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

[In the formula (AI),
R ^{1A to} R ^8A each independently represent —SO ₃ ⁻ , a hydrogen atom, or a saturated hydrocarbon group having 1 to 10 carbon atoms.
R ^9A and R ^10A each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a substituent. The aralkyl group having 7 to 30 carbon atoms that may be present, and the substituent that the aromatic hydrocarbon group and the aralkyl group may have may be —SO ₃ ^— .
R ^{11A to} R ^20A each independently represent —SO ₃ ⁻ , a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.
In the above R ^{1A to} R ^20A , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or —CO—.
R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, The substituent that the aromatic hydrocarbon group may have may be —SO ₃ ^— .
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the aromatic hydrocarbon group has The optional substituent may be —SO ₃ ^— .
In R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or —CO—.
M ^{r +} represents an r-valent metal ion.
k represents the number of SO ₃ ⁻ groups contained in the compound represented by the formula (AI).
However, the compound represented by (AI) has at least two SO ₃ ^- groups.
r represents an integer of 2 or more. ]

[2] The compound according to [1], wherein R ⁵⁵ in formula (AI) is a C 6-20 aromatic hydrocarbon group having a halogen atom.
[3] A colored composition comprising a compound represented by the formula (AI) according to the above [1] or [2]. [4] A fiber material colored with the colored composition according to [3].
[5] A color filter formed from the colored composition according to [3].
[6] A display device including the color filter according to [5].

  The compound of the present invention has good heat resistance, and the color filter formed from the colored composition containing the compound of the present invention has good heat resistance and light resistance.

  The compound of the present invention is a compound represented by formula (AI) (hereinafter sometimes referred to as compound (AI)). The compounds of the present invention include tautomers and salts thereof.

[In the formula (AI),
R ^{1A to} R ^8A each independently represent —SO ₃ ⁻ , a hydrogen atom, or a saturated hydrocarbon group having 1 to 10 carbon atoms.
R ^9A and R ^10A each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a substituent. The aralkyl group having 7 to 30 carbon atoms that may be present, and the substituent that the aromatic hydrocarbon group and the aralkyl group may have may be —SO ₃ ^— .
R ^{11A to} R ^20A each independently represent —SO ₃ ⁻ , a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.
In the above R ^{1A to} R ^20A , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or —CO—.
R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, The substituent that the aromatic hydrocarbon group may have may be —SO ₃ ^— .
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the aromatic hydrocarbon group has The optional substituent may be —SO ₃ ^— .
In R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or —CO—.
M ^{r +} represents an r-valent metal ion.
k represents the number of SO ₃ ⁻ groups contained in the compound represented by the formula (AI).
However, the compound represented by (AI) has at least two SO ₃ ^- groups.
r represents an integer of 2 or more. ]

The saturated hydrocarbon group represented by R ^{1A to} R ^20A , R ⁴⁵ , R ⁴⁶ , R ⁵⁵ may be linear, branched or cyclic. Examples of the linear or branched saturated hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n -Linear alkyl group such as decyl group; isopropyl group, sec-butyl group, tert-butyl group, isopentyl group, 1-methylpentyl group, 2-ethylbutyl group, 1-propylbutyl group, 2-ethylhexyl group, etc. Examples thereof include a branched alkyl group. Carbon number of this saturated hydrocarbon group is 1-10, More preferably, it is 1-8, More preferably, it is 1-6.

The cyclic saturated hydrocarbon group represented by R ^{1A to} R ^20A , R ⁴⁵ , R ⁴⁶ and R ⁵⁵ may be monocyclic or polycyclic. Examples of the cyclic alkyl group include cycloaliphatic saturated hydrocarbon groups such as 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.
Specific examples of the saturated hydrocarbon group represented by R ^{1A to} R ^20A , R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ include groups represented by the following formulae. In the following formula, * represents a bond.

Of the saturated hydrocarbon groups represented by R ^{1A to} R ^20A , R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or —CO— (preferably an oxygen atom). Examples of the group include a group represented by the following formula. In the following formula, * represents a bond.

  1-10 are preferable and, as for carbon number of the group by which the methylene group contained in this saturated hydrocarbon group was substituted by the oxygen atom or -CO- (preferably oxygen atom), 1-6 are more preferable. The saturated hydrocarbon group in which the methylene group is substituted with an oxygen atom or —CO— (preferably an oxygen atom) is preferably a linear alkyl group. Moreover, 1-4 are preferable and, as for carbon number between oxygen atoms, 2-3 are more preferable.

The carbon number of the aromatic hydrocarbon group which may have a substituent represented by R ^{9A to} R ^10A , R ⁴⁵ , R ⁴⁶ , R ⁵⁵ is preferably 6-20, more preferably 6- 15, more preferably 6-12. Examples of the aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, terphenyl group, etc., preferably phenyl group, naphthyl group, tolyl group, xylyl group. More preferably, they are a phenyl group and a naphthyl group, More preferably, it is a phenyl group.

The aralkyl group represented by R ^{9A to} R ^10A is a group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methylene group, an ethylene group or a propylene group in the group described as the aromatic hydrocarbon group. Examples include a group to which an alkanediyl group is bonded. Carbon number of this aralkyl group becomes like this. Preferably it is 7-30, More preferably, it is 7-20, More preferably, it is C7-17. As this aromatic hydrocarbon group, a phenyl group, a naphthyl group, etc. are preferable.

Examples of the substituent in the aromatic hydrocarbon group and aralkyl group represented by R ^{9A to} R ^10A include a halogen atom such as a fluorine atom, a chlorine atom and iodine; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group A hydroxy group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; a methoxycarbonyl group and an ethoxycarbonyl group; alkoxycarbonyl group having 1 to 6 carbon atoms; -SO ₃ ^-, and the like, -SO ₃ ^- may be. However, it is preferable that —SO ₃ ^— is directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, a hydrogen atom bonded to the aromatic hydrocarbon ring is substituted.

Specific examples of the aromatic hydrocarbon group which may have a substituent represented by R ^{9A to} R ^10A include groups represented by the following formulae. In the following formula, * represents a bond.
Specific examples of the aralkyl group which may be substituted include groups in which a methylene group is bonded to the bond of the following aromatic hydrocarbon group.

Examples of the substituent in the aromatic hydrocarbon group represented by R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ include halogen atoms such as fluorine atom, chlorine atom, and iodine; C 1-6 such as chloromethyl group and trifluoromethyl group A haloalkyl group of 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydroxy group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; 6 alkoxycarbonyl group; —SO ₃ ^{— and the} like may be mentioned, and —SO ₃ ^— may be used. However, it is preferable that —SO ₃ ^— is directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, a hydrogen atom bonded to the aromatic hydrocarbon ring is substituted. The substituent in the aromatic hydrocarbon group represented by R ^55, a halogen atom and a haloalkyl group having 1 to 6 carbon atoms are preferred.
Specific examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulae. In the following formula, * represents a bond.

Examples of the halogen atom represented by R ^{11A to} R ^20A include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

R ^1A to R ^8A are each independently, -SO ₃ ^-, is preferably a saturated hydrocarbon group a hydrogen atom or 1 to 10 carbon atoms, -SO ₃ ^-, is a hydrogen atom or a methyl group More preferably, it is a hydrogen atom or a methyl group.

R ^{9A to} R ^10A each independently have a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a substituent. It is preferably an aralkyl group having 7 to 30 carbon atoms, and each independently represents a saturated hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, a methylnaphthyl group; an unsubstituted aralkyl group. More preferably one or more selected from a halogen atom, a methoxy group, an ethoxy group, a sulfamoyl group, a methylsulfonyl group, a methoxycarbonyl group, and an ethoxycarbonyl group, and more preferably an aralkyl group substituted with one type, More preferably, they are each independently a linear alkyl group having 1 to 4 carbon atoms.

From the viewpoints of heat resistance and light resistance, at least one of R ^{11A to} R ^12A is preferably a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and at least one of them is a halogen atom or carbon number. More preferably, it is a 1-8 saturated hydrocarbon group, and it is still more preferable that at least any one is a fluorine atom or a C1-C4 saturated hydrocarbon group.

From the viewpoints of heat resistance and light resistance, at least one of R ^{13A to} R ^14A is preferably a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and at least one of them is a halogen atom or carbon number. More preferably, it is a 1-8 saturated hydrocarbon group, and it is still more preferable that at least any one is a fluorine atom or a C1-C4 saturated hydrocarbon group.

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

R ⁴⁵ , R ⁴⁶ , and R ⁵⁵ are each independently a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent. Preferably, a halogen atom, an aromatic hydrocarbon group optionally substituted with a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, or a methylsulfonyl group, or saturation having 1 to 8 carbon atoms A hydrocarbon group is more preferable, and a saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula is more preferable. In particular, R ⁵⁵ is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms having a halogen atom, and more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms having two or more halogen atoms. preferable. The number of halogen atom of the aromatic hydrocarbon group represented by R ⁵⁵ is preferably 1 to 6, more preferably 1 to 4, more preferably from 2 to 3. The halogen atom is preferably a fluorine atom.
R ⁵⁵ is particularly preferably an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bond.

Examples of ^r- valent metal ions represented by ^{Mr +} include alkaline earth metal ions such as magnesium ion, calcium ion, strontium ion and barium ion; titanium ion, zirconium ion, chromium ion, manganese ion, iron ion and cobalt ion. Transition metal ions such as nickel ion and copper ion; typical metal ions such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion and bismuth ion, alkaline earth metal ion and transition metal ion Alternatively, typical metal ions are preferable, magnesium ions, strontium ions, barium ions, manganese ions or zinc ions are more preferable, and barium ions are more preferable.
r is preferably 2 to 5, more preferably 2 to 4, and still more preferably 2 to 3.

In formula ^{(A-I), M r} + number of the formula (A-I) -SO compound has represented by ₃ ^- number (k) number of the number one less divided by r than (( k-1) / r). Therefore, the compound (AI) is a compound having a valence of 0, that is, an electrically neutral compound.

In the formula (AI), the number of —SO ₃ ^— is 2 or more, preferably 6 or less, and more preferably 4 or less.

—SO ₃ ^— may be contained as any one of (a) R ^{1A to} R ^8A and R ^{11A to} R ^20A , or (b) a carbon which may have a substituent represented by R ^9A and R ^10A. It is bonded to any of an aromatic hydrocarbon group having 6 to 20 and an aralkyl group having 7 to 30 carbon atoms which may have a substituent represented by R ^9A and R ^10A , or (c) Or bonded to any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent represented by R ⁴⁵ , R ⁴⁶ or R ⁵⁵ , or (a) to (c) Preferably, it exists as a combination of (a), (b) or a combination of (a) to (b), more preferably as (a). Of R ^{1A to} R ^8A and R ^{11A to} R ^20A , R ^16A and R ^19A are particularly preferable.

In the above (a) to (c), it is preferable that —SO ₃ ^— is directly bonded to an aromatic hydrocarbon ring of an aromatic hydrocarbon group or an aralkyl group. That is, —SO ₃ ^— preferably substitutes a hydrogen atom bonded to the aromatic hydrocarbon ring.
Two or more —SO ₃ ^— may be bonded to the same aromatic hydrocarbon ring, but are preferably bonded to different aromatic hydrocarbon rings.

  Examples of the compound (AI) include compounds 1 to 514 represented by the formula (AI-1) as shown in Tables 1 to 9 below. In the table, * represents a bond.

However, the compounds represented by Compound (A-I-1) is, -SO ₃ ^- and has two a, the -SO ₃ ^- is a hydrogen atom represented by R ^h, R ^11A ~R ^14A Any two are substituted, preferably any two of the hydrogen atoms represented by R ^h are substituted, and more preferably, in the benzene ring bonded to the nitrogen atom, the bonding position with the nitrogen atom substituted to the R ^h located para to.

  In Tables 1 to 9, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bt represents an n-butyl group, and Ph1 to Ph10 each represents a group represented by the following formula.

Among them, as the compound represented by the formula (AI),
Compound 31 to Compound 90, Compound 121 to Compound 180, Compound 211 to Compound 334, Compound 365 to Compound 424, and Compound 455 to 514 are preferable.
Compound 46 to Compound 60, Compound 61 to Compound 90, Compound 136 to Compound 150, Compound 226 to Compound 240, Compound 271 to Compound 334, Compound 380 to Compound 394, and Compound 470 to 484 are more preferable.
Compound 46 to Compound 60, Compound 61 to Compound 90, Compound 136 to Compound 150, Compound 226 to Compound 240, Compound 271 to Compound 304, Compound 380 to Compound 394, Compound 470 to 484 are more preferable,
Compound 46 to Compound 60, Compound 61 to Compound 90, Compound 136 to Compound 150, Compound 226 to Compound 240, Compound 271 to Compound 294, Compound 380 to Compound 394, Compound 470 to 484 are even more preferable.
Particularly preferred are Compound 46 to Compound 60, Compound 61 to Compound 90, Compound 136 to Compound 150, Compound 226 to Compound 240, Compound 279 to Compound 294, Compound 380 to Compound 394, and Compound 470 to 484.
According to these compounds, both particularly high heat resistance and light resistance can be achieved.

Compound (AI) sulfonates a salt containing the cation moiety of (AI) (hereinafter sometimes referred to as compound (A-II)), and further, acetate, carbonate of r-valent metal M, It can be produced by reacting with a phosphate, sulfate, silicate, cyanide or halide (preferably chloride). Salts containing a cationic portion of (A-I), for example, hydrochloride, phosphate, sulfate, benzenesulfonate, naphthalenesulfonate, perchlorate, BF ₄ salt, PF ₆ salt and Can be mentioned.

  As the sulfonation method, various known methods, for example, Journal of Organic Chemistry, (1994), vol. 59, # 11, p. The method described in 3232-3236 is mentioned.

  The compound (AI) of the present invention can be applied to a fiber product. For example, the fiber material can be colored by kneading, impregnating or adhering to the fiber material.

<Coloring composition>
The coloring composition of this invention contains a coloring agent (A), and a coloring agent (A) contains a compound (AI). The colored composition of the present invention preferably further contains a solvent (E), and more preferably contains a resin (B), a polymerizable compound (C), and a polymerization initiator (D). Furthermore, a polymerization initiation assistant (D1) and a leveling agent (F) may be included.
Hereinafter, the colored composition containing the resin (B), the polymerizable compound (C), and the polymerization initiator (D) may be referred to as a colored curable resin composition.
Moreover, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

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

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

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

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

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

  Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone And N, N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethyl lactate, N-methylpyrrolidone and ethyl 3-ethoxypropionate are more preferred. .

  The content rate of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of a coloring composition, More preferably, it is 75-93 mass%. In other words, the total amount of the solid content of the coloring composition is preferably 5 to 30% by mass, more preferably 7 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness during coating tends to be good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

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

<Colorant (A)>
As the colorant (A), a dye containing the compound (AI) of the present invention as an active ingredient may be used alone. However, for the purpose of toning, that is, to adjust spectral characteristics, other dyes ( A1), pigment (P), or a mixture thereof may be included.

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

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82 83, 89, 94, 98, 99, 162;
C. I. Solvent Red 24, 45, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;
C. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. C. Solvent Green 1, 4, 34, 35; I. Solvent dyes,

C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339,341,345,346,349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Acid Violet 6B, 7, 9, 17, 19, 30, 120, 102;
C. I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes,

C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 2 5,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,

  C. I. C. such as Disperse Yellow 76 I. Disperse dyes,

C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. C. such as Basic Green 1; I. Basic dyes,

C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; I. Reactive dyes,

C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43, 46, 48 53, 56, 63, 71, 74, 85, 86, 88, 90, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53; I. Modern dyes,

C. I. C. of Bat Green 1 etc. I. Vat dye,
Etc.
Of these, blue dyes, violet dyes and red dyes are preferred.
These dyes may be used alone or in combination of two or more.

  In addition, xanthene dyes are preferred for classification by chemical structure. A known substance can be used as the xanthene dye. For example, a compound represented by the formula (1) is preferable.

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

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and heptyl. Straight chain alkyl group having 1 to 20 carbon atoms such as octyl group, nonyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group A branched alkyl group having 3 to 20 carbon atoms such as a group, neopentyl group and 2-ethylhexyl group; 3 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group ˜20 alicyclic saturated hydrocarbon groups.

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

Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group and N- (1,1,2,2) N-substituted sulfamoyl groups such as -tetramethylbutyl) sulfamoyl group; N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N -Propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfur group N, N-2 substituted sulfamoyl groups such as moyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group and N, N-heptylmethylsulfamoyl group, etc. Can be mentioned.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocycle together with the nitrogen atom. Examples of the heterocyclic ring include the following. In the formula, * represents a bond.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms representing R ³ and R ⁴ include those having 1 to 10 carbon atoms. A hydrogen atom contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms representing R ³ and R ⁴ may be substituted with a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group is It may be replaced by —O—, —CO— or —NR ¹¹ —.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
Examples of the saturated hydrocarbon group substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

Examples of the alkyl group having 1 to 6 carbon atoms representing R ⁶ and R ⁷ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert. -A butyl group, an isopentyl group, a neopentyl group, etc. are mentioned.

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

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

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent include a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 8, -SR 8, -SO 2 R ⁸ , —SO ₃ R ⁸ and —SO ₂ NR ⁹ R ¹⁰ may be mentioned. Among these substituents, —R ⁸ is preferable, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable. The _{^{Z +, -SO 3 - - -SO}} 3 in this case N ⁺ (R ¹¹⁾ ₄ are preferred.

Examples of —OR ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group.
Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

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

R ¹ and R ³ may be bonded together to form a ring containing a nitrogen atom together with the nitrogen atom to which they are bonded, and R ² and R ⁴ are bonded to each other to form a nitrogen to which they are bonded. A ring containing a nitrogen atom may be formed together with the atom. Examples of the ring containing a nitrogen atom include the following. In the formula, * represents a bond.

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

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

Wherein ^{(2), R 21, R} 22, R 23 and R ²⁴ each independently represents an alkyl group having 1 to 4 carbon atoms.
p and q represent the integer of 0-5 each independently. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different. ]

Examples of the alkyl group having 1 to 4 carbon atoms representing R ²¹ , R ²² , R ²³ and R ²⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group and tert-butyl. Groups and the like.
R ²¹ and R ²² are preferably each independently a methyl group or an ethyl group. R ²³ and R ²⁴ are preferably methyl groups.
p and q are preferably integers of 0 to 2, and more preferably 0 or 1.

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

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

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

  The pigment (P) is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists).

Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

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

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

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

The content of the compound (AI) is preferably 1% by mass or more and 100% by mass or less, more preferably 10% by mass or more and 100% by mass or less, with respect to the total amount of the colorant (A).
When the dye (A1) is included, the content is preferably 0.5% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 80% by mass or less, with respect to the total amount of the colorant (A). It is. When the pigment (P) is included, the content is preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 70% by mass or less, with respect to the total amount of the colorant (A). More preferably, it is 1 mass% or more and 50 mass% or less.
In the coloring composition, the content of the colorant (A) 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 with respect to the total amount of the solid content. In the colored curable resin composition, the content of the colorant (A) 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 with respect to the total amount of the solid content. Or less, more preferably 5% by mass or more and 50% by mass or less. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as “resin (B)”) is derived from at least one monomer (Ba) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. A copolymer containing structural units.
Examples of such a resin (B) include the following resins [K1] to [K6].
Resin [K1] a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and carbon A copolymer having a structural unit derived from a monomer (b) having a cyclic ether structure of 2 to 4 and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2] Structural unit derived from (a), structural unit derived from (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b) A copolymer having a structural unit derived from (hereinafter sometimes referred to as “(c)”);
Resin [K3] a copolymer having a structural unit derived from (a) and a structural unit derived from (c);
Resin [K4] a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c);
A copolymer having a structural unit obtained by adding (a) to a structural unit derived from the resin [K5] (b) and a structural unit derived from (c);
A copolymer having a structural unit obtained by adding (a) to a structural unit derived from the resin [K6] (b) and further adding a carboxylic anhydride, and a structural unit derived from (c).

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

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

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

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

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

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

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

As the alkanediyl group for R ^c , a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group And hexane-1,6-diyl group.
X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, more preferably a single bond, * —CH _2. CH ₂ —O— (* represents a bond with O).

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

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

  The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination of two or more. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, these content ratios [compound represented by the formula (BI): compound represented by the formula (BII)] are: On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

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

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

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

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

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

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

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

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

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

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

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

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

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By adjusting the amount of (b) used within this range, the storage stability of the colored composition, the developability when forming the pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern are improved. The balance tends to be good. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.

  The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).

  The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

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

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

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

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

  Among these, as the resin (B), the resin [K1] and the resin [K2] are preferable, and the resin [K1] is particularly preferable.

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

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

  The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

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

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

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

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

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

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

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

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

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913).

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.
These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.
Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium-p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluenesulfonate, 4-acetoxyphenylmethyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  As the polymerization initiator (D), 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 is preferable, and an O-acyloxime is preferable. A polymerization initiator containing a compound is more preferable.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

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

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine; 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

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

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

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

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

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

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

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

  When the leveling agent (F) is contained, the content is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0% by mass with respect to the total amount of the coloring composition. .1% by mass or less, more preferably 0.005% by mass or more and 0.05% by mass or less. Note that this content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is in the above range, the flatness of the color filter can be improved.

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

<Method for producing colored composition>
Furthermore, the coloring composition of the present invention containing the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent (E) includes, for example, the coloring agent (A), the resin (B), It can be prepared by mixing a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a leveling agent (F), a polymerization initiation assistant (D1) and other components used as necessary. .
When the pigment (P) is contained, it 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 is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired coloring composition can be prepared by mixing the remaining components with the pigment dispersion obtained in this manner so as to have a predetermined concentration.

  In the present invention, the compound (AI) may be mixed with the solvent (E1) to form a colored dispersion. After preparing the colored dispersion, further mixing with the solvent (E), resin (B), polymerizable compound (C), polymerization initiator (D), etc. used as necessary, to constitute a colored composition, The heat resistance when the color filter is used can be further increased.

As the solvent (E1), any solvent that can be used as the solvent (E) of the colored composition can be used. A particularly excellent solvent (E1) for the purpose of dispersing the compound (AI) is, for example, an ether ester solvent, more preferably one hydroxyl group of alkylene glycol or polyalkylene glycol is etherified, and the remaining hydroxy Solvents in which the groups are esterified, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Examples include monobutyl ether acetate and dipropylene glycol methyl ether acetate. These may be contained alone or in combination.
The amount of the solvent (E1) is, for example, 4 to 1000 parts by mass, preferably 6 to 200 parts by mass, and more preferably 9 to 100 parts by mass with respect to 1 part by mass of the compound (AI).

  In preparing the colored dispersion, it is preferable to use a dispersant. As the dispersant, for example, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic can be used. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk, BYK (Bic Chemie) and the like.

  The amount of the dispersant is, for example, 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 90 parts by mass, and particularly preferably 10 to 80 parts by mass with respect to 100 parts by mass of the compound (AI). Part by mass.

  Moreover, when the dye (A1) is contained in the coloring composition, a part or all, preferably all of the dye (A1) may be contained in advance in the colored dispersion as necessary. The amount of the dye (A1) in the colored dispersion is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 with respect to 100 parts by mass of the compound (AI). -10 parts by mass.

  The colored dispersion may contain a part or the whole of the resin (B) used in the colored composition, preferably a part, if necessary. By including the resin (B) in advance, the dispersibility of the colored composition can be further improved. The solid content conversion amount of the resin (B) in the colored dispersion is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, more preferably 20 to 100 parts by mass of the compound (AI). 70 parts by mass.

In preparing the dispersion, it is preferable to finely disperse using a dispersion apparatus after appropriately adding necessary components. A bead mill device can be used as the dispersing device. The beads used are generally hard beads such as zirconia beads, and the particle size thereof is selected from the range of 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, more preferably. 0.1 to 0.5 mm.
Further, the solution may be prepared by dissolving the compound (AI) in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
It is preferable to filter the colored composition after mixing with a filter having a pore size of about 0.01 to 10 μm.

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

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

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

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

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

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

  According to the coloring composition containing the compound of the present invention, a color filter excellent in heat resistance and light resistance can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
In the following, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type), UV-VIS (JASCO V-650).

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

  The following reaction was performed in a nitrogen atmosphere. After charging 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a condenser and a stirrer, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, followed by stirring for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours. After removing the water by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, it stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of the compound represented by the formula (C-I-2). Yield 53%.

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

Identification of compound represented by formula (X-II-2) (mass spectrometry) ionization mode = ESI +: m / z = 687.3 [M-Cl] ⁺
Exact Mass: 722.3

  The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer was charged 2.0 parts of the compound represented by the formula (X-II-2) and 7.3 parts of dichloromethane, and the reaction solution was ice-cooled. Next, 1.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred overnight while raising the temperature to room temperature. Next, the reaction solution was diluted with 34.0 parts of N, N-dimethylformamide while cooling with ice. Next, the diluted reaction solution was poured into 140.0 parts of toluene, and then stirred for 30 minutes. Next, stirring was stopped and decantation was performed to obtain a blue-violet viscous solid. Further, the blue-violet viscous solid was dried at 60 ° C. under reduced pressure to obtain 2.3 parts of a compound represented by the formula (XI-1). Yield 100%.

Identification of Compound Represented by Formula (XI-1) (Mass Spectrometry) Ionization Mode = ESI +: m / z = 847.3 [M + H] ⁺
ESI−: m / z = 845.5 [M−H] ⁻
Exact Mass: 846.2

[Example 1]
The following reaction was performed in a nitrogen atmosphere. To a flask equipped with a condenser and a stirrer, 2.0 parts of the compound represented by the formula (XI-2) and 166.7 parts of ion-exchanged water were added and stirred at 40 ° C. for 30 minutes. In a beaker, 5.8 parts of barium chloride dihydrate and 34.6 parts of ion-exchanged water were added and stirred for 30 minutes. While maintaining the aqueous solution of the compound represented by the formula (XI-2) prepared above at 40 ° C., an aqueous barium chloride solution was added dropwise and stirred for 1 hour and 20 minutes. The obtained reaction suspension was filtered, and the collected solid was suspended and washed with 66.7 parts of ion-exchanged water, and then washed with 20.0 parts of ion-exchanged water. The obtained solid was dried under reduced pressure at 60 ° C. to obtain 1.9 parts of a compound represented by the formula (AI-1). Yield 89%.

[Example 2]
When a reaction similar to that of Example 1 was performed using magnesium chloride hexahydrate instead of barium chloride dihydrate, a compound represented by the formula (AI-2) was obtained.

Example 3
When the same reaction as in Example 1 was carried out using zinc chloride instead of barium chloride dihydrate, a compound represented by the formula (AI-3) was obtained.

Example 4
When a reaction similar to that of Example 1 was performed using manganese chloride tetrahydrate instead of barium chloride dihydrate, a compound represented by the formula (AI-4) was obtained.

Example 5
When a reaction similar to that of Example 1 was performed using strontium chloride instead of barium chloride dihydrate, a compound represented by the formula (AI-5) was obtained.

Example 6
The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 0.27 parts of bis (dibenzylideneacetone) palladium (0) (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-tri 0.57 parts of isopropyl biphenyl (manufactured by Sigma Aldrich), 42.1 parts of sodium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 parts of 4,4′-dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After charging, a mixed solution of 48.3 parts of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 432 parts of toluene was added dropwise to the flask. The reaction solution was stirred for 2 hours while heating to 80 ° C. in an oil bath. The reaction solution was cooled in an ice bath and then filtered to obtain a solid and a filtrate. This solid is designated as crude A1 and the filtrate as filtrate A1. The obtained crude product A1 was washed with 50 parts of toluene and then washed twice with 250 parts of ion-exchanged water to obtain a solid. This solid is designated as a rough body B1. The filtrate A1, 50 parts of toluene, 229 parts of ion-exchanged water and 20.8 parts of 35% hydrochloric acid were added to the bottom discharge flask and stirred for 1 hour, followed by liquid separation to obtain an organic layer. The obtained organic layer was separated and washed with a mixed solution of 238 parts of ion-exchanged water and 12.5 parts of sodium carbonate, and then dried over 150 parts of magnesium sulfate, and the solid was removed by filtration. The obtained organic layer was distilled to obtain a solid. This solid is designated as crude body C1. Crude body B1 and coarse body C1 were introduced into a flask equipped with a stirrer, and 4 times the mass of acetonitrile was added to the total mass of coarse body B1 and coarse body C1, followed by stirring for 1 hour. The solid obtained by filtering the mixed solution was washed with 1 mass of acetonitrile with respect to the total mass of the crude product B1 and the crude product C1. The washed solid was dried at 60 ° C. under reduced pressure to obtain 75.9 parts of a compound represented by the formula (C-I-2). Yield 90.6%.

  The following reaction was performed in a nitrogen atmosphere. 50 parts of the compound represented by the formula (C-I-2) and 188 parts of N, N-dimethylformamide were added to a flask equipped with a condenser and a stirrer, and stirred for 30 minutes while cooling in an ice bath. 40 parts of potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask, and the mixture was further stirred for 1 hour while being cooled in an ice bath. While the reaction solution was ice-cooled, 55.6 parts of iodoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. The reaction solution was heated to 35 ° C. using an oil bath, stirred for 5 hours, and then allowed to cool to room temperature. To another flask equipped with a stirrer, 1000 parts of a 10% aqueous sodium chloride solution was added, and the reaction solution was added dropwise while stirring. The mixture was stirred for 30 minutes and filtered to obtain a solid. The obtained solid was washed three times with 500 parts of ion-exchanged water and dried at 60 ° C. under reduced pressure to obtain 53.0 parts of a compound represented by the formula (CI-3). Yield 93.5%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.8 parts of a compound represented by the formula (BI-2), 15.0 parts of a compound represented by the formula (CI-3) and 30 parts of toluene Then, 7.2 parts of phosphorus oxychloride was added and stirred at 100 ° C. for 7 hours. The reaction mixture was then cooled to room temperature and diluted with 23 parts of methyl ethyl ketone. Next, a mixed solution of 90 parts of ion-exchanged water and 7.5 parts of 35% aqueous hydrochloric acid was poured into the diluted reaction solution, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was evaporated using an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (X-II-6) as a blue-violet solid. The yield of blue-violet solid was 31.0 parts.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 21.2 parts of the compound represented by the formula (X-II-6) and 74.0 parts of methylene chloride were added and stirred for 30 minutes. The reaction solution was ice-cooled and 21.4 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added while maintaining the internal temperature at 10 ° C., and then the reaction solution was warmed to room temperature and stirred for 9 hours. Next, the reaction solution was ice-cooled and diluted with a mixed solution of 42 parts of N, N-dimethylformamide and 3.3 parts of ion-exchanged water while maintaining the internal temperature at 10 ° C. The diluted reaction solution was poured into 740 parts of toluene and stirred for 30 minutes to precipitate a viscous solid. After discharging the oil layer by decantation, 212 parts of toluene was added to the resulting viscous solid and stirred for 30 minutes. To the viscous solid obtained by discharging the oil layer by decantation, 550 parts of 20% brine was added and stirred for 1 hour, and then a blue solid was collected by filtration. The obtained solid was washed with 381 parts of 20% brine and dried under reduced pressure at 35 ° C. The obtained solid and 50 parts of methanol were put into a flask equipped with a stirrer and stirred for 30 minutes, followed by filtration to separate the solid and the filtrate. This filtrate is designated as filtrate A2. The collected solid was washed with 50 parts of methanol and separated into a solid and a filtrate by filtration. This filtrate is designated as filtrate B2. Filtrate A2 and filtrate B2 were mixed and the solvent was removed with an evaporator, and then dried under reduced pressure at 35 ° C. to obtain a compound represented by the formula (XI-6) as a blue-violet solid. The yield of the blue-violet solid was 267.3 parts.

  To a flask equipped with a condenser and a stirrer, 25.0 parts of the compound represented by the formula (XI-6), 39.4 parts of barium chloride dihydrate and 322 parts of ion-exchanged water were added, and the temperature was 40 ° C. After stirring for 2 hours, the reaction suspension was filtered. The solid collected by filtration and 313 parts of ion-exchanged water were put into a flask equipped with a stirrer and stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 250 parts of ion-exchanged water and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (AI-6) as a blue-violet solid. The yield was 21.6 parts and the yield was 80.5%.

Identification of Compound Represented by Formula (AI-6) (Mass Spectrometry) Ionization Mode = ESI +: m / z = 931.5 [M-Ba + 2H] ⁺
Exact Mass [M-Ba]: 929.3

Example 7
The following reaction was performed in a nitrogen atmosphere. After putting 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile into a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. After adding 40.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. After 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. An aqueous solution in which 79.2 parts of sodium monochloroacetate was dissolved in 120 parts of ion-exchanged water was added to the flask, and 60.4 parts of a 30% aqueous sodium hydroxide solution was added, followed by stirring at room temperature for 18 hours. Further, 600 parts of ion-exchanged water was added to the flask, followed by stirring for 1 hour, and the yellowish white solid precipitated was collected by filtration. The obtained yellowish white solid was washed with 120 parts of acetonitrile and then with 560 parts of ion-exchanged water. A yellow-white solid after washing, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 156 parts of toluene are charged into a flask equipped with a stirrer, and 2 at room temperature. Stir for hours. To this, 80.8 parts of 30% aqueous sodium hydroxide solution was added dropwise over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. To the obtained organic layer, 156 parts of ion exchanged water was added and subjected to liquid separation washing, and then 156 parts of ion exchanged water and 0.1 part of 35% hydrochloric acid were added to carry out liquid separation washing. The obtained organic layer was concentrated with an evaporator and then dried under reduced pressure at 35 ° C. to obtain a compound represented by the formula (BI-3) as a white solid. The yield was 43.4 parts and the yield was 58.0%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 13.2 parts of the compound represented by the formula (BI-3), 19.0 parts of the compound represented by the formula (CI-3) and 38 parts of toluene. Then, 9.2 parts of phosphorus oxychloride was added and stirred at 100 ° C. for 7 hours. The reaction mixture was then cooled to room temperature and diluted with 29 parts of methyl ethyl ketone. Next, a mixed solution of 114 parts of ion exchange water and 10 parts of 35% aqueous hydrochloric acid was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was evaporated using an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (X-II-7) as a blue-violet solid. The yield of blue-violet solid was 39.4 parts.

The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 38.4 parts of the compound represented by the formula (X-II-7) and 112 parts of methylene chloride and stirred for 30 minutes. The reaction solution was ice-cooled and 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added while keeping the internal temperature at 10 ° C., and then the reaction solution was warmed to room temperature and stirred for 9 hours. Next, the reaction solution was cooled with ice and diluted with a mixed solution of 64 parts of N, N-dimethylformamide and 4.9 parts of ion-exchanged water while maintaining the internal temperature at 10 ° C. The diluted reaction solution was poured into 1120 parts of toluene and stirred for 30 minutes to precipitate a viscous solid. After discharging the oil layer by decantation, 320 parts of toluene was added to the resulting viscous solid and stirred for 30 minutes. To the viscous solid obtained by discharging the oil layer by decantation, 832 parts of 20% brine was added and stirred for 1 hour, and then a blue solid was collected by filtration. The obtained blue solid was washed with 576 parts of 20% brine and dried under reduced pressure at 35 ° C. The solid obtained in a flask equipped with a stirrer and 128 parts of methanol were added, stirred for 30 minutes, filtered, and separated into a solid and a filtrate. This filtrate is designated as filtrate A3. The solid collected by filtration was washed with 192 parts of methanol and separated into a solid and a filtrate by filtration. This filtrate is designated as filtrate B3. The filtrate A3 and the filtrate B3 were mixed and the solvent was removed with an evaporator, and then dried under reduced pressure at 40 ° C. to obtain a compound represented by the formula (XI-7) as a blue-violet solid. The yield of blue-violet solid was 38.3 parts.

  To a flask equipped with a condenser and a stirrer was added 28.0 parts of the compound represented by the formula (XI-7), 43.2 parts of barium chloride dihydrate and 356 parts of ion-exchanged water, and the mixture was heated to 40 ° C. After stirring for 2 hours, the reaction suspension was filtered. The solid collected in a flask equipped with a stirrer and 350 parts of ion-exchanged water were added and stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 280 parts of ion-exchanged water and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (AI-7) as a blue-violet solid. The yield was 24.5 parts, and the yield was 81.7%.

Identification of Compound Represented by Formula (AI-7) (Mass Spectrometry) Ionization Mode = ESI−: m / z = 949.5 [M−Ba + 2H] ⁻
Exact Mass [M-Ba]: 947.28

Example 8
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 5.59 parts of potassium thiocyanate and 39.4 parts of acetonitrile, and stirred at room temperature for 30 minutes. Next, 10.0 parts of 2-trifluoromethylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, 6.48 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred at room temperature for 2 hours. Next, 16.7 parts of sodium chloroacetate dissolved in 25.1 parts of ion-exchanged water was added dropwise and stirred for 30 minutes. Next, 16.6 parts of a 10% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 12 hours. Thereafter, 127.0 parts of ion-exchanged water was poured into the flask and stirred for 1 hour. Thereafter, the aqueous layer was removed by a liquid separation operation to obtain an organic layer. This organic layer was dried under reduced pressure using an evaporator to obtain a light brown liquid intermediate.
The intermediate dissolved in 33.1 parts of toluene was added dropwise to an acetic acid aqueous solution prepared from 34.5 parts of ion-exchanged water and 7.2 parts of acetic acid, and stirred for 2 hours. Next, 21.6 parts of 10% aqueous sodium hydroxide solution was added dropwise and stirred for 30 minutes. After 34.5 parts of ion-exchanged water was further added dropwise, an organic layer was obtained by a liquid separation operation. Next, the organic layer is washed with an aqueous hydrochloric acid solution prepared from 0.1 part hydrochloric acid and 34.5 parts ion-exchanged water, and the obtained organic layer is evaporated with an evaporator and dried at 60 ° C. under reduced pressure. Thus, the compound represented by the formula (BI-4) was obtained as a pale yellow oily product. The yield was 9.95 parts, and the yield was 52.6%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 8.1 parts of the compound represented by the formula (BI-4), 10.0 parts of the compound represented by the formula (CI-3) and 15. After adding 5 parts, 4.9 parts of phosphorus oxychloride was then added and stirred at 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 45.4 parts of methyl ethyl ketone. Next, 100 parts of 0.5N hydrochloric acid aqueous solution was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. To the obtained organic layer, 100 parts of a 0.5N hydrochloric acid aqueous solution was poured, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was evaporated using an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (X-II-8) as a blue-violet solid. The yield of blue-violet solid was 18.0 parts.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 12.9 parts of the compound represented by the formula (X-II-8) was dissolved in 45 parts of chloroform, and then the solution was ice-cooled to bring the internal temperature to 10 ° C. Kept. Next, 12.2 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask and stirred for 5 hours while raising the temperature to room temperature. The reaction solution was then diluted with 25.5 parts of N, N-dimethylformamide while cooling with ice. The diluted reaction solution was poured into 600 parts of ethyl acetate and then stirred for 30 minutes to precipitate a viscous solid. The oil layer was discharged by decantation and washed with saturated brine to obtain a blue-violet solid. The viscous solid is obtained by suction filtration, washed with 100 parts of a 5% aqueous hydrochloric acid solution, followed by washing with 50 parts of ion-exchanged water, and then dried at 60 ° C. under reduced pressure to obtain the formula (XI-8). Was obtained as a blue-violet powder. The yield of blue-violet powder was 14.7 parts.

  To a flask equipped with a condenser and a stirrer is added 14.7 parts of the compound represented by the formula (XI-8), 19.3 parts of methanol and 105.9 parts of ion-exchanged water, and 30 minutes at 40 ° C. Stir. An aqueous solution in which 22.1 parts of barium chloride dihydrate was dissolved in 71 parts of ion-exchanged water and kept at 40 ° C. was dropped into the flask and stirred for 2 hours to obtain a reaction suspension. The resulting reaction suspension was filtered to obtain a solid. The obtained solid was washed with 71 parts of ion-exchanged water and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (AI-8) as a blue-violet solid. The yield was 14.2 parts and the yield was 90.3%.

Identification of Compound Represented by Formula (AI-8) (Mass Spectrometry) Ionization Mode = ESI−: m / z = 981.4 [M−Ba + 2H] ⁻
Exact Mass [M-Ba]: 979.29

Example 9
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 16.5 parts of potassium thiocyanate and 116 parts of acetonitrile, and stirred at room temperature for 30 minutes. Then, 25.0 parts of 2,5-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into the flask over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, 19.2 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred at room temperature for 2 hours. Next, an aqueous solution in which 49.5 parts of sodium chloroacetate was dissolved in 74.2 parts of ion-exchanged water was dropped into the flask and stirred for 30 minutes. Next, 49.1 parts of a 10% aqueous sodium hydroxide solution was added dropwise to the flask and stirred at room temperature for 12 hours. Thereafter, 377 parts of ion-exchanged water was poured into the reaction solution and stirred for 1 hour to obtain a suspension. The suspension was filtered to obtain a light brown powder. Thereafter, the light brown powder was washed with 116 parts of acetonitrile to obtain a white powder intermediate.
A solution prepared by dissolving the intermediate in 98 parts of toluene was added dropwise to an acetic acid aqueous solution prepared from 102 parts of ion-exchanged water and 21.3 parts of acetic acid, and stirred for 2 hours. Next, 63.8 parts of 10% aqueous sodium hydroxide solution was added dropwise and stirred for 30 minutes, and 102 parts of ion-exchanged water was further added dropwise, and then an organic layer was obtained by a liquid separation operation. The organic layer was washed with water and the aqueous layer was removed. Next, it was washed with an aqueous hydrochloric acid solution prepared from 0.1 part hydrochloric acid and 102 parts ion-exchanged water, and the organic layer obtained was evaporated with an evaporator and dried at 60 ° C. under reduced pressure to obtain the formula (B- The compound represented by I-5) was obtained as a pale yellow oily product. The yield was 29.35 parts, and the yield was 57.2%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 7.7 parts of the compound represented by the formula (BI-5), 10.0 parts of the compound represented by the formula (CI-3) and 15. After adding 5 parts, 4.9 parts of phosphorus oxychloride was then added and stirred at 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 45.4 parts of methyl ethyl ketone. Next, 100 parts of 0.5N hydrochloric acid aqueous solution was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. Further, 100 parts of a 0.5 N hydrochloric acid aqueous solution was poured, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was evaporated with an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (X-II-9) as a blue-violet solid. The yield of blue-violet solid was 17.3 parts.

  The following reaction was performed in a nitrogen atmosphere. After dissolving 12.4 parts of the compound represented by the formula (X-II-9) in 44.8 parts of chloroform in a flask equipped with a condenser and a stirrer, the solution was ice-cooled and the internal temperature was 10. Kept at ℃. Next, 12.2 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask and stirred for 5 hours while raising the temperature to room temperature. The reaction solution was then diluted with 25.5 parts of N, N-dimethylformamide while cooling with ice. The diluted reaction solution was poured into 600 parts of ethyl acetate and then stirred for 30 minutes to precipitate a viscous solid. The oil layer was discharged by decantation and washed with saturated brine to obtain a blue-violet solid. The viscous solid is obtained by suction filtration, washed with 100 parts of a 5% aqueous hydrochloric acid solution, followed by washing with 50 parts of ion-exchanged water, and then dried at 60 ° C. under reduced pressure to obtain the formula (XI-9). Was obtained as a blue-violet powder. The yield of blue-violet powder was 14.2 parts.

  To a flask equipped with a condenser and a stirrer was added 14.2 parts of the compound represented by the formula (XI-9), 19.3 parts of methanol and 105.9 parts of ion-exchanged water, and 30 minutes at 40 ° C. Stir. An aqueous solution in which 22.1 parts of barium chloride dihydrate was dissolved in 71 parts of ion-exchanged water and kept at 40 ° C. was dropped into the flask and stirred for 2 hours to obtain a reaction suspension. The resulting reaction suspension was filtered to obtain a solid. The obtained solid was washed with 70.6 parts of ion-exchanged water and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (AI-9) as a blue-violet solid. The yield was 9.0 parts and the yield was 58.7%.

Identification of Compound Represented by Formula (AI-9) (Mass Spectrometry) Ionization Mode = ESI−: m / z = 949.4 [M−Ba + 2H] ⁻
Exact Mass [M-Ba]: 947.28

Example 10
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 15.8 parts of potassium thiocyanate and 72.0 parts of acetonitrile, and then stirred at room temperature for 30 minutes. After 18.0 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. After 24.9 parts of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. An aqueous solution in which 39.7 parts of sodium monochloroacetate was dissolved in 54 parts of ion-exchanged water was added to the flask, and 30.3 parts of a 30% aqueous sodium hydroxide solution was added to the flask, followed by stirring at room temperature for 18 hours. . After adding 270 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and the yellowish white solid precipitated was collected by filtration. The obtained yellowish white solid was washed with 54 parts of acetonitrile and then washed with 257 parts of ion-exchanged water. A yellowish white solid after washing, 90 parts of ion-exchanged water, 20.9 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 90 parts of toluene are charged into a flask equipped with a stirrer at room temperature for 2 hours. Stir. To this, 47 parts of 30% aqueous sodium hydroxide solution was added dropwise over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. After 90 parts of ion-exchanged water was added to the obtained organic layer for separation and washing, 90 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for separation and washing. The obtained organic layer was dried with magnesium sulfate, and then the solid was filtered off. The obtained organic layer was concentrated with an evaporator and then dried under reduced pressure at 35 ° C. The formula (BI-6) was expressed. Was obtained as a white solid. The yield was 13.4 parts and the yield was 29.8%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 8.5 parts of the compound represented by the formula (BI-6), 10.0 parts of the compound represented by the formula (CI-3) and 27 parts of toluene. And stirred at room temperature for 10 minutes. 4.8 parts of phosphorus oxychloride was added and stirred at 100 ° C. for 7 hours. The reaction mixture was cooled to room temperature and diluted with 40 parts of methyl ethyl ketone. A mixed solution of 90 parts of ion exchange water and 5 parts of 35% aqueous hydrochloric acid was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. A mixed solution of 90 parts of ion-exchanged water and 5 parts of 35% hydrochloric acid aqueous solution was poured into the obtained organic layer, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was evaporated with an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (X-II-10) as a blue-violet solid. The yield of blue-violet solid was 20.9 parts.

  The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 15.0 parts of the compound represented by the formula (X-II-10) and 47 parts of chloroform and stirred at room temperature for 10 minutes. While the solution was ice-cooled and the internal temperature was kept at 10 ° C., 12.3 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask, and then the reaction solution was warmed to room temperature and stirred for 9 hours. did. The reaction solution was ice-cooled and diluted with a mixed solution of 27 parts of N, N-dimethylformamide and 2 parts of ion-exchanged water while keeping the internal temperature at 10 ° C. The diluted reaction solution was poured into 940 parts of toluene and then stirred for 30 minutes to precipitate a viscous solid. After draining the oil layer by decantation, 175 parts of toluene was added to the resulting viscous solid and stirred for 30 minutes. To the viscous solid obtained by discharging the oil layer by decantation, 350 parts of 20% brine was added and stirred for 1 hour, and then a blue solid was collected by filtration. The resulting blue solid was washed with 350 parts of 20% saline. The blue solid after washing and 50 parts of methanol were put into a flask equipped with a stirrer, stirred for 30 minutes, filtered, and separated into a solid and a filtrate. This filtrate is designated as filtrate A4. The collected solid was washed with 50 parts of methanol and separated into a solid and a filtrate by filtration. This filtrate is designated as filtrate B4. Filtrate A4 and filtrate B4 were mixed and the solvent was removed by an evaporator, followed by drying at 60 ° C. under reduced pressure to obtain a compound represented by the formula (XI-10) as a blue-violet solid. The yield of blue-violet solid was 24.9 parts.

  To a flask equipped with a condenser and a stirrer was added 20.0 parts of the compound represented by the formula (XI-10), 17.7 parts of barium chloride dihydrate and 189 parts of ion-exchanged water, and the mixture was heated to 40 ° C. After stirring for 2 hours, the reaction suspension was filtered. The filtered solid and 250 parts of ion-exchanged water were added to a flask equipped with a stirrer and stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 200 parts of ion-exchanged water and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (AI-10) as a blue-violet solid. The yield was 27.6 parts, and the yield was 96.6%.

Identification of compound represented by formula (AI-10) (mass spectrometry) ionization mode = ESI +: m / z = 1015.5 [M−Ba + 2H] ⁺
Exact Mass [M-Ba]: 1013.3

Example 11
The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 14.0 parts of potassium thiocyanate and 63.9 parts of acetonitrile were added, followed by stirring at room temperature for 30 minutes. After 18.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, the mixture was stirred at room temperature for 1 hour. After dropping 22.1 parts of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) into the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. An aqueous solution in which 35.2 parts of sodium monochloroacetate was dissolved in 48 parts of ion-exchanged water was added to the flask, and 26.8 parts of a 30% aqueous sodium hydroxide solution were added, followed by stirring at room temperature for 18 hours. After adding 270 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and the yellowish white solid precipitated was collected by filtration. The obtained yellowish white solid was washed with 54 parts of acetonitrile and then washed with 257 parts of ion-exchanged water. A yellowish white solid after washing, 90 parts of ion-exchanged water, 20.9 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 90 parts of toluene are charged into a flask equipped with a stirrer at room temperature for 2 hours. Stir. To this, 42 parts of 30% aqueous sodium hydroxide solution was added dropwise over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. After 90 parts of ion-exchanged water was added to the obtained organic layer for liquid separation washing, 90 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for liquid separation washing. The obtained organic layer was dried with magnesium sulfate, and then the solid was filtered off. The obtained organic layer was concentrated with an evaporator and then dried under reduced pressure at 60 ° C. The formula (BI-7) represents Was obtained as a white solid. The yield was 5.1 parts and the yield was 12.1%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 5.1 parts of the compound represented by the formula (BI-7), 5.9 parts of the compound represented by the formula (CI-3), and 8. 9 parts were added and stirred at room temperature for 10 minutes. 2.9 parts of phosphorus oxychloride was added here, and it stirred at 100 degreeC for 7 hours. The reaction mixture was cooled to room temperature and diluted with 23.6 parts of methyl ethyl ketone. A mixed solution of 53 parts of ion exchange water and 3 parts of 35% aqueous hydrochloric acid was poured into the diluted reaction solution, and the aqueous layer was removed by a liquid separation operation. A mixed solution of 53 parts of ion-exchanged water and 3 parts of 35% hydrochloric acid aqueous solution was poured into the obtained organic layer, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was evaporated with an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (X-II-11) as a blue-violet solid. The yield of blue-violet solid was 13.1 parts.

  The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 7.9 parts of the compound represented by the formula (X-II-11) and 26 parts of chloroform and stirred at room temperature for 10 minutes. 6.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask while the solution was ice-cooled and the internal temperature was kept at 10 ° C., and then the reaction solution was warmed to room temperature and stirred for 9 hours. did. The reaction solution was ice-cooled and diluted with a mixed solution of 15 parts of N, N-dimethylformamide and 1 part of ion-exchanged water while keeping the internal temperature at 10 ° C. The diluted reaction solution was poured into 513 parts of toluene and stirred for 30 minutes to precipitate a viscous solid. After discharging the oil layer by decantation, 95 parts of toluene was added to the resulting viscous solid and stirred for 30 minutes. To the viscous solid obtained by discharging the oil layer by decantation, 191 parts of 20% brine was added and stirred for 1 hour, and then a blue solid was collected by filtration. The resulting blue solid was washed with 191 parts of 20% saline. The blue solid after washing and 17 parts of methanol were put into a flask equipped with a stirrer, stirred for 30 minutes, filtered, and separated into a solid and a filtrate. This filtrate is designated as filtrate A5. The solid collected by filtration was washed with 17 parts of methanol and separated into a solid and a filtrate by filtration. This filtrate is designated as filtrate B5. Filtrate A5 and filtrate B5 were mixed and the solvent was removed by an evaporator, followed by drying under reduced pressure at 60 ° C. to obtain a compound represented by the formula (XI-11) as a blue-violet solid. The amount of blue-violet solid obtained was 9.3 parts.

  To a flask equipped with a condenser and a stirrer was added 9.3 parts of the compound represented by the formula (XI-11), 11.8 parts of barium chloride dihydrate and 105 parts of ion-exchanged water, and the mixture was heated to 40 ° C. After stirring for 2 hours, the reaction suspension was filtered. The filtered solid and 116 parts of ion-exchanged water were added to a flask equipped with a stirrer and stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 93 parts of ion-exchanged water and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (AI-11) as a blue-violet solid. The yield was 5.4 parts and the yield was 60.5%.

Identification of Compound Represented by Formula (A-I-11) (Mass Spectrometry) Ionization Mode = ESI +: m / z = 1033.5 [M-Ba + 2H] ⁺
Exact Mass [M-Ba]: 1031.3

Example 12
The following reaction was performed in a nitrogen atmosphere. 8.9 parts of potassium thiocyanate and 40 parts of acetonitrile were charged into a flask equipped with a condenser and a stirrer, and then stirred at room temperature for 30 minutes. 10.0 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, and then stirred at room temperature for 1 hour. 10.8 parts of N-ethyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into the flask over 30 minutes, and then stirred at room temperature for 1 hour. An aqueous solution in which 22.0 parts of sodium monochloroacetate was dissolved in 30 parts of ion-exchanged water was added to the flask, and 16.8 parts of a 30% aqueous sodium hydroxide solution were added, followed by stirring at room temperature for 18 hours. After adding 150 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and a yellowish white solid precipitated was collected by filtration. The obtained yellowish white solid was washed with 30 parts of acetonitrile and then with 143 parts of ion-exchanged water. A yellow-white solid after washing, 50 parts of ion-exchanged water, 11.6 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 50 parts of toluene are charged into a flask equipped with a stirrer at room temperature for 2 hours. Stir. To this, 26 parts of 30% aqueous sodium hydroxide solution was added dropwise over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. To the obtained organic layer, 50 parts of ion-exchanged water was added for liquid separation washing, and then 50 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for liquid separation washing. The obtained organic layer was dried with magnesium sulfate, and then the solid was filtered off. The organic layer was concentrated with an evaporator and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (BI-8). Obtained as an orange liquid. The yield was 12.1 parts and the yield was 54.9%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 7.4 parts of a compound represented by the formula (BI-8), 10.0 parts of a compound represented by the formula (CI-3) and 8 parts of toluene And stirred at room temperature for 10 minutes. 4.8 parts of phosphorus oxychloride was added here, and it stirred at 100 degreeC for 7 hours. The reaction mixture was cooled to room temperature and diluted with 40 parts of methyl ethyl ketone. A mixed solution of 90 parts of ion exchange water and 5 parts of 35% aqueous hydrochloric acid was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. A mixed solution of 90 parts of ion-exchanged water and 5 parts of 35% hydrochloric acid aqueous solution was poured into the obtained organic layer, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was evaporated with an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (X-II-12) as a blue-violet solid. The yield of blue-violet solid was 21.1 parts.

  The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 15.0 parts of the compound represented by the formula (X-II-12) and 44 parts of chloroform and stirred at room temperature for 10 minutes. The solution was ice-cooled and 12.1 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added while maintaining the internal temperature at 10 ° C., and then the reaction solution was warmed to room temperature and stirred for 9 hours. The reaction solution was ice-cooled and diluted with a mixed solution of 25 parts of N, N-dimethylformamide and 2 parts of ion-exchanged water while keeping the internal temperature at 10 ° C. The diluted reaction solution was poured into 879 parts of toluene and then stirred for 30 minutes to precipitate a viscous solid. After discharging the oil layer by decantation, 163 parts of toluene was added to the resulting viscous solid and stirred for 30 minutes. To the viscous solid obtained by discharging the oil layer by decantation, 326 parts of 20% brine was added and stirred for 1 hour, and then a blue solid was collected by filtration. The resulting blue solid was washed with 326 parts of 20% brine. The washed blue solid and 30 parts of methanol were put into a flask equipped with a stirrer, stirred for 30 minutes, filtered, and separated into a solid and a filtrate. This filtrate is designated as filtrate A6. The solid collected by filtration was washed with 30 parts of methanol and separated into a solid and a filtrate by filtration. This filtrate is designated as filtrate B6. Filtrate A6 and filtrate B6 were mixed and the solvent was removed with an evaporator, and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (XI-12) as a blue-violet solid. The yield of blue-violet solid was 22.0 parts.

  To a flask equipped with a condenser and a stirrer was added 20.0 parts of the compound represented by the formula (XI-12), 19.8 parts of barium chloride dihydrate and 199 parts of ion-exchanged water, and the mixture was heated to 40 ° C. After stirring for 2 hours, the reaction suspension was filtered. The filtered solid and 25 parts of ion-exchanged water were added to a flask equipped with a stirrer and stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 20 parts of ion-exchanged water and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (AI-12) as a blue-violet solid. The yield of blue-violet solid was 14.2 parts.

Identification of Compound Represented by Formula (A-I-12) (Mass Spectrometry) Ionization Mode = ESI +: m / z = 967.5 [M-Ba + 2H] ⁺
Exact Mass [M-Ba]: 965.29

Example 13
The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 14.4 parts of potassium thiocyanate and 78 parts of acetonitrile were added, followed by stirring at room temperature for 30 minutes. After 21.8 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. After 21.1 parts of N-ethyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. An aqueous solution in which 43.2 parts of sodium monochloroacetate was dissolved in 59 parts of ion-exchanged water was added to the flask, and 32.9 parts of a 30% aqueous sodium hydroxide solution were added, followed by stirring at room temperature for 18 hours. After adding 327 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and a yellowish white solid precipitated was collected by filtration. The obtained yellowish white solid was washed with 65 parts of acetonitrile and then with 312 parts of ion-exchanged water. A yellow-white solid after washing, 109 parts of ion-exchanged water, 25.3 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 109 parts of toluene are charged into a flask equipped with a stirrer at room temperature for 2 hours. Stir. To this, 51 parts of a 30% aqueous sodium hydroxide solution was added dropwise over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. To the obtained organic layer, 109 parts of ion-exchanged water was added for separation and washing, and then 109 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for separation and washing. The obtained organic layer was dried with magnesium sulfate, and then the solid was filtered off. The obtained organic layer was concentrated with an evaporator and then dried under reduced pressure at 60 ° C. The formula (BI-9) was expressed. Was obtained as an orange-white solid. The yield was 24.3 parts and the yield was 49.5%.

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 15.6 parts of the compound represented by the formula (BI-9), 20.0 parts of the compound represented by the formula (CI-3) and 30 parts of toluene. And stirred at room temperature for 10 minutes. 9.7 parts of phosphorus oxychloride was added here, and it stirred at 100 degreeC for 7 hours. The reaction mixture was cooled to room temperature and diluted with 80 parts of methyl ethyl ketone. A mixed solution of 180 parts of ion-exchanged water and 10 parts of 35% aqueous hydrochloric acid was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. A mixed solution of 180 parts of ion-exchanged water and 10 parts of 35% hydrochloric acid aqueous solution was poured into the obtained organic layer, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was evaporated with an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (X-II-13) as a blue-violet solid. The yield of blue-violet solid was 43.2 parts.

  The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 25.0 parts of the compound represented by the formula (X-II-13) and 74 parts of chloroform and stirred at room temperature for 10 minutes. The reaction solution was ice-cooled and 20.1 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added while maintaining the internal temperature at 10 ° C., and then the reaction solution was warmed to room temperature and stirred for 9 hours. The reaction solution was ice-cooled and diluted with a mixed solution of 43 parts of N, N-dimethylformamide and 3 parts of ion-exchanged water while keeping the internal temperature at 10 ° C. The diluted reaction solution was poured into 1486 parts of toluene and stirred for 30 minutes to precipitate a viscous solid. After discharging the oil layer by decantation, 276 parts of toluene was added to the resulting viscous solid and stirred for 30 minutes. To the viscous solid obtained by discharging the oil layer by decantation, 552 parts of 20% brine was added and stirred for 1 hour, and then a blue solid was collected by filtration. The resulting blue solid was washed with 552 parts of 20% brine. The blue solid after washing and 50 parts of methanol were put into a flask equipped with a stirrer, stirred for 30 minutes, filtered, and separated into a solid and a filtrate. This filtrate is designated as filtrate A7. The collected solid was washed with 50 parts of methanol and separated into a solid and a filtrate by filtration. This filtrate is designated as filtrate B7. Filtrate A7 and filtrate B7 were mixed and the solvent was removed by an evaporator, followed by drying under reduced pressure at 60 ° C. to obtain a compound represented by the formula (XI-13) as a blue-violet solid. The yield of blue-violet solid was 34.3 parts.

  To a flask equipped with a condenser and a stirrer was added 30.0 parts of the compound represented by the formula (XI-13), 31.6 parts of barium chloride dihydrate and 308 parts of ion-exchanged water, and the mixture was heated to 40 ° C. After stirring for 2 hours, the reaction suspension was filtered. The filtered solid and 375 parts of ion-exchanged water were added to a flask equipped with a stirrer and stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 300 parts of ion-exchanged water and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (AI-13) as a blue-violet solid. The yield was 22.6 parts, and the yield was 99.4%.

Identification of Compound Represented by Formula (A-I-13) (Mass Spectrometry) Ionization Mode = ESI +: m / z = 985.5 [M−Ba + 2H] ⁺
Exact Mass [M-Ba]: 983.3

[Heat resistance evaluation]
About 3000 μg of each compound was increased from 45 ° C. to 550 ° C. at 5 ° C./min using a Seiko Instruments Inc. thermogravimetric / differential calorimeter (TG / DTA6200). Table 10 shows the temperature at which a 5% weight loss from the initial weight was observed for each compound.

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

[Resin synthesis example 2]
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] a mixture of decan-9-yl acrylate (content ratio is 50:50 in molar ratio) (trade name “E-DCPA”, manufactured by Daicel Corporation) 289 parts of propylene glycol monomethyl ether acetate 125 parts The solution dissolved in was dropped over about 5 hours using a dropping pump. On the other hand, a solution obtained by dissolving 33 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was dropped into the flask over another 6 hours using another dropping pump. did. After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a solid content of 35.1%. The weight average molecular weight of the obtained resin (B-2) was 9200, the molecular weight distribution was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g.

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

(Preparation of colored curable resin composition)
Example 14
Colorant (A): Compound (AI-1) 20 parts;
Alkali-soluble resin (B): Resin (B-1) (in terms of solid content) 47.7 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 25.7 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.6 parts;
Solvent (E): 176 parts of propylene glycol monomethyl ether acetate;
Solvent (E): N-methylpyrrolidone 345 parts;
Solvent (E): 34 parts of ethyl lactate; and Leveling agent (F): Polyether-modified silicone oil (solid content conversion)
(Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.04 parts were mixed to obtain a colored curable resin composition.

[Examples 15 and 16, Comparative Example 1]
Example 14 was repeated except that compound (AI-2), compound (AI-3) or compound (XI-2) was used instead of compound (AI-1). A colored curable resin composition was obtained.

[Production of color filters]
The colored curable resin composition was applied on a 2-inch square glass substrate (# 1737; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), exposure was performed at an exposure amount (based on 365 nm) of 150 mJ / cm ^{2 in} an air atmosphere. A photomask was not used. The colored composition layer after exposure was post-baked in an oven at 180 ° C. for 20 minutes to produce a color filter (film thickness: 2.0 μm).

[Heat resistance evaluation]
The color filter produced by the above method is heated in an oven at 230 ° C. for 2 hours, and the difference (ΔY) in the stimulus value Y before and after the coating film is heated is measured by a colorimeter (OSP-SP-200; manufactured by OLYMPUS). And evaluated according to the following criteria. The results are shown in Table 11.
A: Less than 7.0 B: 7.0 or more

[Dispersion Preparation Method]
Example 17
10.0 parts of compound (A-I-2), 5.0 parts of dispersant BYK LPN-6919 (propylene glycol monomethyl ether acetate solution with a solid content of 60%), and (resin B-2) solution (solid) 11.4 parts of 35.1%) and 173.6 parts of propylene glycol monomethyl ether acetate, weighed 600 parts of 0.4 μm zirconia beads, and shaken for 1 hour using a paint conditioner (manufactured by LAU). Thus, Dispersion 1 was prepared.

(Preparation of colored curable resin composition)
Dispersion 1; 400 parts;
Alkali-soluble resin (B): Resin (B-1) (solid content conversion) 33.7 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 25.7 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.6 parts;
Solvent (E): Propylene glycol monomethyl ether acetate 189 parts; and Leveling agent (F): Polyether-modified silicone oil (solid content conversion)
(Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.04 parts were mixed to obtain a colored curable resin composition.

[Heat resistance test]
The coating film of the colored curable resin composition obtained from the dispersion was heated in an oven at 230 ° C. for 2 hours, and the difference (ΔY) in the stimulation value Y before and after the coating film was heated was measured with a colorimeter (OSP-SP- 200; manufactured by OLYMPUS) and evaluated according to the following criteria. The results are shown in Table 11.
A: Less than 7.0 B: 7.0 or more

Example 18
<Dispersion preparation>
10.0 parts of compound (AI-6), 5.0 parts of dispersant BYK LPN-6919 (propylene glycol monomethyl ether acetate solution having a solid content of 60%), and (resin B-2) solution (solid) 11.4 parts of 35.1%) and 173.6 parts of propylene glycol monomethyl ether acetate are weighed and mixed. Then, 600 parts of zirconia beads having a particle diameter of 0.4 μm are added, and a paint conditioner (manufactured by LAU) is used. Then, the mixture was shaken for 1 hour, and the zirconia beads were removed by filtration through a wire mesh to prepare dispersion 2.

<Preparation of colored curable resin composition>
Dispersion 2; 400 parts;
Alkali-soluble resin (B): Resin (B-1) (solid content conversion) 33.7 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 25.7 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.6 parts;
Solvent (E): 189 parts of propylene glycol monomethyl ether acetate; and leveling agent (H): polyether-modified silicone oil (solid content conversion)
(Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.04 parts were mixed to obtain a colored curable resin composition.

[Examples 19 to 26]
Dispersions 3 to 10 were obtained in the same manner as in Example 18, except that the compounds shown in Table 12 were used instead of the compounds (AI-6). Moreover, the colored curable resin composition was obtained by the method similar to Example 18 using these dispersion liquids.
Table 12 shows the correspondence between the compounds and the dispersions used in Examples 18 to 26.

<Preparation of colored coating film>
A colored curable resin composition is applied on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating so that the film thickness after post-baking is 2 μm, and then pre-baked at 100 ° C. for 3 minutes. did. After standing to cool, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), it was irradiated with light at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. After light irradiation, post-baking was performed at 220 ° C. for 20 minutes in an oven to obtain a colored coating film.

<Heat resistance test>
The colored coating film obtained by the above method is heated in an oven at 230 ° C. for 2 hours, and the stimulation value Y before and after the heating of the colored coating film is measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). Measurement was made and the difference (ΔY) was evaluated according to the following criteria. The results are shown in Table 13.
AA: Less than 3.0 A: 3.0 or more and less than 7.0 B: 7.0 or more

<Light resistance test>
An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd .; cuts light of 380 nm or less) is placed on the colored coating film obtained by the above method, and a light resistance tester (Suntest CPS +: Toyo Seiki Co., Ltd.). Xenon lamp light for 24 hours. The stimulus value Y before and after the light resistance test of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS), and the difference (ΔY) was evaluated according to the following criteria. The results are shown in Table 13.
AA: Less than 3.0 A: 3.0 or more and less than 7.0 B: 7.0 or more

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

Claims (6)

A compound represented by formula (AI).

[In the formula (AI),
R ^{1A to} R ^8A each independently represent —SO ₃ ⁻ , a hydrogen atom, or a saturated hydrocarbon group having 1 to 10 carbon atoms.
R ^9A and R ^10A each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a substituent. The aralkyl group having 7 to 30 carbon atoms that may be present, and the substituent that the aromatic hydrocarbon group and the aralkyl group may have may be —SO ₃ ^— .
R ^{11A to} R ^20A each independently represent —SO ₃ ⁻ , a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.
In the above R ^{1A to} R ^20A , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or —CO—.
R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, The substituent that the aromatic hydrocarbon group may have may be —SO ₃ ^— .
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the aromatic hydrocarbon group has The optional substituent may be —SO ₃ ^— .
In R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or —CO—.
M ^{r +} represents an r-valent metal ion.
k represents the number of SO ₃ ⁻ groups contained in the compound represented by the formula (AI).
However, the compound represented by (AI) has at least two SO ₃ ^- groups.
r represents an integer of 2 or more. ] The compound according to claim 1, wherein R ⁵⁵ in formula (AI) is a C 6-20 aromatic hydrocarbon group having a halogen atom.   The coloring composition containing the compound represented by the formula (AI) of Claim 1 or 2.   A fiber material colored with the colored composition according to claim 3.   A color filter formed from the colored composition according to claim 3.   A display device comprising the color filter according to claim 5.