CN113454167B

CN113454167B - Coloring composition, compound, color filter and display device

Info

Publication number: CN113454167B
Application number: CN202080014741.9A
Authority: CN
Inventors: 织田胜成
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2019-02-18
Filing date: 2020-02-14
Publication date: 2023-08-15
Anticipated expiration: 2040-02-14
Also published as: WO2020170957A1; JP2020132878A; TW202035387A; KR20210127754A; CN113454167A

Abstract

The purpose of the present invention is to provide a coloring composition comprising a compound having a maximum absorption wavelength on the longest wavelength side of an absorption spectrum and/or a compound having a shoulder wavelength on the longest wavelength side of the absorption spectrum, said compound being longer than the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of conventionally known c.i. pigment yellow 138. The present invention relates to a coloring composition comprising a compound represented by formula (I) and a solvent.

Description

Coloring composition, compound, color filter and display device

Technical Field

The invention relates to a coloring composition, a compound, a color filter and a display device.

Background

The coloring composition is used for manufacturing color filters used in display devices such as liquid crystal display devices and electroluminescent display devices. As a colorant contained in the coloring composition, c.i. pigment yellow 138 is known (patent document 1).

(C.I. pigment yellow 138)

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open publication No. 2013-82906

Disclosure of Invention

In recent years, a display has been developed to expand a displayable color reproduction area, and as one of them, a color filter is required to have a darker color. In order to meet the requirements, a coloring composition containing a compound having a maximum absorption wavelength on the longest wavelength side of the absorption spectrum and/or a compound having a wavelength of a shoulder on the longest wavelength side of the absorption spectrum on the wavelength side longer than the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of conventionally known c.i. pigment yellow 138 is required.

The wavelength of the shoulder on the longest wavelength side of the absorption spectrum refers to the average value of the wavelength of the inflection point on the longest wavelength side of the absorption spectrum and the wavelength of the inflection point on the 2 nd long wavelength side of the absorption spectrum when the compound does not have the maximum absorption wavelength on the longest wavelength side of the absorption spectrum on the wavelength side longer than the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of c.i. pigment yellow 138 and has 2 or more inflection points on the wavelength side longer than the maximum absorption wavelength on the longest wavelength side of the absorption spectrum.

The present invention provides the following [1] to [6].

[1] A coloring composition comprising a compound represented by the following formula (I) and a solvent.

In the formula (I) of the formula (I),

R ¹ ～R ⁵ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -SO ₃ M、－CO ₂ M, MM a C1-40 hydrocarbon group or a C1-40 heterocyclic group,

the-C (-) (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-Si (-) (-) -,

the-CH (-) -, which constitutes the 1-valent hydrocarbon group and the 1-valent heterocyclic group, may be substituted with-N (-) -,

-ch=constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-n=,

-CH constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group ₂ Can be substituted by-O-, -S-, -S (O) ₂ -or-CO-,

the hydrogen atoms constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be takenSubstituted by halogen atoms, cyano groups, nitro groups, -SO ₃ M、－CO ₂ M or MM.

R ¹ And R is ² 、R ² And R is ³ R is as follows ³ And R is ⁴ May be bonded to each other to form a ring, respectively.

M represents a hydrogen atom, an alkali metal atom, a metal atom which may have a ligand, or N (Z) ¹ )(Z ² )(Z ³ )(Z ⁴ )。

MM represents an alkali metal atom, a metal atom which may have a ligand, or N (Z) ¹ )(Z ² )(Z ³ )(Z ⁴ )。

Z ¹ ～Z ⁴ Each independently represents a hydrogen atom, a 1-valent hydrocarbon group having 1 to 40 carbon atoms or a 1-valent heterocyclic group having 1 to 40 carbon atoms,

the hydrogen atoms constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with a halogen atom, cyano group, nitro group, -SO ₃ M、－CO ₂ M or MM.

Q ¹ And Q ² Each independently represents a 2-valent hydrocarbon group or a 2-valent heterocyclic group,

the-C (-) (-) -constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted with-Si (-) (-) -,

the-CH (-) -, which constitutes the 2-valent hydrocarbon group and the 2-valent heterocyclic group, may be substituted with-N (-) -,

-ch=constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted with-n=,

-CH constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group ₂ Can be substituted foris-O-, -S (O) ₂ -or-CO-,

the hydrogen atoms constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted with halogen atoms, cyano groups, nitro groups, -SO ₃ M、－CO ₂ M or MM.

Z ¹ ～Z ⁴ When there are plural, M and MM, respectively, they may be the same as or different from each other.]

[2] The coloring composition according to [1], wherein the resin is contained.

[3] The coloring composition according to any one of [1] to [2], wherein the coloring composition comprises a polymerizable compound and a polymerization initiator.

[4] A color filter formed from the coloring composition according to any one of [1] to [3 ].

[5] A display device comprising the color filter of [4 ].

[6] A compound represented by formula (I).

In the formula (I) of the formula (I),

the hydrogen atoms constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with a halogen atom, a cyano group, a nitro group, a,－SO ₃ M、－CO ₂ M or MM.

-CH constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group ₂ Can be substituted by-O-, -S-, -S (O) ₂ -or-CO-,

According to the present invention, there are provided coloring compositions and compounds useful for forming darker color filters than coloring compositions comprising c.i. pigment yellow 138.

Detailed Description

[ coloring composition ]

The coloring composition of the present invention contains a compound represented by the formula (I) (hereinafter, sometimes referred to as compound (I)) and a solvent (hereinafter, sometimes referred to as solvent (E)).

In the formula (I) of the formula (I),

hydrogen atoms constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic groupThe substituents may be halogen atoms, cyano groups, nitro groups, -SO ₃ M、－CO ₂ M or MM.

The compound (I) also includes tautomers thereof, and salts thereof.

The compound (I) may be used as a colorant.

The coloring composition of the present invention may contain 1 or 2 or more compounds (I).

The coloring composition of the present invention may contain a resin (hereinafter, sometimes referred to as a resin (B)).

The coloring composition of the present invention may contain a polymerizable compound (hereinafter, may be referred to as a polymerizable compound (C)).

The coloring composition of the present invention may contain a polymerization initiator (hereinafter, may be referred to as a polymerization initiator (D)).

The coloring composition of the present invention may contain a polymerization initiator aid (hereinafter, may be referred to as a polymerization initiator aid (D1)).

The coloring composition of the present invention may contain a colorant other than the compound (I) (hereinafter, may be referred to as a colorant (A1), and the compound (I) and the colorant (A1) may be collectively referred to as "colorant (a)").

The colorant (A1) may contain 1 or 2 or more colorants.

The colorant (A1) preferably contains 1 or more selected from yellow colorant, orange colorant, red colorant and green colorant.

The coloring composition of the present invention may contain a leveling agent (hereinafter, may be referred to as leveling agent (F)).

The coloring composition of the present invention may contain an antioxidant (hereinafter, sometimes referred to as an antioxidant (G)).

[ Compound (I) ]

The present invention will be described more specifically below with reference to the partial structures of the compound (I), but in each partial structure, even when only a substituent bonded to the ring structure is bonded to a certain portion of the ring structure, the following examples include a case where the substituent is bonded to all portions of the ring structure. When 1 or 2 or more substituents are bonded to the ring structure, the substituents may be the same or different, respectively.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom, and a bromine atom are preferable.

R ¹ ～R ⁵ And Z ¹ ～Z ⁴ The number of carbon atoms of the hydrocarbon group is 1 to 40, preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 18, particularly preferably 1 to 12.

R ¹ ～R ⁵ And Z ¹ ～Z ⁴ The 1-valent hydrocarbon group having 1 to 40 carbon atoms represented may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated, and may be a chain or cyclic (alicyclic hydrocarbon group).

As R ¹ ～R ⁵ And Z ¹ ～Z ⁴ Examples of the saturated or unsaturated chain hydrocarbon group represented include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, tetracontyl, pentatriacontyl, hexatriacontyl, heptatriacontyl, octatriacontyl, nonatriacontyl, and tetracontyl; isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylbutyl, 3-dimethylbutyl, 1, 3-tetramethylbutyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, neopentyl, 1-dimethylpropyl, 2-methylpentyl, 3-ethylpentyl, 1, 3-dimethylbutyl, 2-propylpentyl, 1-ethyl-1, 2-dimethylpropyl, 1-methylpentyl, 4- - Branched alkyl groups such as methylhexyl, 5-methylhexyl, 2-ethylhexyl, 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 3-ethylheptyl, 2-dimethylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1-methyloctyl, 1-ethylheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl and 1-butylhexyl; vinyl (vinyl), propenyl (e.g., 1-propenyl, 2-propenyl (allyl)), 1-methylvinyl, butenyl (e.g., 1-butenyl, 2-butenyl, 3-butenyl), 3-methyl-1-butenyl, 1, 3-butadienyl, 1- (2-propenyl) vinyl, 1- (1-methylvinyl) vinyl, 1, 2-dimethyl-1-propenyl, pentenyl (e.g., 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl), 1- (1, 1-dimethylethyl) vinyl, 1, 3-dimethyl-1-butenyl, hexenyl (e.g., 1-hexenyl, 5-hexenyl), heptenyl (e.g., 1-heptenyl, 6-heptenyl), octenyl (e.g., 1-octenyl, 7-octenyl), nonenyl (e.g., 1-nonenyl, 8-nonenyl), decenyl (e.g., 1-decenyl, 9-decenyl), undecenyl, dodecenyl, tridecenyl, pentadecenyl, tetradecenyl, hexadecenyl, nonadecenyl, 1-dodecenyl, nonadecenyl, 1-methyl, 2-dodecenyl, and the like; alkynyl groups such as ethynyl, propynyl (e.g., 1-propynyl, 2-propynyl), octynyl (e.g., 1-octynyl, 7-octynyl), butynyl, pentynyl, hexynyl, heptynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecylynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecyl, nonadecynyl, and eicosynyl; etc. The number of carbon atoms of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 18, particularly preferably 1 to 12. Among them, a linear or branched alkyl group having 1 to 12 carbon atoms is particularly preferable.

As R ¹ ～R ⁵ And Z ¹ ～Z ⁴ A saturated or unsaturated alicyclic hydrocarbon group represented by formula (I), examples thereof include cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1, 2-dimethylcyclohexyl, 1, 3-dimethylcyclohexyl, 1, 4-dimethylcyclohexyl, 2, 3-dimethylcyclohexyl, 2, 4-dimethylcyclohexyl, 2, 5-dimethylcyclohexyl 2, 6-dimethylcyclohexyl, 3, 4-dimethylcyclohexyl, 3, 5-dimethylcyclohexyl, 2-dimethylcyclohexyl, 3-dimethylcyclohexyl, 4-dimethylcyclohexyl, cyclooctyl cycloalkyl groups such as 2,4, 6-trimethylcyclohexyl, 2, 6-tetramethylcyclohexyl, 3, 5-tetramethylcyclohexyl, 4-pentylcyclohexyl, 4-octylcyclohexyl and 4-cyclohexylcyclohexyl; cyclohexenyl (e.g., cyclohex-1-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl), cycloalkenyl such as cycloheptenyl and cyclooctenyl; norbornyl, adamantyl and bicyclo [2.2.2]Octyl and other saturated or unsaturated polycyclic hydrocarbon groups; etc. The number of carbon atoms of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, still more preferably 3 to 18, particularly preferably 3 to 12. Among them, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl are particularly preferable.

As R ¹ ～R ⁵ And Z ¹ ～Z ⁴ Examples of the aromatic hydrocarbon group include phenyl, o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, 3, 5-di (tert-butylphenyl), 3, 5-di (tert-butyl) -4-methylphenyl, 4-butylphenyl, 4-pentylphenyl, 2, 6-bis (1-methylethyl) phenyl, 2,4, 6-tris (1-methylethyl) phenyl, 4-cyclohexylphenyl, 2,4, 6-trimethylphenyl and 4-Octylphenyl, 4- (1, 3-tetramethylbutyl) phenyl, 1-naphthyl, 2-naphthyl, 6-methyl-2-naphthyl, 5,6,7, 8-tetrahydro-1-naphthyl, 5,6,7, 8-tetrahydro-2-naphthyl, fluorenyl, phenanthryl, anthracenyl, 2-dodecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl, perylenyl,Aromatic hydrocarbon groups such as a group and a pyrenyl group; etc. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, still more preferably 6 to 18, and particularly preferably 6 to 12.

R ¹ ～R ⁵ And Z ¹ ～Z ⁴ The hydrocarbyl group represented by the above-mentioned (for example, an aromatic hydrocarbyl group and at least one of a chain hydrocarbyl group and an alicyclic hydrocarbyl group) may be a hydrocarbyl group, and examples thereof include aralkyl groups such as benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl, (2-ethylphenyl) methyl, (3-ethylphenyl) methyl, (4-ethylphenyl) methyl, (2- (tert-butyl) phenyl) methyl, (3- (tert-butyl) phenyl) methyl, (4- (tert-butyl) phenyl) methyl, (3, 5-dimethylphenyl) methyl, 1-phenylethyl, 1-diphenylethyl, phenethyl, 1-methyl-1-phenylethyl, (1-naphthyl) methyl and (2-naphthyl) methyl; arylalkenyl groups such as 1-phenylvinyl, 2-phenylvinyl (phenylvinyl), 2-diphenylvinyl, and 2-phenyl-2- (1-naphthyl) vinyl; aryl alkynyl groups such as phenyl ethynyl; phenyl groups having 1 or more phenyl groups bonded thereto, such as biphenyl and terphenyl; cyclohexylmethylphenyl, benzyl phenyl, (dimethyl (phenyl) methyl) phenyl, and the like.

The number of carbon atoms is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 18, particularly preferably 4 to 12. The lower limit of these ranges is preferably 7.

R ¹ ～R ⁵ And Z ¹ ～Z ⁴ The group represented by the above-mentioned hydrocarbon group (e.g., chain hydrocarbon group and alicyclic hydrocarbon group) may be, for example, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, or cycloAn alkyl group having 1 or more alicyclic hydrocarbon groups bonded thereto, such as a pentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a (2-methylcyclohexyl) methyl group, a cyclohexylethyl group, or an adamantylmethyl group.

The number of carbon atoms is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 18, particularly preferably 4 to 12.

R ¹ ～R ⁵ And Z ¹ ～Z ⁴ The 1-valent heterocyclic group having 1 to 40 carbon atoms represents a group containing a heteroatom as a constituent of a ring. The 1-valent heterocyclic group having 1 to 40 carbon atoms may be a single ring or multiple rings. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

The number of carbon atoms of the heterocyclic group is preferably 3 to 30, more preferably 3 to 20, still more preferably 3 to 18, particularly preferably 3 to 12.

Examples of the nitrogen atom-containing heterocycle include monocyclic saturated heterocycles such as aziridine, azetidine, pyrrolidine, piperidine and piperazine; pyrrole such as pyrrole, 1-methylpyrole, 2, 5-dimethylpyrrole, pyrazole such as pyrazole, 1-methylpyrazole, 2-methylpyrazole, 3-methylpyrazole, 4-methylpyrazole, 5-methylpyrazole, imidazole, 1,2, 3-triazole, 1,2, 4-triazole, and other 5-membered unsaturated heterocyclic ring; 6-membered ring unsaturated heterocyclic rings such as pyridine, pyridazine, pyrimidine, 6-methylpyrimidine and the like, pyrazine and 1,3, 5-triazine; a fused bicyclic heterocyclic ring such as indazole, indoline, isoindoline, indole, indolizine, benzimidazole, quinoline, isoquinoline, 5,6,7, 8-tetrahydro (3-methyl) quinoxaline, quinoxaline such as 3-methyl quinoxaline, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazole, or benzopiperidine; condensed tricyclic heterocycles such as carbazole, acridine and phenazine; etc.

Examples of the oxygen atom-containing heterocycle include oxetane, tetrahydrofuran, tetrahydropyran, and 1, 3-di-Alkane and 1, 4-di->Saturated heterocyclic rings having a single ring system such as an alkane, 1-cyclopentyldioxolane and 2-cyclopentyldioxolane; 1, 4-dioxaspiro [4.5 ]]Decane, 1, 4-dioxaspiro [4.5 ]]Nonane, 1, 4-dioxaspiro [4.4 ]]Bicyclic saturated heterocyclic ring such as nonane; lactone-based heterocycles such as α -caprolactone, β -propiolactone, γ -butyrolactone, γ -valerolactone and δ -valerolactone; furan, such as furan, 2, 3-dimethylfuran and 2, 5-dimethylfuran, and the like; 6-membered ring system unsaturated heterocyclic ring such as 2H-pyran and 4H-pyran; benzofuran such as 1-benzofuran, benzopyran such as 4-methylbenzopyran, methylenedioxybenzene, 1, 3-methylenedioxybenzene, benzodi>Condensed bicyclic heterocycles such as alkane, chroman, and isochroman; fused tricyclic heterocycles such as xanthene and dibenzofuran; etc.

Examples of the sulfur atom-containing heterocyclic ring include 5-membered ring saturated heterocyclic rings such as dithiolane; 6-membered ring saturated heterocyclic rings such as thiane, 1, 3-dithiane, 2-methyl-1, 3-dithiane and the like; thiophene such as thiophene, 3-methylthiophene and 2-carboxythiophene, 5-membered ring-system unsaturated heterocycle and 6-membered ring-system unsaturated heterocycle such as thiopyran such as 2H-thiopyran and 4H-thiopyran; a fused bicyclic heterocycle such as benzothiopyran, benzothiophene, etc.; condensed tricyclic heterocycles such as thianthrene and dibenzothiophene; etc.

Examples of the heterocyclic ring containing a nitrogen atom and an oxygen atom include monocyclic saturated heterocyclic rings such as morpholine, 2-pyrrolidone, 1-methyl-2-pyrrolidone, 2-piperidone, 1-methyl-2-piperidone and 2-methyl-2-piperidone;azole, 4-methyl->Azole and the like->Azole, 2-methylisoxygen->Azole, 3-methylisoxygen->Azole, 4-methyl isoAzole, 5-methylisoxygen->Azole et al>Monocyclic unsaturated heterocycles such as oxazoles; benzo->Azole, benzisoxazole>Azole, benzo->Oxazine, benzodi->Condensed bicyclic heterocycles such as alkanes and benzimidazolines; pheno->Condensed tricyclic heterocycles such as oxazine; etc.

Examples of the heterocyclic ring containing a nitrogen atom and a sulfur atom include monocyclic heterocyclic rings such as thiazole, e.g., thiazole, 2-methylthiazole, 3-methylthiazole, 4-methylthiazole, 5-methylthiazole, 2, 4-dimethylthiazole, and the like; fused bicyclic heterocycles such as benzothiazole; fused tricyclic heterocycles such as phenothiazine; etc.

The bonding position of the heterocyclic group is a position after any hydrogen atom contained in each heterocyclic ring is detached.

The heterocyclic group may be a combination of the heterocyclic ring described above and the hydrocarbon group described above, and examples thereof include a tetrahydrofuryl group and the like.

The heterocyclic group may be a group represented by the following formula. The binding site is denoted by the symbol.

the hydrogen atoms constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with a halogen atom, cyano group, nitro group, -SO ₃ M、－CO ₂ M or MM. Examples of such groups include the following groups.

For example, the number of the cells to be processed, examples thereof include trichloromethyl, trifluoromethyl, 2-trifluoroethyl, 2-dibromoethyl, 2, 3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, diethylaminoethyl, (4-methoxyphenyl) methyl, (2-methoxyphenyl) methyl, (3-methoxyphenyl) methyl, (4-nitrophenyl) methyl, (2, 4-dichlorophenyl) methyl (4-fluorophenyl) methyl, (3, 5-difluorophenyl) methyl, 2-trifluoro-1-trifluoromethyl-1-phenylethyl, (phenoxy) (phenyl) methyl, (benzyloxy) (phenyl) methyl, pyrrolylmethyl, pyrrolylethyl, (4-aminophenyl) methyl, (4-cyanophenyl) methyl, 2-hydroxy-1-methyl-1-phenylethyl, 2-chloro-1-methyl-1-phenylethyl; -CH ₂ CH ₂ OCH ₂ CH ₃ 、－CH ₂ CH ₂ O(CH ₂ ) ₃ CH ₃ 、－(CH ₂ CH ₂ O) ₂ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₃ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₄ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₅ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₆ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₇ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₈ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₉ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₁₀ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₁₁ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₁₂ CH ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₁₃ CH ₃ 、－CH ₂ CH ₂ OH、－(CH ₂ CH ₂ O) ₂ H、－(CH ₂ CH ₂ O) ₃ H、－(CH ₂ CH ₂ O) ₄ H、－(CH ₂ CH ₂ O) ₅ H、－(CH ₂ CH ₂ O) ₆ H、－(CH ₂ CH ₂ O) ₇ H、－(CH ₂ CH ₂ O) ₈ H、－(CH ₂ CH ₂ O) ₉ H、－(CH ₂ CH ₂ O) ₁₀ H、－(CH ₂ CH ₂ O) ₁₁ H、－(CH ₂ CH ₂ O) ₁₂ H、－(CH ₂ CH ₂ O) ₁₃ H、－CH ₂ CH ₂ OCH ₃ 、－(CH ₂ CH ₂ O) ₂ CH ₃ 、－(CH ₂ CH ₂ O) ₃ CH ₃ 、－(CH ₂ CH ₂ O) ₄ CH ₃ 、－(CH ₂ CH ₂ O) ₅ CH ₃ 、－(CH ₂ CH ₂ O) ₆ CH ₃ 、－(CH ₂ CH ₂ O) ₇ CH ₃ 、－(CH ₂ CH ₂ O) ₈ CH ₃ 、－(CH ₂ CH ₂ O) ₉ CH ₃ 、－(CH ₂ CH ₂ O) ₁₀ CH ₃ 、－(CH ₂ CH ₂ O) ₁₁ CH ₃ 、－(CH ₂ CH ₂ O) ₁₂ CH ₃ 、－(CH ₂ CH ₂ O) ₁₃ CH ₃ And the like-CH of the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group ₂ -a group substituted with-O-; and alkyl groups having a substituent (hereinafter, they may be referred to as groups of group a).

Examples thereof include aryl groups having substituents such as 4-bromophenyl group, 4-nitrophenyl group, 4-methoxyphenyl group, 2, 4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 4,5, 8-trichloro-2-naphthyl group, anthraquinone group and 2-aminoanthraquinone group (hereinafter, these groups may be referred to as groups B).

Examples thereof include formyl; acetyl, propionyl, butyryl, 2-dimethylpropionyl, pentanoyl, hexanoyl, 2-ethylhexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, heneicosanoyl, benzoyl,

and a carbonyl group to which the groups of the above groups A to B or the above 1-valent hydrocarbon group or 1-valent heterocyclic group are bonded,

preferably a carbonyl group to which a hydrocarbon group having 1 to 30 carbon atoms, the groups of the above groups A to B or a group preferable to the above 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded,

more preferably a carbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms, the groups of the above groups A to B or a group preferable to the above 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded,

Further preferably a carbonyl group to which a hydrocarbon group having 1 to 18 carbon atoms, the groups of the above groups A to B or a group preferable to the above 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded,

particularly preferred is a carbonyl group to which a hydrocarbon group having 1 to 12 carbon atoms, a group of the above groups A to B, or a group preferred as the above 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded.

The binding site is denoted by the symbol.

Examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, pentoxycarbonyl, hexoxycarbonyl, (2-ethylhexyl) oxycarbonyl, heptoxycarbonyl, octoxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, eicosyloxycarbonyl,

and an oxycarbonyl group to which the groups of the above groups A to B or the above 1-valent hydrocarbon group or 1-valent heterocyclic group are bonded,

the oxycarbonyl group to which a hydrocarbon group having 1 to 30 carbon atoms, a group of the above-mentioned group a to group B, or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is preferable, the oxycarbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms, a group of the above-mentioned group a to group B, or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is more preferable, the oxycarbonyl group to which a hydrocarbon group having 1 to 18 carbon atoms, a group of the above-mentioned group a to group B, or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is more preferable, and the oxycarbonyl group to which a hydrocarbon group having 1 to 12 carbon atoms, a group of the above-mentioned group a to group B, or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is more preferable. The binding site is denoted by the symbol.

Examples thereof include a formyloxy group; acetoxy, propionyloxy, butyryloxy, (2, 2-dimethylpropionyl) oxy, pentanoyloxy, hexanoyloxy, (2-ethylhexanoyloxy) oxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, heneicosanoyloxy, benzoyloxy, vinylcarbonyloxy, (2-propenyl) carbonyloxy, (1-methylethenyl) carbonyloxy, and carbonyloxy to which groups A to B are bonded or to which group A to group B are bonded or to which group A is bonded or to which group B is bonded,

the carbonyloxy group to which the hydrocarbon group having 1 to 30 carbon atoms, the group of the group A to group B or the group preferable to the 1-valent hydrocarbon group or the 1-valent heterocyclic group is bonded is preferable, the carbonyloxy group to which the hydrocarbon group having 1 to 20 carbon atoms, the group of the group A to group B or the group preferable to the 1-valent hydrocarbon group or the 1-valent heterocyclic group is bonded is more preferable, the hydrocarbon group having 1 to 18 carbon atoms, the group of the group A to group B or the group preferable to the 1-valent hydrocarbon group or the 1-valent heterocyclic group is more preferable, and the carbonyloxy group to which the hydrocarbon group having 1 to 12 carbon atoms, the group of the group A to group B or the group preferable to the 1-valent hydrocarbon group or the 1-valent heterocyclic group is bonded is particularly preferable.

For example, a hydroxyl group; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, neopentyloxy, 1-ethyl-1, 2-dimethylpropoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, (2-ethylhexyl) oxy, stearyloxy, eicosyloxy, 1-phenylethoxy, 1-methyl-1-phenylethoxy, phenoxy, benzyloxy, 2, 3-dimethylphenoxy, 2, 4-dimethylphenoxy, 2, 5-dimethylphenoxy, 2, 6-dimethylphenoxy, 3, 4-dimethylphenoxy, 3, 5-dimethylphenoxy, 2, 3-dicyanophenoxy, 2, 4-dicyanophenoxy, 2, 5-dicyanophenoxy, 2, 6-dicyanophenoxy, 3, 4-dicyanophenoxy, 3, 5-dicyanophenoxy, 4-methoxyphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-ethoxyphenoxy, 3-ethoxyphenoxy; trichloromethoxy, trifluoromethoxy, 2-trifluoroethoxy, 2, 3-tetrafluoropropoxy 3, 3-trifluoro-2-trifluoromethyl-2-methylpropoxy, 2-butoxyethoxy, 2-nitropropoxy, -OCH ₂ CH ₂ OH、－O(CH ₂ CH ₂ O) ₄ H、－OCH ₂ CF ₂ CF ₂ H、－OCH ₂ CH ₂ O(CH ₂ ) ₃ CH ₃ 、－OCH ₂ CH ₂ OCH ₂ CH ₃ 、－O(CH ₂ CH ₂ O) ₂ CH ₂ CH ₃ 、－O(CH ₂ CH ₂ O) ₄ CH ₂ CH ₃ 、－OCH ₂ CH ₂ O(CH ₂ ) ₃ CH ₃ 、

/>

And an oxy group to which the groups of the above groups A to B or the above 1-valent hydrocarbon group or 1-valent heterocyclic group are bonded,

the hydroxyl group or the hydroxyl group bonded to the hydrocarbon group having 1 to 30 carbon atoms, the group having 1 to 30 carbon atoms, or the group having 1 to 20 carbon atoms, or the group having 1 to 18 carbon atoms, or the group having 1 to 12 carbon atoms, or the group having 1 to 1 carbon atoms, is preferable, and the hydroxyl group or the hydroxyl group having 1 to 12 carbon atoms, the group having 1 to 1 carbon atoms, or the group having 1 to 1 carbon atoms is more preferable. The binding site is denoted by the symbol.

For example, mercapto groups; methylthio, ethylthio, propylthio, butylthio, t-butylthio, pentylthio, hexylthio, (2-ethylhexyl) thio, heptylthio, octylthio, nonylthio, decylthio, undecylthio, dodecylthio, eicosanylthio, phenylthio, o-tolylthio,

And a mercapto group in which a hydrogen atom is substituted with the group A to group B or the 1-valent hydrocarbon group or the 1-valent heterocyclic group,

preferably a mercapto group or a mercapto group having a hydrocarbon group of 1 to 30 carbon atoms, a group of the above groups A to B or a group preferable to the above 1-valent hydrocarbon group or 1-valent heterocyclic group, more preferably a mercapto group or a mercapto group having a hydrocarbon group of 1 to 20 carbon atoms, a group of the above groups A to B or a group preferable to the above 1-valent hydrocarbon group or 1-valent heterocyclic group, further, it is preferable that the hydrogen atom is replaced with a mercapto group or a mercapto group having 1 to 18 carbon atoms, a group of the above-mentioned groups A to B or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group, and particularly preferable is that the hydrogen atom is replaced with a mercapto group or a mercapto group having 1 to 12 carbon atoms, a group of the above-mentioned groups A to B or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group. The binding site is denoted by the symbol.

Examples thereof include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2-ethylhexyl) sulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, undecylsulfonyl, dodecylsulfonyl, eicosylsulfonyl, phenylsulfonyl, p-toluenesulfonyl,

And a sulfonyl group to which the groups of the above groups A to B or the above 1-valent hydrocarbon group or 1-valent heterocyclic group are bonded,

the sulfonyl group to which a hydrocarbon group having 1 to 30 carbon atoms, a group of the above-mentioned group A to group B, or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is preferable, the sulfonyl group to which a hydrocarbon group having 1 to 20 carbon atoms, a group of the above-mentioned group A to group B, or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is more preferable, the sulfonyl group to which a hydrocarbon group having 1 to 18 carbon atoms, a group of the above-mentioned group A to group B, or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is more preferable, and the sulfonyl group to which a hydrocarbon group having 1 to 12 carbon atoms, a group of the above-mentioned group A to group B, or a group preferable to the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is more preferable. The binding site is denoted by the symbol.

For example, a sulfamoyl group; n-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N- (sec-butyl) sulfamoyl, N- (tert-butyl) sulfamoyl, N-pentylsulfamoyl, N- (1-ethylpropyl) sulfamoyl, N-hexylsulfamoyl, N- (2-ethylhexyl) sulfamoyl, N-heptylsulfamoyl, N-octylsulfamoyl, N-nonylsulfamoyl, N-decylsulfamoyl, N-undecylsulfamoyl, N-dodecylsulfamoyl, N-eicosylsulfamoyl, N-phenylsulfamoyl, -SO ₂ NH(CH ₂ ) ₂ N(CH ₂ CH ₃ ) ₂ 、－SO ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ And sulfamoyl groups substituted with 1 group A to group B or 1 hydrocarbon group or 1 heterocyclic group;

n, N-dimethyl sulfamoyl, N-ethyl-N-methyl sulfamoyl, N-diethyl sulfamoyl, N-propyl-N-methyl sulfamoyl, N-dipropyl sulfamoyl, N-isopropyl-N-methyl sulfamoyl, N-diisopropyl sulfamoyl, N-diisobutyl sulfamoyl, N-di (sec-butyl) sulfamoyl, N- (tert-butyl) -N-methyl sulfamoyl, N, N-di (tert-butyl) sulfamoyl, N-butyl-N-methylsulfamoyl, N-dibutylsulfamoyl, N-butyl-N-octylsulfamoyl, N-dipentylsulfamoyl, N-bis (1-ethylpropyl) sulfamoyl, N-butyl-N-hexylsulfamoyl, N-hexyl-N-methylsulfamoyl, N, N-dihexylsulfamoyl group, N- (2-ethylhexyl) -N-methylsulfamoyl group, N-bis (2-ethylhexyl) sulfamoyl group, N-diheptylsulfamoyl group, N-octyl-N-methylsulfamoyl group, N-dioctylsulfamoyl group, N-dinonylsulfamoyl group, N-decyl-N-methylsulfamoyl group, N-undecyl-N-methylsulfamoyl group, N-dodecyl-N-methylsulfamoyl group, N-eicosyl-N-methylsulfamoyl group, N-phenyl-N-methylsulfamoyl group, N-diphenylsulfamoyl group, sulfamoyl group substituted with 2 groups selected from the group A to the group B described above, the above-mentioned 1-valent hydrocarbon group and the above-mentioned 1-valent heterocyclic group, and the like,

Preferably a sulfamoyl group, -SO, substituted with 1 or 2 groups selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, the group of groups A to B, the group preferred for the above-mentioned 1-valent hydrocarbon group and the group preferred for the above-mentioned 1-valent heterocyclic group ₂ NH(CH ₂ ) ₂ N(CH ₂ CH ₃ ) ₂ Or a sulfamoyl group, more preferably a sulfamoyl group, -SO, substituted with 1 or 2 groups selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a group of the above groups A to B, a group preferred for the above 1-valent hydrocarbon group and a group preferred for the above 1-valent heterocyclic group ₂ NH(CH ₂ ) ₂ N(CH ₂ CH ₃ ) ₂ Or a sulfamoyl group, more preferably a sulfamoyl group, -SO, substituted with 1 or 2 groups selected from the group consisting of a hydrocarbon group having 1 to 18 carbon atoms, a group of the above groups A to B, a group preferred for the above 1-valent hydrocarbon group and a group preferred for the above 1-valent heterocyclic group ₂ NH(CH ₂ ) ₂ N(CH ₂ CH ₃ ) ₂ Or a sulfamoyl group, particularly preferably a sulfamoyl group, -SO, substituted with 1 or 2 groups selected from the group consisting of a hydrocarbon group having 1 to 12 carbon atoms, a group of the above groups A to B, a group preferred for the above 1-valent hydrocarbon group and a group preferred for the above 1-valent heterocyclic group ₂ NH(CH ₂ ) ₂ N(CH ₂ CH ₃ ) ₂ Or sulfamoyl.

For example, carbamoyl; n-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-isopropylcarbamoyl, N-butylcarbamoyl, N-isobutylcarbamoyl, N- (sec-butylcarbamoyl, N- (tert-butyl) amino) Formyl, N-pentylcarbamoyl, N- (1-ethylpropyl) carbamoyl, N-hexylcarbamoyl, N- (2-ethylhexyl) carbamoyl, N-heptylcarbamoyl, N-octylcarbamoyl, N-nonylcarbamoyl, N-decylcarbamoyl, N-undecylcarbamoyl, N-dodecylcarbamoyl, N-eicosylcarbamoyl, N-phenylcarbamoyl, -CONH (CH) ₂ ) ₂ N(CH ₂ CH ₃ ) ₂ 、－CONHCH ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₃ And carbamoyl groups substituted with 1 of the groups A to B or the 1-valent hydrocarbon group or the 1-valent heterocyclic group;

n, N-dimethylcarbamoyl, N-ethyl-N-methylcarbamoyl, N-diethylcarbamoyl, N-propyl-N-methylcarbamoyl, N-dipropylcarbamoyl, N-isopropyl-N-methylcarbamoyl, N-diisopropylcarbamoyl, N-diisobutylcarbamoyl, N-di (sec-butyl) carbamoyl, N- (tert-butyl) -N-methylcarbamoyl, N, N-di (tert-butyl) carbamoyl, N-butyl-N-methylcarbamoyl, N-dibutylcarbamoyl, N-butyl-N-octylcarbamoyl, N-dipentylcarbamoyl, N-bis (1-ethylpropyl) carbamoyl, N-butyl-N-hexylcarbamoyl, N-hexyl-N-methylcarbamoyl, N, N-dihexylcarbamoyl, N- (2-ethylhexyl) -N-methylcarbamoyl, N-bis (2-ethylhexyl) carbamoyl, N-diheptylcarbamoyl, N-octyl-N-methylcarbamoyl, N-dioctylcarbamoyl, N-dinonylcarbamoyl, N-decyl-N-methylcarbamoyl, N-undecyl-N-methylcarbamoyl, N-dodecyl-N-methylcarbamoyl, N-eicosyl-N-methylcarbamoyl, N-phenyl-N-methylcarbamoyl, N-diphenylcarbamoyl, substituted with a group selected from the above groups A to B, carbamoyl groups of 2 of the above-mentioned 1-valent hydrocarbon groups and the above-mentioned 1-valent heterocyclic groups, and the like,

Preferably, a carbamoyl group or a carbamoyl group substituted with 1 or 2 selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, a group preferred by the above-mentioned group A to group B, and a group preferred by the above-mentioned group 1 heterocyclic group, more preferably, a carbamoyl group or a carbamoyl group substituted with 1 or 2 selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a group preferred by the above-mentioned group A to group B, a group preferred by the above-mentioned group 1 hydrocarbon group, and a group preferred by the above-mentioned group 1 heterocyclic group, further preferably, a carbamoyl group or a carbamoyl group substituted with 1 or 2 selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a group preferred by the above-mentioned group A to group B, a group preferred by the above-mentioned group 1 hydrocarbon group, and a group preferred by the above-mentioned group 1 to group B, and a carbamoyl group preferred by the above-mentioned group 1 to group preferred by the above-mentioned 1 heterocyclic group or a carbamoyl group preferred by the above-mentioned group 1 to 2.

For example, an amino group; n-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino, N-isobutylamino, N- (sec-butylamino), N- (tert-butylamino), N-pentylamino, N- (1-ethylpropyl) amino, N-hexylamino, N- (2-ethylhexyl) amino, N-heptylamino, N-octylamino, N-nonylamino, N-decylamino, N-undecylamino, N-dodecylamino, N-eicosylamino, N-phenylamino, and amino substituted with 1 group A to group B described above or 1-valent hydrocarbon group or 1-valent heterocyclic group described above, and the like;

N, N-dimethylamino, N-ethyl-N-methylamino, N-diethylamino, N-propyl-N-methylamino, N-dipropylamino, N-isopropyl-N-methylamino, N-diisopropylamino, N-diisobutylamino, N-di (sec-butyl) amino, N- (tert-butyl) -N-methylamino, N, N-di (tert-butyl) amino, N-butyl-N-methylamino, N-dibutylamino, N-butyl-N-octylamino, N-dipentylamino, N-bis (1-ethylpropyl) amino, N-butyl-N-hexylamino, N-hexyl-N-methylamino, N, N-dihexylamino, N- (2-ethylhexyl) -N-methylamino, N-bis (2-ethylhexyl) amino, N-diheptylamino, N-octyl-N-methylamino, N-dioctylamino, N-dinonylamino, N-decyl-N-methylamino, N-undecyl-N-methylamino, N-dodecyl-N-methylamino, N-eicosyl-N-methylamino, N-phenyl-N-methylamino, N-diphenylamino, and amino substituted with 2 of the groups selected from the groups A to B described above, the 1-valent hydrocarbon group described above, and the 1-valent heterocyclic group described above, and the like,

Preferably, 1 or 2 amino groups or amino groups selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, a group selected from the group A to group B, a group selected from the group consisting of the group 1-valent hydrocarbon groups, and a group selected from the group 1-valent heterocyclic groups are substituted, more preferably, 1 or 2 amino groups or amino groups selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a group selected from the group A to group B, a group selected from the group 1-valent hydrocarbon groups, and a group selected from the group 1-valent heterocyclic groups are substituted, still more preferably, 1 or 2 amino groups selected from the group consisting of a hydrocarbon group having 1 to 18 carbon atoms, a group selected from the group A to group B, a group selected from the group 1-valent hydrocarbon groups, and a group selected from the group 1-valent heterocyclic groups are substituted, and particularly preferably, 1 or 2 amino groups selected from the group 1-valent hydrocarbon groups, the group selected from the group 1-valent heterocyclic groups.

For example, a formylamino group is mentioned; acetylamino, propionylamino, butyrylamino, (2, 2-dimethylpropionylamino), pentanoylamino, (2-ethylhexanoylamino), heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoylamino, dodecanoylamino, heneicosanoylamino, benzoylamino,

And a carbonylamino group having the group A to group B or the 1-valent hydrocarbon group or the 1-valent heterocyclic group bonded thereto,

the carbonylamino group to which the hydrocarbon group having 1 to 30 carbon atoms, the group A to group B described above or the group preferred by the group 1-valent hydrocarbon group or the group 1-valent heterocyclic group described above is bonded is preferable, the hydrocarbon group having 1 to 20 carbon atoms, the group A to group B described above or the group preferred by the group 1-valent hydrocarbon group or the group 1-valent heterocyclic group described above is more preferable, the hydrocarbon group having 1 to 18 carbon atoms, the group A to group B described above or the group preferred by the group 1-valent hydrocarbon group or the group 1-valent heterocyclic group described above is more preferable, and the hydrocarbon group having 1 to 12 carbon atoms, the group A to group B described above or the group preferred by the group 1-valent hydrocarbon group or the group 1-valent heterocyclic group described above is particularly preferable. The binding site is denoted by the symbol.

For example, there may be mentioned-SiH ₃ ；－Si(CH ₃ ) ₃ 、－Si(CH ₂ CH ₃ ) ₃ 、－Si((CH ₂ ) ₂ CH ₃ ) ₃ 、－Si(CH(CH ₃ ) ₂ ) ₃ 、－Si((CH ₂ ) ₃ CH ₃ ) ₃ 、－Si((CH ₂ ) ₄ CH ₃ ) ₃ 、－Si((CH ₂ ) ₅ CH ₃ ) ₃ 、－Si((CH ₂ ) ₆ CH ₃ ) ₃ 、－Si((CH ₂ ) ₇ CH ₃ ) ₃ 、－Si((CH ₂ ) ₈ CH ₃ ) ₃ 、－Si((CH ₂ ) ₉ CH ₃ ) ₃ 、－Si((CH ₂ ) ₁₀ CH ₃ ) ₃ 、－Si((CH ₂ ) ₁₁ CH ₃ ) ₃ 、－Si((CH ₂ ) ₁₂ CH ₃ ) ₃ 、－Si(C ₆ H ₅ ) ₃ 、－Si(C ₁₀ H ₇ ) ₃ 、－Si(CH ₃ ) ₂ (CH ₂ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₂ CH ₃ )、－Si(CH ₃ ) ₂ (CH(CH ₃ ) ₂ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₃ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₅ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₇ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₉ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₁₁ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₁₃ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₁₅ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₁₇ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₁₉ CH ₃ )、－Si(CH ₃ ) ₂ ((CH ₂ ) ₂₉ CH ₃ )、－Si(CH ₃ ) ₂ (C ₆ H ₅ )、－Si(CH ₃ )(C ₆ H ₅ ) ₂ 、－Si(CH ₃ ) ₂ (C ₁₀ H ₇ ) and-SiH substituted with 1, 2 or 3 of the above groups A to B, the above 1-valent hydrocarbon group and the above 1-valent heterocyclic group ₃ Etc.;

－Si(OH) ₃ ；－Si(OCH ₃ ) ₃ 、－Si(OCH ₂ CH ₃ ) ₃ 、－Si(O(CH ₂ ) ₂ CH ₃ ) ₃ 、－Si(OCH(CH ₃ ) ₂ ) ₃ 、－Si(O(CH ₂ ) ₃ CH ₃ ) ₃ 、－Si(O(CH ₂ ) ₄ CH ₃ ) ₃ 、－Si(O(CH ₂ ) ₅ CH ₃ ) ₃ 、－Si(O(CH ₂ ) ₆ CH ₃ ) ₃ 、－Si(O(CH ₂ ) ₇ CH ₃ ) ₃ 、－Si(O(CH ₂ ) ₈ CH ₃ ) ₃ 、－Si(O(CH ₂ ) ₉ CH ₃ ) ₃ 、－Si(O(CH ₂ ) ₁₀ CH ₃ ) ₃ 、－Si(O(CH ₂ ) ₁₁ CH ₃ ) ₃ 、－Si(OC ₆ H ₅ ) ₃ 、－Si(OC ₁₀ H ₇ ) ₃ 、－Si(OCH ₃ ) ₂ (OCH ₂ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₂ CH ₃ )、－Si(OCH ₃ ) ₂ (OCH(CH ₃ ) ₂ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₃ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₅ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₇ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₉ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₁₁ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₁₃ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₁₅ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₁₇ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₁₉ CH ₃ )、－Si(OCH ₃ ) ₂ (O(CH ₂ ) ₂₉ CH ₃ )、－Si(OCH ₃ ) ₂ (OC ₆ H ₅ )、－Si(OCH ₃ )(OC ₆ H ₅ ) ₂ 、－Si(OCH ₃ ) ₂ (OC ₁₀ H ₇ ) and-Si (OH) substituted with 1, 2 or 3 of the groups selected from the above groups A to B, the above 1-valent hydrocarbon group and the above 1-valent heterocyclic group ₃ Etc.;

－SiH(OH) ₂ ；－Si(CH ₃ )(OCH ₃ ) ₂ 、－Si((CH ₂ ) ₁₁ CH ₃ )(O(CH ₂ ) ₁₁ CH ₃ ) ₂ 、－Si(C ₆ H ₅ )(OC ₆ H ₅ ) ₂ 、－Si(CH ₃ )(OH) ₂ 、－Si((CH ₂ ) ₃₆ CH ₃ )(OH) ₂ 、－Si(C ₆ H ₅ )(OH) ₂ and 1, 2 or 3 of the above groups A to B, the above 1-valent hydrocarbon group and the above 1-valent heterocyclic group are substituted－SiH(OH) ₂ Etc.;

－SiH ₂ (OH)；－Si(CH ₃ ) ₂ (OCH ₃ )、－Si((CH ₂ ) ₁₁ CH ₃ ) ₂ (O(CH ₂ ) ₁₁ CH ₃ )、－Si(C ₆ H ₅ ) ₂ (OC ₆ H ₅ )、－Si(CH ₃ ) ₂ (OH)、－Si((CH ₂ ) ₁₇ CH ₃ ) ₂ (OH)、－Si(C ₆ H ₅ ) ₂ (OH), and-SiH substituted with 1, 2 or 3 of the above groups A to B, the above 1-valent hydrocarbon group and the above 1-valent heterocyclic group ₂ (OH) and the like.

Preferably substituted with-SiH of 1, 2 or 3 selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, the above groups A to B, a group preferred for the above 1-valent hydrocarbon group and a group preferred for the above 1-valent heterocyclic group ₃ 、－Si(OH) ₃ 、－SiH(OH) ₂ and-SiH ₂ (OH), or-Si (OH) ₃ More preferably 1, 2 or 3-SiH groups selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms, groups A to B described above, groups preferred for the above-mentioned 1-valent hydrocarbon groups and groups preferred for the above-mentioned 1-valent heterocyclic groups ₃ 、－Si(OH) ₃ 、－SiH(OH) ₂ and-SiH ₂ (OH), or-Si (OH) ₃ Further preferably substituted with-SiH of 1, 2 or 3 selected from the group consisting of a hydrocarbon group having 1 to 18 carbon atoms, the above groups A to B, a group preferred for the above 1-valent hydrocarbon group and a group preferred for the above 1-valent heterocyclic group ₃ 、－Si(OH) ₃ 、－SiH(OH) ₂ and-SiH ₂ (OH), or-Si (OH) ₃ Particularly preferably substituted with-SiH of 1, 2 or 3 groups selected from the group consisting of hydrocarbon groups having 1 to 12 carbon atoms, groups A to B described above, groups preferred for the above-mentioned 1-valent hydrocarbon groups and groups preferred for the above-mentioned 1-valent heterocyclic groups ₃ 、－Si(OH) ₃ 、－SiH(OH) ₂ and-SiH ₂ (OH), or-Si (OH) ₃ 。

Examples thereof include phthaloyl subunits which may have a substituentAminomethyl group (C) ₆ H ₄ (CO) ₂ N－CH ₂ Examples of the substituent include at least 1 selected from the group consisting of the halogen atom, the groups A to B, the 1-valent hydrocarbon group and the 1-valent heterocyclic group.

As other groups, there may be mentioned-SCOCH ₃ 、

The binding site is denoted by the symbol.

The 1-valent hydrocarbon group or the 1-valent heterocyclic group may be substituted with-SO ₃ ^- N ⁺ (C ₁₂ H ₂₅ )(CH ₃ ) ₃ 、－CO ₂ ^- N ⁺ (C ₁₂ H ₂₅ )(CH ₃ ) ₃ 、－SO ₃ ^- 、－CO ₂ ^- Etc.

R ¹ And R is ² 、R ² And R is ³ And R is ³ And R is ⁴ Respectively, can be bonded to each other to form a ring.

Examples of the alkali metal atom represented by M and MM include alkali metal atoms such as lithium atom, sodium atom and potassium atom.

Examples of the metal atom which may have a ligand and which is represented by M and MM include metal atoms belonging to groups IIA to VA of the periodic Table of elements. The metal atom which may have a metal atom of a ligand is more preferably Mg, ca, sr, ba, cd, ni, zn, cu, hg, fe, co, sn, pb, mn, al, cr, rh, ir, pd, ti, zr, hf, si, ge, still more preferably Mg, ca, sr, ba, ni, zn, cu, fe, co, sn, mn, al, cr, and particularly preferably Mg, ca, sr, ba, ni, zn, cu, fe, co, mn, al, cr.

The ligand which may have a metal atom of the ligand is not particularly limited, and may be, for example, a halogen atom, NO ₃ 、SO ₄ 、CH ₃ CO ₂ OH, or the like, ligands coordinated to the metal atom and in the same ligandThe carbon atom, nitrogen atom, oxygen atom, sulfur atom, or the like contained may be coordinated to the same metal atom, and in the metal atom, a plurality of different ligands may be coordinated to the same metal atom, and an oligomer or a polymer may be formed. When the compound (I) contains a metal atom which may have a ligand, the ligand further contains the compound (I) from which the metal atom which may have a ligand has been removed. The compound (I) of the present invention also contains such an oligomer or polymer. Wherein the charge of the compound (I) is 0.

Examples of the compound (I) include metal salts represented by the following formulas (EN 1) to (EN 5). Wherein the structures shown in formulas (EN 1) to (EN 5) () represent repeated bonding as in the case of oligomers and polymers. For example, the metal salt represented by formula (EN 1) represents that the same ligand is coordinated to the same metal atom. For example, the metal salts represented by the formulas (EN 2) to (EN 3) represent oligomers in which a plurality of different ligands are coordinated to the same metal atom. For example, the metal salts represented by the formulas (EN 4) to (EN 5) represent oligomers or polymers in which a plurality of different ligands are coordinated to the same metal atom.

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N (Z) represented as M and MM ¹ )(Z ² )(Z ³ )(Z ⁴ ) NH can be mentioned ₄ ；NH ₃ ((CH ₂ ) ₇ CH ₃ )、NH ₃ ((CH ₂ ) ₁₁ CH ₃ )、NH ₃ ((CH ₂ ) ₁₇ CH ₃ ) Equal NH ₄ A group substituted with 1 alkyl group; n (CH) ₃ ) ₃ ((CH ₂ ) ₁₅ CH ₃ )、N(CH ₃ ) ₃ ((CH ₂ ) ₁₁ CH ₃ )、N(CH ₃ ) ₂ ((CH ₂ ) ₁₁ CH ₃ ) ₂ 、N(CH ₃ ) ₂ ((CH ₂ ) ₁₇ CH ₃ ) ₂ Equal NH ₄ A group substituted with 4 alkyl groups; and NH substituted with 1, 2, 3 or 4 of the above groups A to B, the above 1-valent hydrocarbon group and the above 1-valent heterocyclic group ₄ Etc.

M is preferably a hydrogen atom; an alkali metal atom; mg which may have a ligand, ca which may have a ligand, sr which may have a ligand, ba which may have a ligand, ni which may have a ligand, zn which may have a ligand, cu which may have a ligand, fe which may have a ligand, co which may have a ligand, sn which may have a ligand, mn which may have a ligand, al which may have a ligand, cr which may have a ligand; NH (NH) ₄ ；NH ₃ ((CH ₂ ) ₇ CH ₃ )、NH ₃ ((CH ₂ ) ₁₁ CH ₃ )、NH ₃ ((CH ₂ ) ₁₇ CH ₃ ) Equal NH ₄ A group substituted with 1 alkyl group; n (CH) ₃ ) ₃ ((CH ₂ ) ₁₅ CH ₃ )、N(CH ₃ ) ₃ ((CH ₂ ) ₁₁ CH ₃ )、N(CH ₃ ) ₂ ((CH ₂ ) ₁₁ CH ₃ ) ₂ 、N(CH ₃ ) ₂ ((CH ₂ ) ₁₇ CH ₃ ) ₂ Equal NH ₄ A group having 4 alkyl groups substituted thereon,

more preferably a hydrogen atom; a sodium atom, a potassium atom; mg which may have a ligand, ca which may have a ligand, sr which may have a ligand, ba which may have a ligand, ni which may have a ligand, zn which may have a ligand, cu which may have a ligand, fe which may have a ligand, co which may have a ligand, mn which may have a ligand, al which may have a ligand, cr which may have a ligand; NH (NH) ₄ ；NH ₃ ((CH ₂ ) ₇ CH ₃ )、NH ₃ ((CH ₂ ) ₁₁ CH ₃ )、NH ₃ ((CH ₂ ) ₁₇ CH ₃ ) Equal NH ₄ A group substituted with 1 alkyl group; n (CH) ₃ ) ₃ ((CH ₂ ) ₁₅ CH ₃ )、N(CH ₃ ) ₃ ((CH ₂ ) ₁₁ CH ₃ )、N(CH ₃ ) ₂ ((CH ₂ ) ₁₁ CH ₃ ) ₂ 、N(CH ₃ ) ₂ ((CH ₂ ) ₁₇ CH ₃ ) ₂ Equal NH ₄ A group substituted with 4 alkyl groups.

MM is preferably an alkali metal atom; mg which may have a ligand, ca which may have a ligand, sr which may have a ligand, ba which may have a ligand, ni which may have a ligand, zn which may have a ligand, cu which may have a ligand, fe which may have a ligand, co which may have a ligand, sn which may have a ligand, mn which may have a ligand, al which may have a ligand, cr which may have a ligand; NH (NH) ₄ ；NH ₃ ((CH ₂ ) ₇ CH ₃ )、NH ₃ ((CH ₂ ) ₁₁ CH ₃ )、NH ₃ ((CH ₂ ) ₁₇ CH ₃ ) Equal NH ₄ A group substituted with 1 alkyl group; n (CH) ₃ ) ₃ ((CH ₂ ) ₁₅ CH ₃ )、N(CH ₃ ) ₃ ((CH ₂ ) ₁₁ CH ₃ )、N(CH ₃ ) ₂ ((CH ₂ ) ₁₁ CH ₃ ) ₂ 、N(CH ₃ ) ₂ ((CH ₂ ) ₁₇ CH ₃ ) ₂ Equal NH ₄ A group having 4 alkyl groups substituted thereon,

more preferably a sodium atom, a potassium atom; mg which may have a ligand, ca which may have a ligand, sr which may have a ligand, ba which may have a ligand, ni which may have a ligand, zn which may have a ligand, cu which may have a ligand, fe which may have a ligand, co which may have a ligand, mn which may have a ligand, al which may have a ligand, cr which may have a ligand; NH (NH) ₄ ；NH ₃ ((CH ₂ ) ₇ CH ₃ )、NH ₃ ((CH ₂ ) ₁₁ CH ₃ )、NH ₃ ((CH ₂ ) ₁₇ CH ₃ ) NH of etc ₄ A group substituted with 1 alkyl group; n (CH) ₃ ) ₃ ((CH ₂ ) ₁₅ CH ₃ )、N(CH ₃ ) ₃ ((CH ₂ ) ₁₁ CH ₃ )、N(CH ₃ ) ₂ ((CH ₂ ) ₁₁ CH ₃ ) ₂ 、N(CH ₃ ) ₂ ((CH ₂ ) ₁₇ CH ₃ ) ₂ Equal NH ₄ A group substituted with 4 alkyl groups.

Q ¹ And Q ² Each independently represents a 2-valent hydrocarbon group or a 2-valent heterocyclic group, -C (-) (-) -constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted with-Si (-) (-) -constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group, -CH (-) -constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted with-N (-) -, and-ch=constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted with-n=, constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group ₂ Can be substituted by-O-, -S-, -S (O) ₂ -or-CO-, the hydrogen atoms constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted with a halogen atom, cyano group, nitro group, -SO ₃ M、－CO ₂ M or MM. As the group substituted for the hydrogen atom constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group, a halogen atom, cyano group, nitro group, -SO group is preferable ₃ H or-CO ₂ H。

Q ¹ And Q ² May be the same or different, and is preferably the same. Q (Q) ¹ And Q ² The groups represented by the formulas (QQ 1) to (QQ 19) are preferable.

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[ formula (QQ 1) to formula (QQ 19), R ^Q1 ～R ^Q94 Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -SO ₃ M、－CO ₂ M, MM a 1-valent hydrocarbon group having 1 to 40 carbon atoms or a 1-valent heterocyclic group having 1 to 40 carbon atoms, -C (-) (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-Si (-) (-) -and-CH (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-N (-) -, and-ch=constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-n=, and-ch=constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group ₂ Can be substituted by-O-, -S-, -S (O) ₂ -or-CO-, the hydrogen atoms constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with a halogen atom, cyano group, nitro group, -SO ₃ M、－CO ₂ M or MM. R is R ^Q1 ～R ^Q94 Can be respectively combined with R ^Q1 ～R ^Q94 More than 1 of them are bonded to form a ring. M and MM are as defined above. The binding site is denoted by the symbol.]

As R ^Q1 ～R ^Q94 Represented 1-valent hydrocarbon group having 1 to 40 carbon atoms or 1-valent heterocyclic group having 1 to 40 carbon atoms, and-C (-) (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-Si (-) (-) -, -CH (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-N (-) -, and-ch=constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-n=, and-CH constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group ₂ Can be substituted by-O-, -S-, -S (O) ₂ -or-CO-, the hydrogen atoms constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with halogen atoms, cyano groups, nitro groups, -SO ₃ M、－CO ₂ Examples of the M or MM group include R ¹ ～R ⁵ And Z ¹ ～Z ⁴ Represented 1-valent hydrocarbon group having 1 to 40 carbon atoms or 1-valent heterocyclic group having 1 to 40 carbon atoms, and-C (-) (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-Si (-) (-) -, -CH (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-N (-) -, and-ch=constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted with-n=, and-CH constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group ₂ Can be substituted by-O-, -S-, -S (O) ₂ -or-CO-, constituting the 1-valent hydrocarbonThe hydrogen atoms of the radicals and the 1-valent heterocyclic radicals may be substituted by halogen atoms, cyano groups, nitro groups, -SO ₃ M、－CO ₂ M or MM is the same group.

As R ^Q1 ～R ^Q94 Preferred groups include those mentioned as R ¹ ～R ⁵ And Z ¹ ～Z ⁴ Preferred groups are the same.

Q ¹ And Q ² The group represented by the formulas (QQ 1) to (QQ 12) is preferable, the group represented by the formulas (QQ 1) to (QQ 5) is more preferable, the group represented by the formulas (QQ 1) to (QQ 4) is more preferable, the group represented by the formulas (QQ 1) and (QQ 2) is particularly preferable, and the group represented by the formula (QQ 2) is more preferable.

Examples of the formulae (QQ 1) to (QQ 19) include the following formulae (Qa 1) to (Qa 50); formulas (Qb 1) to (Qb 27); formulas (Qc 1) to (Qc 56); formulas (Qd 1) to (Qd 41); formulas (Qe 1) to (Qe 16); formulas (Qf 1) to (Qf 15); formulas (Qg 1) to (Qg 40); formulas (Qh 1) to (Qh 40); formulas (Qj 1) to (Qj 29); formulas (Qk 1) to (Qk 22); formulae (Qm 1) to (Qm 20); formulas (Qn 1) to (Qn 16); formulas (Qo 1) to (Qo 15); formulas (Qp 1) to (Qp 83); formulas (Qq 1) to (Qq 72); formulas (Qr 1) to (Qr 17); formulas (Qs 1) to (Qs 26); formulas (Qt 1) to (Qt 26); formulas (Qu 1) to (Qu 17); formulas (Qv 1) to (Qv 26); formulas (Qx 1) to (Qx 2); and groups represented by the formulae (Qy 1) to (Qy 10). Wherein, the bonding site is represented by ambroxol.

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Examples of the compound (I) include compounds represented by the formula (Ia) shown in tables 1 to 14 below, or alkali metal salts thereof. "Q" in tables 1 to 14 ¹ "column sum" Q ² The symbols in the columns correspond to the groups represented by the above formulas, respectively. The binding site is denoted by the symbol.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

TABLE 11

TABLE 12

TABLE 13

TABLE 14

Examples of the compound (I) include compounds represented by the formula (Ib) shown in tables 15 to 31 below, or alkali metal salts thereof.

In the formula (Ib), R is ^Ib1 ～R ^Ib5 Either one of them is a substituent other than a hydrogen atom (hereinafter, sometimes referred to as an RR group), and the other 4 are hydrogen atoms. "Q" in tables 15 to 31 ¹ "column sum" Q ² The symbols in the columns correspond to the groups represented by the above formulas, respectively. The symbol indicated in the column "RR" in tables 15 to 31 represents an RR group, and is the same as the following formulas (a 1) to (a 69); formulas (b 1) to (b 4); formulas (c 1) to (c 4); formulas (d 1) to (d 5); formulas (e 1) to (e 20); formulas (f 1) to (f 5); formulas (g 1) to (g 9); formulas (h 1) to (h 9); formulas (j 1) to (j 9); formulas (k 1) to (k 4); formulas (m 1) to (m 9); formulas (n 1) to (n 3); formulas (o 1) to (o 5); formulas (p 1) to (p 23); formulas (q 1) to (q 26); formulas (r 1) to (r 26); the numerical values described in columns "No" in tables 15 to 31 correspond to the groups represented by the formulas (s 1) to (s 26), and each of the numerical values represents a position where the RR group is substituted, and "1" represents that the RR group is substituted by R ^Ib1 "2" means that RR groups are substituted for R ^Ib2 "3" means that RR group is substituted for R ^Ib3 "4" means that RR group is substituted for R ^Ib4 "5" means that RR group is substituted for R ^Ib5 . The binding site is denoted by the symbol.

TABLE 15

TABLE 16

TABLE 17

TABLE 18

TABLE 19

TABLE 20

TABLE 21

TABLE 22

TABLE 23

TABLE 24

TABLE 25

TABLE 26

TABLE 27

TABLE 28

TABLE 29

TABLE 30

TABLE 31

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Examples of the compound (I) include compounds represented by the formula (If) shown in tables f1 to f44 below, or alkali metal salts thereof. "Q" in tables f1 to f44 ¹ "column sum" Q ² The symbols in the columns correspond to the groups represented by the above formulas, respectively. The binding site is denoted by the symbol.

[ Table f1]

[ Table f2]

[ Table f3]

[ Table f4]

[ Table f5]

[ Table f6]

[ Table f7]

[ Table f8]

[ Table f9]

[ Table f10]

[ Table f11]

[ Table f12]

[ Table f13]

[ Table f14]

[ Table f15]

[ Table f16]

[ Table f17]

[ Table f18]

[ Table f19]

[ Table f20]

[ Table f21]

[ Table f22]

[ Table f23]

[ Table f24]

[ Table f25]

[ Table f26]

[ Table f27]

Table f28

[ Table f29]

[ Table f30]

[ Table f31]

[ Table f32]

Table f33

[ Table f34]

[ Table f35]

Table f36

[ Table f37]

[ Table f38]

[ Table f39]

[ Table f40]

[ Table f41]

[ Table f42]

[ Table f43]

[ Table f44]

Examples of the compound (I) include compounds represented by the formula (It) shown in tables t1 to t5, and compounds represented by the formula (Iu) shown in tables u1 to u11, and alkali metal salts thereof. The column "aq" in tables t1 to t5 and tables u1 to u11, “Q ¹ "column," Q ² "column sum" Q ^u+1 The symbols in the columns correspond to the groups represented by the above formulas and the groups represented by the following formulas (aq 1) to (aq 36), respectively. "Q" in tables u1 to u11 ^u+1 "column represents Q in the compound represented by the formula (Iu) ¹ Represented radicals and Q ² The radicals represented are the radicals denoted by the radicals "Q ^u+1 "the symbol in column corresponds to the group. Of the groups represented by the following formulas (aq 1) to (aq 36), # represents Q ¹ Is used for the preparation of a polymer,&representation and Q ² Is a binding site of (a).

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[ Table t1]

[ Table t2]

[ Table t3]

[ Table t4]

[ Table t5]

[ Table u1]

Table u2

Table u3

[ Table u4]

[ Table u5]

Table u6

Table u7

Table u8

Table u9

Table u10

Table u11

Examples of the compound (I) include compounds represented by the formulae (Ia 1) to (Ia 2216) and (Ib 1) to (Ib 1312), compounds represented by the formulae (If 1) to (If 13090), compounds represented by the formulae (It 1) to (It 900), and compounds represented by the formulae (Iu 1) to (Iu 3238) each of which is substituted with a compound selected from the group consisting of-SO ₃ H、-CO ₂ H、-SO ₃ NH ₄ 、-CO ₂ NH ₄ 、-SO ₂ NH ₂ 、－CONH ₂ Phthalimidomethyl (C) ₆ H ₄ (CO) ₂ N－CH ₂ －)、－SO ₂ NH(CH ₂ ) ₂ N(CH ₂ CH ₃ ) ₂ 、－N(CH ₃ )((CH ₂ ) ₁₁ CH ₃ ) And 1 or more of fluorine atom, chlorine atom and bromine atom.

For example, the compound represented by the formula (Ia 1) of Table 1 is substituted with-SO ₃ The compounds of H are shown below. Wherein, in the formula, - (SO) ₃ H) Representation of-SO ₃ H replaces all or more than 1 hydrogen atoms of the compound represented by the formula (Ia 1).

Examples of the above-mentioned compound include compounds in which all hydrogen atoms of the aromatic ring represented by the formulae (Ic 1) to (Ic 12) are substituted with 1 or more selected from fluorine atoms, chlorine atoms and bromine atoms.

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Examples of the compound (I) include compounds represented by the formulae (Ia 1) to (Ia 2216) and (Ib 1) to (Ib 1312), compounds represented by the formulae (If 1) to (If 13090), compounds represented by the formulae (It 1) to (It 900), and compounds represented by the formulae (Iu 1) to (Iu 3238) each of which is substituted with 1 to 6 compounds selected from the group consisting of-SO ₃ H、－CO ₂ H、－SO ₃ NH ₄ 、－CO ₂ NH ₄ 、－SO ₂ NH ₂ 、－CONH ₂ Phthalimidomethyl (C) ₆ H ₄ (CO) ₂ N－CH ₂ －)、－SO ₂ NH(CH ₂ ) ₂ N(CH ₂ CH ₃ ) ₂ 、－N(CH ₃ )((CH ₂ ) ₁₁ CH ₃ ) And 1 or more of fluorine atom, chlorine atom and bromine atom.

For example, in the compound represented by the formula (Ia 1) of Table 1, 1 to 6-SOs are substituted ₃ The compounds of H are shown below. Wherein, in the formula, - (SO) ₃ H) _1～6 Representation of-SO ₃ H is substituted for 1 to 6 hydrogen atoms in the compound represented by the formula (Ia 1).

Examples of the compound (I) include compounds represented by the formulae (Ia 1) to (Ia 2216) and (Ib 1) to (Ib 1312), compounds represented by the formulae (If 1) to (If 13090), compounds represented by the formulae (It 1) to (It 900), and tables of the formulae (Iu 1) to (Iu 3238)The compounds shown are substituted with a compound selected from-SO ₃ ^- and-CO ₂ ^- More than 1 anion selected from Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ 、Ni ²⁺ 、Zn ²⁺ 、Fe ²⁺ 、Co ²⁺ 、Sn ²⁺ 、Mn ²⁺ 、Al ³⁺ 、Fe ³⁺ 、Cr ³⁺ 、Sn ⁴⁺ 、Mn ⁴⁺ 、Cu ²⁺ 、Li ⁺ 、Na ⁺ And K ⁺ Metal salts composed of 1 or more cations.

Examples of the compound (I) include anions represented by the following formulas (Id) and (Ih) shown in tables 32 to 33 and tables h1 to h6, and an anion selected from Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ 、Ni ²⁺ 、Zn ²⁺ 、Fe ²⁺ 、Co ²⁺ 、Sn ²⁺ 、Mn ²⁺ 、Al ³⁺ 、Fe ³⁺ 、Cr ³⁺ 、Sn ⁴⁺ 、Mn ⁴⁺ 、Cu ²⁺ 、Li ⁺ 、Na ⁺ And K ⁺ Metal salts composed of 1 or more cations.

"Q" in tables 32 to 33 and tables h1 to h6 ¹ "column sum" Q ² The symbols in the columns correspond to the groups represented by the above formulas and the groups represented by the following formulas (Qw 1) to (Qw 11), respectively.

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TABLE 32

TABLE 33

[ Table h1]

[ Table h2]

[ Table h3]

[ Table h4]

[ Table h5]

[ Table h6]

Examples of the metal salts include metal salts represented by the formula (Ie) shown in tables 34 to 38 and metal salts represented by the formula (Ik) shown in tables k1 to k 14. As the symbols described in the columns "Met" in tables 34 to 38 and tables k1 to k14, mg2+ represents Mg ²⁺ Ca2+ represents Ca ²⁺ Sr2+ represents Sr ²⁺ Ba2+ represents Ba ²⁺ Ni2+ represents Ni ²⁺ Zn2+ represents Zn ²⁺ Fe2+ represents Fe ²⁺ Co2+ represents Co ²⁺ Sn2+ represents Sn ²⁺ Mn < 2+ > represents Mn ²⁺ Al3+ represents Al ³⁺ Fe3+ represents Fe ³⁺ Cr3+ represents Cr ³⁺ Sn4+ represents Sn ⁴⁺ Mn4+ represents Mn ⁴⁺ Cu < 2+ > represents Cu ²⁺ Li+ represents Li ⁺ Na+ represents Na ⁺ K+ represents K ⁺ 。

"Q" in tables 34 to 38 and tables k1 to k14 ¹ "column sum" Q ² The symbols in the columns correspond to the groups represented by the above formulas, respectively. M in the formulas (Ie) and (Ik) is an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10. N in the formulas (Ie) and (Ik) is an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10. In the case where the compound (I) of the present invention is the oligomer or polymer, the compound (I) is represented by the smallest integer indicating the ratio of the number of ligands to the number of metal atoms, where m and n indicate that the charge of the compound (I) is zero.

TABLE 34

TABLE 35

TABLE 36

TABLE 37

TABLE 38

[ Table k1]

[ Table k2]

[ Table k3]

[ Table k4]

[ Table k5]

[ Table k6]

[ Table k7]

[ Table k8]

[ Table k9]

[ Table k10]

[ Table k11]

[ Table k12]

[ Table k13]

[ Table k14]

As the compound (I), compounds represented by the formulas (Ia 1) to (Ia 2216) are preferable; compounds represented by the formulas (If 1) to (If 13090); compounds represented by the formulas (It 1) to (It 900); and compounds represented by the formulae (Iu 1) to (Iu 3238); a compound represented by the formula (Ib 8); a compound represented by the formula (Ib 14); the compound represented by the formula (Ia 1) to (Ia 2216), the compound represented by the formula (If 1) to (If 13090), the compound represented by the formula (It 1) to (It 900), the compound represented by the formula (Iu 1) to (Iu 3238), the compound represented by the formula (Ib 8) and the compound represented by the formula (Ib 14) are substituted with a compound selected from the group consisting of-SO ₃ H、-CO ₂ H、-SO ₃ NH ₄ 、-CO ₂ NH ₄ 、-SO ₂ NH ₂ 、-CONH ₂ Phthalimidomethyl (C) ₆ H ₄ (CO) ₂ N-CH ₂ -)、-SO ₂ NH(CH ₂ ) ₂ N(CH ₂ CH ₃ ) ₂ 、-N(CH ₃ )((CH ₂ ) ₁₁ CH ₃ ) A compound having 1 or more of a fluorine atom, a chlorine atom and a bromine atom; and the compound represented by the formula (Ia 1) to (Ia 2216), the compound represented by the formula (If 1) to (If 13090), the compound represented by the formula (It 1) to (It 900), the compound represented by the formula (Iu 1) to (Iu 3238), the compound represented by the formula (Ib 8) and the compound represented by the formula (Ib 14) are substituted with a compound selected from the group consisting of-SO ₃ ^- and-CO ₂ ^- More than 1 anion selected from Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ 、Ni ²⁺ 、Zn ²⁺ 、Fe ²⁺ 、Co ²⁺ 、Sn ²⁺ 、Mn ²⁺ 、Al ³⁺ 、Fe ³⁺ 、Cr ³⁺ 、Sn ⁴⁺ 、Mn ⁴⁺ 、Cu ²⁺ 、Li ⁺ 、Na ⁺ And K ⁺ Metal salts composed of 1 or more cations,

more preferably compounds represented by the formulas (Ia 1) to (Ia 2216); compounds represented by the formulas (If 1) to (If 13090); compounds represented by the formulas (It 1) to (It 900); compounds represented by the formulae (Iu 1) to (Iu 3238); the compound represented by the formula (Ia 1) to (Ia 2216), the compound represented by the formula (If 1) to (If 13090), the compound represented by the formula (It 1) to (It 900), the compound represented by the formula (Iu 1) to (Iu 3238), the compound represented by the formula (Ib 8) and the compound represented by the formula (Ib 14) are substituted with a compound selected from the group consisting of-SO ₃ H、－CO ₂ H、－SO ₃ NH ₄ 、－CO ₂ NH ₄ A compound having 1 or more of a fluorine atom, a chlorine atom and a bromine atom; and anions represented by formulas (Id 1) to (Id 304) and anions represented by formulas (Ih 1) to (Ih 1666) and selected from Mg ²⁺ 、Ca ²⁺ 、Sr ²⁺ 、Ba ²⁺ 、Ni ²⁺ 、Zn ²⁺ 、Fe ²⁺ 、Co ²⁺ 、Sn ²⁺ 、Mn ²⁺ 、Al ³⁺ 、Fe ³⁺ 、Cr ³⁺ 、Sn ⁴⁺ 、Mn ⁴⁺ 、Cu ²⁺ 、Li ⁺ 、Na ⁺ And K ⁺ Metal salts composed of 1 or more cations,

further preferred are compounds represented by the formulae (Ia 1) to (Ia 2216); compounds represented by the formulas (If 1) to (If 13090); compounds represented by the formulas (It 1) to (It 900); compounds represented by the formulae (Iu 1) to (Iu 3238); the compound represented by the formula (Ia 1) to (Ia 2216), the compound represented by the formula (If 1) to (If 13090), the compound represented by the formula (It 1) to (It 900), the compound represented by the formula (Iu 1) to (Iu 3238), the compound represented by the formula (Ib 8) and the compound represented by the formula (Ib 14) are substituted with a compound selected from the group consisting of-SO ₃ H、－CO ₂ H、－SO ₃ NH ₄ 、－CO ₂ NH ₄ A compound having 1 or more of a chlorine atom and a bromine atom; compounds represented by the formulas (Ie 1) to (Ie 76); and compounds represented by the formulas (Ik 1) to (Ik 114); compounds represented by the formulas (Ik 1615) to (Ik 1633); compounds represented by the formulas (Ik 1822) to (Ik 1983); a compound represented by the formula (Ie 117); a compound represented by the formula (Ie 123); a compound represented by the formula (Ik 172); a compound represented by the formula (Ik 171); a compound represented by the formula (Ik 1777); a compound represented by the formula (Ik 181); a compound represented by the formula (Ik 397); a compound represented by the formula (Ie 273); and a compound represented by the formula (Ie 116),

particularly preferred are compounds represented by the formulae (Ia 1) to (Ia 2216); compounds represented by the formulas (If 1) to (If 13090); compounds represented by the formulas (It 1) to (It 900); compounds represented by the formulae (Iu 1) to (Iu 3238); a compound represented by the formula (Ib 8); and a compound represented by the formula (Ib 14),

Still more preferably, the compounds represented by the formulae (Ia 1) to (Ia 1241), the compounds represented by the formulae (It 1) to (It 900),

particularly preferred are a compound represented by formula (Ia 1), a compound represented by formula (Ia 2), a compound represented by formula (Ia 3), a compound represented by formula (Ia 10), a compound represented by formula (Ia 22), a compound represented by formula (Ia 23), a compound represented by formula (Ia 33), a compound represented by formula (Ia 35), a compound represented by formula (Ia 315), a compound represented by formula (Ia 696), a compound represented by formula (Ia 703), a compound represented by formula (Ia 973), a compound represented by formula (It 232), a compound represented by formula (It 242) and a compound represented by formula (It 750),

very preferable are a compound represented by formula (Ia 1), a compound represented by formula (Ia 2), a compound represented by formula (Ia 3), a compound represented by formula (Ia 22), a compound represented by formula (Ia 23), a compound represented by formula (Ia 35), a compound represented by formula (Ia 696), a compound represented by formula (Ia 703), a compound represented by formula (Ia 973), a compound represented by formula (It 232), a compound represented by formula (It 242) and a compound represented by formula (It 750),

most preferred are a compound represented by formula (Ia 1), a compound represented by formula (Ia 2), a compound represented by formula (Ia 3), a compound represented by formula (Ia 696), a compound represented by formula (Ia 703), a compound represented by formula (Ia 973), a compound represented by formula (It 232), a compound represented by formula (It 242), and a compound represented by formula (It 750).

The compound represented by the formula (I) can be produced by reacting the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) and the compound represented by the formula (pt 3).

In the formulas (pt 1) to (pt 3), R ¹ ～R ⁵ 、Q ¹ And Q ² The same meaning as described above is indicated.

The amount of the compound represented by the formula (pt 2) used in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) and the compound represented by the formula (pt 3) is usually 0.1 to 30 mol, preferably 1 to 20 mol, more preferably 1 to 16 mol, still more preferably 1 to 10 mol, based on 1 mol of the compound represented by the formula (pt 1).

The amount of the compound represented by the formula (pt 3) used in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) and the compound represented by the formula (pt 3) is usually 0.1 to 30 mol, preferably 1 to 20 mol, more preferably 1 to 16 mol, still more preferably 1 to 10 mol, based on 1 mol of the compound represented by the formula (pt 1).

The reaction temperature is usually-100 to 300 ℃, preferably 0 to 280 ℃, more preferably 50 to 250 ℃, still more preferably 100 to 230 ℃, particularly preferably 150 to 200 ℃.

The reaction time is usually 0.5 to 500 hours.

The reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) and the compound represented by the formula (pt 3) is usually carried out in the presence of a solvent.

The solvent may be water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; an amine solvent; ether solvents such as diethyl ether, tetrahydrofuran, and diphenyl ether; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and methyl benzoate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, and tetralin; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; nitrohydrocarbon solvents such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide and the like,

diphenyl ether, methyl benzoate, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, tetrahydronaphthalene, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, 2-chloronaphthalene, nitrobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide,

More preferably, diphenyl ether, methyl benzoate, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, tetrahydronaphthalene, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, 2-chloronaphthalene, nitrobenzene, N-methylpyrrolidone,

methyl benzoate may be further preferred.

The amount of the solvent to be used is usually 1 to 1000 parts by mass based on 1 part by mass of the compound represented by the formula (pt 1) in the reaction between the compound represented by the formula (pt 1) and the compound represented by the formula (pt 2) and the compound represented by the formula (pt 3).

In the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) and the compound represented by the formula (pt 3), preferably 1 or more kinds selected from the group consisting of an acid and a metal salt coexist.

Examples of the acid include inorganic acids such as hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, fluorosulfonic acid, and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; carboxylic acids such as acetic acid, trifluoroacetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, benzoic acid, and tartaric acid; for example, hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and carboxylic acid may be preferable, carboxylic acid may be more preferable, and benzoic acid may be further preferable.

The amount of the acid used in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) and the compound represented by the formula (pt 3) is usually 1 to 90 moles, preferably 1 to 70 moles, more preferably 1 to 50 moles, still more preferably 1 to 30 moles, relative to 1 mole of the compound represented by the formula (pt 1).

Examples of the metal salt include zinc chloride and aluminum chloride.

The amount of the metal salt used in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) and the compound represented by the formula (pt 3) is usually 0.01 to 30 moles, preferably 0.01 to 20 moles, more preferably 0.01 to 10 moles, still more preferably 0.01 to 3 moles, relative to 1 mole of the compound represented by the formula (pt 1).

The method for extracting the compound (I) from the reaction mixture is not particularly limited, and extraction can be performed by various known methods. For example, after the completion of the reaction, the compound (I) in the reaction mixture may be dissolved in a solvent such as methanol, in which the compound (I) other than the compound (I) is dissolved in a solvent, and the reaction mixture may be thoroughly mixed and then filtered to extract the compound (I). The compound (I) can be extracted by washing the obtained residue with an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide, or a mixed solvent thereof, an alkaline aqueous solution such as an aqueous sodium hydroxide solution, or an acidic aqueous solution such as hydrochloric acid, and then washing with a low boiling point alcohol such as water, methanol, or a mixed solvent thereof. Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, the solvent of the reaction mixture may be distilled off after the completion of the reaction, and the resulting residue may be purified by column chromatography, recrystallization, or the like, or the reaction mixture may be purified by column chromatography, recrystallization, or the like after the completion of the reaction. After the completion of the reaction, the compound (I) in the reaction mixture may be dissolved in a solvent such as methanol, in which the compound (I) other than the compound (I) is dissolved in a solvent, and the reaction mixture may be thoroughly mixed and then filtered to extract the compound (I). Purification can be further performed by column chromatography and/or recrystallization, etc.

The compound represented by the formula (I) can be produced by reacting the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) (hereinafter, sometimes referred to as compound (I '))), then hydrolyzing the compound represented by the formula (I') in the presence of a base to produce the compound represented by the formula (IM 1) (hereinafter, sometimes referred to as compound (IM 1)), and further, by reacting the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3).

In the formula (pt 1), the formula (pt 2), the formula (pt 3), the formula (I') and the formula (IM 1), R ¹ ～R ⁵ 、Q ¹ 、Q ² The same meaning as described above is indicated.

The amount of the compound represented by the formula (pt 2) used in the reaction of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 2) is usually 0.1 to 60 mol, preferably 1 to 40 mol, more preferably 1 to 32 mol, and even more preferably 2 to 20 mol, based on 1 mol of the compound represented by the formula (pt 1).

The amount of the compound represented by the formula (pt 3) used in the reaction of the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3) is usually 0.1 to 30 moles, preferably 1 to 20 moles, more preferably 1 to 16 moles, still more preferably 1 to 10 moles, based on 1 mole of the compound represented by the formula (IM 1).

The reaction temperature in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) or the reaction temperature in the reaction of the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3) is usually-100 to 300 ℃, preferably 0 to 280 ℃, more preferably 50 to 250 ℃, still more preferably 100 to 230 ℃, particularly preferably 150 to 200 ℃.

The reaction time for the reaction of the compound represented by formula (pt 1) with the compound represented by formula (pt 2) or the reaction time for the reaction of the compound represented by formula (IM 1) with the compound represented by formula (pt 3) is usually 0.5 to 500 hours.

The reaction of the compound represented by formula (pt 1) with the compound represented by formula (pt 2) or the reaction of the compound represented by formula (IM 1) with the compound represented by formula (pt 3) is usually carried out in the presence of a solvent.

As a solvent in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) or the reaction of the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3), water can be mentioned; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; an amine solvent; ether solvents such as diethyl ether, tetrahydrofuran, and diphenyl ether; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and methyl benzoate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, and tetralin; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; nitrohydrocarbon solvents such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and the like,

methyl benzoate may be further preferred.

The amount of the solvent used in the reaction of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 2) is usually 1 to 1000 parts by mass based on 1 part by mass of the compound represented by the formula (pt 1).

The amount of the solvent used in the reaction of the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3) is usually 1 to 1000 parts by mass based on 1 part by mass of the compound represented by the formula (IM 1).

In the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) or the reaction of the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3), preferably 1 or more kinds selected from the group consisting of an acid and a metal salt coexist.

Examples of the acid in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) or the reaction of the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3) include inorganic acids such as hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, fluorosulfonic acid, and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; carboxylic acids such as acetic acid, trifluoroacetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, benzoic acid, and tartaric acid are preferably hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and carboxylic acids, more preferably carboxylic acids, and even more preferably benzoic acid.

The amount of the acid used in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) is usually 1 to 90 moles, preferably 1 to 70 moles, more preferably 1 to 50 moles, still more preferably 1 to 30 moles, relative to 1 mole of the compound represented by the formula (pt 1).

The amount of the acid used in the reaction of the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3) is usually 1 to 90 moles, preferably 1 to 70 moles, more preferably 1 to 50 moles, still more preferably 1 to 30 moles, relative to 1 mole of the compound represented by the formula (IM 1).

Examples of the metal salt in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) or the reaction of the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3) include zinc chloride and aluminum chloride.

The amount of the metal salt used in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 2) is usually 0.01 to 30 moles, preferably 0.01 to 20 moles, more preferably 0.01 to 10 moles, still more preferably 0.01 to 3 moles, relative to 1 mole of the compound represented by the formula (pt 1).

The amount of the metal salt used in the reaction of the compound represented by the formula (IM 1) with the compound represented by the formula (pt 3) is usually 0.01 to 30 moles, preferably 0.01 to 20 moles, more preferably 0.01 to 10 moles, still more preferably 0.01 to 3 moles, relative to 1 mole of the compound represented by the formula (IM 1).

The method for extracting the compound represented by the formula (I') from the reaction mixture in the reaction of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 2) is not particularly limited, and extraction can be performed by a variety of known methods. For example, after the completion of the reaction, the compound (I ') in the reaction mixture may be not easily dissolved, and a solvent such as methanol in which the compound other than the compound (I ') is easily dissolved may be sufficiently mixed with the reaction mixture, followed by filtration to extract (I '). The compound (I') can be obtained by washing the obtained residue with an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide or a mixed solvent thereof, an alkaline aqueous solution such as an aqueous sodium hydroxide solution, or an acidic aqueous solution such as hydrochloric acid, and then washing the residue with a low boiling point alcohol such as water or methanol or a mixed solvent thereof. Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, the solvent of the reaction mixture may be distilled off after the completion of the reaction, and the resulting residue may be purified by column chromatography, recrystallization, or the like, or the reaction mixture may be purified by column chromatography, recrystallization, or the like after the completion of the reaction. After the completion of the reaction, the compound (I ') may be extracted by sufficiently mixing a solvent such as methanol, in which the compound (I ') in the reaction mixture is not easily dissolved and the compound other than the compound (I ') is easily dissolved, with the reaction mixture, and then filtering the mixture. Purification can be further performed by column chromatography and/or recrystallization, etc.

The method for extracting the compound represented by the formula (I) from the reaction mixture in the reaction of the compound represented by the formula (IM 1) and the compound represented by the formula (pt 3) is not particularly limited, and extraction can be performed by a variety of known methods. For example, after the completion of the reaction, the compound (I) in the reaction mixture may be dissolved in a solvent such as methanol, in which the compound (I) other than the compound (I) is dissolved in a solvent, and the reaction mixture may be thoroughly mixed and then filtered to extract the compound (I). The compound (I) can be extracted by washing the obtained residue with an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide, or a mixed solvent thereof, an alkaline aqueous solution such as an aqueous sodium hydroxide solution, or an acidic aqueous solution such as hydrochloric acid, and then washing with a low boiling point alcohol such as water, methanol, or a mixed solvent thereof. Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, the solvent of the reaction mixture may be distilled off after the completion of the reaction, and the resulting residue may be purified by column chromatography, recrystallization, or the like, or the reaction mixture may be purified by column chromatography, recrystallization, or the like after the completion of the reaction. After the completion of the reaction, the compound (I) in the reaction mixture may be dissolved in a solvent such as methanol, in which the compound (I) other than the compound (I) is dissolved in a solvent, and the reaction mixture may be thoroughly mixed and then filtered to extract the compound (I). Purification can be further performed by column chromatography and/or recrystallization, etc.

Examples of the base in the hydrolysis reaction of the compound represented by the following formula (I') include triethylamine, 4- (N, N-dimethylamino) pyridine, piperidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, organic bases such as 1, 5-diazabicyclo [4.3.0] non-5-ene, metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, organic metal compounds such as methyl lithium, butyl lithium, tert-butyl lithium and phenyl lithium, inorganic bases such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide and potassium hydroxide, preferably inorganic bases such as sodium hydroxide, sodium hydroxide and potassium hydroxide, more preferably sodium hydroxide and potassium hydroxide, particularly preferably potassium hydroxide.

The amount of the base used in the hydrolysis reaction of the compound represented by the formula (I ') is usually 0.1 to 100 moles, preferably 1 to 70 moles, more preferably 2 to 40 moles, based on 1 mole of the compound represented by the formula (I') in the presence of the base.

The amount of water used in the hydrolysis reaction of the compound represented by the formula (I ') is usually 1 to 1000 parts by mass, preferably 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, still more preferably 1 to 50 parts by mass, based on 1 part by mass of the compound represented by the formula (I') in the presence of a base.

The reaction temperature in the hydrolysis reaction of the compound represented by the formula (I') is usually 0 to 100 ℃, preferably 5 to 100 ℃, more preferably 20 to 100 ℃, still more preferably 40 to 100 ℃, particularly preferably 60 to 100 ℃, in the presence of a base.

The reaction time for the hydrolysis reaction of the compound represented by the formula (I') is usually 0.5 to 120 hours, preferably 1 to 72 hours, more preferably 1 to 24 hours in the presence of a base.

The method for extracting the compound represented by the formula (IM 1) from the reaction mixture in the hydrolysis reaction of the compound represented by the formula (I') in the presence of a base is not particularly limited, and extraction can be carried out by various known methods. For example, after the completion of the reaction, an acidic aqueous solution such as hydrochloric acid is added to the reaction mixture to neutralize the reaction mixture, and then the reaction mixture is filtered to extract the compound (IM 1). The compound (IM 1) can be obtained by washing the obtained residue with an alkaline aqueous solution such as an aqueous sodium hydroxide solution and/or an acidic aqueous solution such as hydrochloric acid, with an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide, a ketone solvent such as acetone, an alcohol solvent such as methanol, a nitrile solvent such as acetonitrile, water or a mixed solvent thereof. Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, the solvent of the reaction mixture may be distilled off after the completion of the reaction, and the resulting residue may be purified by column chromatography, recrystallization, or the like, or the reaction mixture may be purified by column chromatography, recrystallization, or the like after the completion of the reaction.

The compound represented by the formula (I) can be produced by reacting the compound represented by the formula (pt 1) with the compound represented by the formula (pt 3) to produce the compound represented by the formula (IM 2) (hereinafter, sometimes referred to as compound (IM 2)), and then reacting the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2).

Formula (pt 1), formula (pt 2), formula (pt 3), formula (IM 2), R ¹ ～R ⁵ 、Q ¹ 、Q ² The same meaning as described above is indicated.

The amount of the compound represented by the formula (pt 3) used in the reaction of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 3) is usually 0.1 to 10 mol, preferably 0.1 to 5 mol, more preferably 0.5 to 2 mol, and even more preferably 0.8 to 1.5 mol, based on 1 mol of the compound represented by the formula (pt 1).

The reaction temperature in the reaction of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 3) is usually-100 to 300 ℃, preferably 0 to 280 ℃, more preferably 50 to 250 ℃, still more preferably 100 to 230 ℃, and particularly preferably 120 to 200 ℃.

The reaction time in the reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 3) is usually 0.5 to 500 hours.

The reaction of the compound represented by the formula (pt 1) with the compound represented by the formula (pt 3) is usually carried out in the presence of a solvent.

The solvent used in the reaction of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 3) is water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; an amine solvent; ether solvents such as diethyl ether, tetrahydrofuran, and diphenyl ether; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and methyl benzoate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, and tetralin; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; nitrohydrocarbon solvents such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide and the like,

phenol, diphenyl ether, methyl benzoate, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, tetralin, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, 2-chloronaphthalene, nitrobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide,

More preferably, phenol, diphenyl ether, methyl benzoate, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, tetralin, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, 2-chloronaphthalene, nitrobenzene, N-methylpyrrolidone,

phenol and methyl benzoate may be further preferable,

phenol is particularly preferred.

The amount of the solvent used in the reaction of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 3) is usually 1 to 1000 parts by mass, preferably 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 1 to 50 parts by mass, based on 1 part by mass of the compound represented by the formula (pt 1).

The method for extracting the compound (IM 2) from the reaction mixture in the reaction of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 3) is not particularly limited, and extraction can be performed by various known methods. For example, after the completion of the reaction, a solvent such as methanol in which the compound (IM 2) in the reaction mixture is not easily dissolved and the compound other than the compound (IM 2) is easily dissolved may be sufficiently mixed with the reaction mixture, and then the mixture may be filtered to extract (IM 2). The compound (IM 2) can be obtained by washing the obtained residue with an alkaline aqueous solution such as an aqueous sodium hydroxide solution and/or an acidic aqueous solution such as hydrochloric acid, with an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide, a ketone solvent such as acetone, an alcohol solvent such as methanol, a nitrile solvent such as acetonitrile, water or a mixed solvent thereof. Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, the solvent of the reaction mixture may be distilled off after the completion of the reaction, and the resulting residue may be purified by column chromatography, recrystallization, or the like, or the reaction mixture may be purified by column chromatography, recrystallization, or the like after the completion of the reaction. After the completion of the reaction, the reaction mixture may be added to a solvent such as methanol in which the compound (IM 2) in the reaction mixture is not easily dissolved and the compounds other than the compound (IM 2) are easily dissolved, and the mixture may be thoroughly mixed and then filtered to extract (IM 2). Purification can be further performed by column chromatography and/or recrystallization, etc.

The amount of the compound represented by the formula (pt 2) used in the reaction of the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2) is usually 0.1 to 30 moles, preferably 1 to 20 moles, more preferably 1 to 16 moles, still more preferably 1 to 10 moles, based on 1 mole of the compound represented by the formula (IM 2).

The reaction temperature in the reaction of the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2) is usually-100 to 300 ℃, preferably 0 to 280 ℃, more preferably 50 to 250 ℃, still more preferably 100 to 230 ℃, and particularly preferably 150 to 200 ℃.

The reaction time for the reaction of the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2) is usually 0.5 to 500 hours.

The reaction of the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2) is usually carried out in the presence of a solvent.

The solvent used in the reaction of the compound represented by the formula (IM 2) and the compound represented by the formula (pt 2) is water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; an amine solvent; ether solvents such as diethyl ether, tetrahydrofuran, and diphenyl ether; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and methyl benzoate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, and tetralin; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; nitrohydrocarbon solvents such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide and the like,

methyl benzoate may be further preferred.

The amount of the solvent used in the reaction of the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2) is usually 1 to 1000 parts by mass based on 1 part by mass of the compound represented by the formula (IM 2).

In the reaction of the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2), 1 or more kinds selected from the group consisting of an acid and a metal salt are preferably coexistent.

Examples of the acid in the reaction of the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2) include inorganic acids such as hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, fluorosulfonic acid, and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; carboxylic acids such as acetic acid, trifluoroacetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, benzoic acid, and tartaric acid are preferably hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and carboxylic acids, more preferably carboxylic acids, and even more preferably benzoic acid.

The amount of the acid used in the reaction of the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2) is usually 1 to 90 moles, preferably 1 to 70 moles, more preferably 1 to 50 moles, still more preferably 1 to 30 moles, relative to 1 mole of the compound represented by the formula (IM 2).

Examples of the metal salt in the reaction of the compound represented by the formula (IM 2) and the compound represented by the formula (pt 2) include zinc chloride and aluminum chloride.

The amount of the metal salt used in the reaction of the compound represented by the formula (IM 2) with the compound represented by the formula (pt 2) is usually 0.01 to 30 mol, preferably 0.01 to 20 mol, more preferably 0.01 to 10 mol, still more preferably 0.01 to 3 mol, relative to 1 mol of the compound represented by the formula (IM 2).

The method for extracting the compound represented by the formula (I) from the reaction mixture in the reaction of the compound represented by the formula (IM 2) and the compound represented by the formula (pt 2) is not particularly limited, and extraction can be performed by a variety of known methods. For example, after the completion of the reaction, the compound (I) in the reaction mixture may be dissolved in a solvent such as methanol, in which the compound (I) other than the compound (I) is dissolved in a solvent, and the reaction mixture may be thoroughly mixed and then filtered to extract the compound (I). The compound (I) can be extracted by washing the obtained residue with an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide, or a mixed solvent thereof, an alkaline aqueous solution such as an aqueous sodium hydroxide solution, or an acidic aqueous solution such as hydrochloric acid, and then washing with a low boiling point alcohol such as water, methanol, or a mixed solvent thereof. Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, the solvent of the reaction mixture may be distilled off after the completion of the reaction, and the resulting residue may be purified by column chromatography, recrystallization, or the like, or the reaction mixture may be purified by column chromatography, recrystallization, or the like after the completion of the reaction. After the completion of the reaction, the compound (I) in the reaction mixture may be dissolved in a solvent such as methanol, in which the compound (I) other than the compound (I) is dissolved in a solvent, and the reaction mixture may be thoroughly mixed and then filtered to extract the compound (I). Purification can be further performed by column chromatography and/or recrystallization, etc.

The reaction time for the reaction of the compound represented by formula (pt 1) with the compound represented by formula (pt 3) is usually 0.5 to 500 hours.

phenol and methyl benzoate may be further preferable,

phenol is particularly preferred.

The method for extracting the compound (IM 2) from the reaction mixture in the reaction of the compound represented by the formula (pt 1) and the compound represented by the formula (pt 3) is not particularly limited, and extraction can be performed by various known methods. For example, after the completion of the reaction, a solvent such as methanol in which the compound (IM 2) in the reaction mixture is not easily dissolved and the compound other than the compound (IM 2) is easily dissolved may be sufficiently mixed with the reaction mixture, and then the mixture may be filtered to extract (IM 2). The compound (IM 2) can be obtained by washing the obtained residue with an alkaline aqueous solution such as an aqueous sodium hydroxide solution and/or an acidic aqueous solution such as hydrochloric acid, with an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide, a ketone solvent such as acetone, an alcohol solvent such as methanol, a nitrile solvent such as acetonitrile, water or a mixed solvent thereof. Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, the solvent of the reaction mixture may be distilled off after the completion of the reaction, and the resulting residue may be purified by column chromatography, recrystallization, or the like, or the reaction mixture may be purified by column chromatography, recrystallization, or the like after the completion of the reaction. After the completion of the reaction, a solvent such as methanol, in which the compound (IM 2) in the reaction mixture is not easily dissolved and the compound other than the compound (IM 2) is easily dissolved, may be sufficiently mixed with the reaction mixture, and then the mixture may be filtered to extract (IM 2). Purification can be further performed by column chromatography and/or recrystallization, etc.

methyl benzoate may be further preferred.

The method for extracting the compound represented by the formula (I) from the reaction mixture in the reaction of the compound represented by the formula (IM 2) and the compound represented by the formula (pt 2) is not particularly limited, and extraction can be performed by a variety of known methods. For example, after the completion of the reaction, the compound (I) in the reaction mixture may be dissolved in a solvent such as methanol, in which the compound (I) other than the compound (I) is dissolved in a solvent, and the reaction mixture may be thoroughly mixed and then filtered to extract the compound (I). The compound (I) is obtained by washing the obtained residue with an alkaline aqueous solution such as an aqueous sodium hydroxide solution and/or an acidic aqueous solution such as hydrochloric acid, and then washing the residue with a low-boiling alcohol such as water or methanol, or a mixed solvent thereof. Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, the solvent of the reaction mixture may be distilled off after the completion of the reaction, and the resulting residue may be purified by column chromatography, recrystallization, or the like, or the reaction mixture may be purified by column chromatography, recrystallization, or the like after the completion of the reaction. After the completion of the reaction, the compound (I) in the reaction mixture may be dissolved in a solvent such as methanol, in which the compound (I) other than the compound (I) is dissolved in a solvent, and the reaction mixture may be thoroughly mixed and then filtered to extract the compound (I). Purification can be further performed by column chromatography and/or recrystallization, etc.

The introduction of a sulfo group or-SO group into the compound (I) can be carried out by reacting the compound (I) with a sulfonating agent such as fuming sulfuric acid or chlorosulfonic acid ₃ M. In the compound (I), a sulfo group or-SO group is introduced ₃ The compound of M (hereinafter, sometimes referred to as "sulfonated compound (I)") is also a compound of the present invention.

SO in oleum ₃ The amount of (a) to be used is usually 1 to 200 moles, preferably 2 to 150 moles, more preferably 3 to 100 moles, still more preferably 5 to 80 moles, per 1 mole of the compound (I).

SO in oleum ₃ The fuming sulfuric acid is usually 1 to 90 parts by mass, preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and still more preferably 15 to 50 parts by mass, based on 100 parts by mass of fuming sulfuric acid.

The amount of chlorosulfonic acid to be used is usually 1 to 500 moles, preferably 1 to 300 moles, more preferably 1 to 200 moles, still more preferably 1 to 150 moles, based on 1 mole of the compound (I).

Introduction into Compound (I) Using chlorosulfonic acidSulfo or-SO groups ₃ At M, the reaction may be carried out in the presence of a solvent. Examples of the solvent include halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene.

The amount of the solvent to be used is usually 1 to 1000 parts by mass based on 1 part by mass of the compound (I).

The reaction temperature for sulfonation is usually-20 to 200 ℃, preferably-10 to 150 ℃, more preferably 0 to 100 ℃. The reaction time is usually 0.5 to 300 hours.

The method for extracting the sulfonated compound (I) from the reaction mixture is not particularly limited, and extraction can be performed by various known methods. For example, the sulfonated compound (I) may be extracted by dropping the reaction mixture into ice after the completion of the reaction, and filtering the resulting mixture. Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, after the completion of the reaction, the reaction mixture is added dropwise to ice, and the obtained mixture is mixed with an alcohol solvent such as methanol, acetonitrile or the like, a nitrile solvent such as acetonitrile or the like, or a hydrophilic organic solvent such as a mixed solvent thereof, in which the sulfonated compound (I) is not easily dissolved but the compounds other than the sulfonated compound (I) are easily dissolved, and filtered to extract the sulfonated compound (I). Purification can be further performed by column chromatography and/or recrystallization, etc. Alternatively, the sulfonated compound (I) can be extracted by adding dropwise the reaction mixture to ice after the completion of the reaction, neutralizing the obtained mixture with an aqueous solution of ammonia, a water-soluble amine or a mixture thereof, mixing the mixture with an alcohol solvent such as methanol, a nitrile solvent such as acetonitrile, a hydrophilic organic solvent such as a mixed solvent thereof, and the like, filtering the mixture, and distilling off the solvent of the obtained filtrate. Purification can be further performed by column chromatography and/or recrystallization, etc.

By having-SO ₃ H and/or-CO ₂ The compound (I) of H (hereinafter, sometimes referred to as "acid group-containing compound (I)") is reacted with a salt having MM to produce a compound having-SO ₃ (MM) and/or-CO ₂ Compound (I) of (MM) (hereinafter, sometimes referred to as "MM-containing compound (I)").

The amount of the salt having MM to be used is usually 0.01 to 100 mol, preferably 0.02 to 50 mol, more preferably 0.1 to 30 mol, based on 1 mol of the acid group-containing compound (I).

The reaction temperature is usually 0 to 100 ℃, preferably 0 to 80 ℃, more preferably 0 to 60 ℃, still more preferably 0 to 40 ℃.

The reaction time is usually 0.5 to 500 hours.

The reaction of the acid group-containing compound (I) with the salt having MM is usually carried out in the presence of a solvent. The solvent may be water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; an amine solvent; ether solvents such as diethyl ether, tetrahydrofuran, and diphenyl ether; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and methyl benzoate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, and tetralin; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; nitrohydrocarbon solvents such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide and the like,

Preferably water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, and 2-propanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and their mixed solvents, more preferably water.

The amount of the solvent to be used is usually 1 to 1000 parts by mass, preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, based on 1 part by mass of the acid group-containing compound (I).

The reaction of the acid group-containing compound (I) with a salt having MM may be carried out in the presence of a base.

Examples of the base include organic bases such as triethylamine, 4- (N, N-dimethylamino) pyridine, piperidine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, organic metal compounds such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and metal alkoxides such as methyllithium, butyllithium, tert-butyllithium, and phenyllithium, inorganic bases such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, and potassium hydroxide, preferably inorganic bases, more preferably lithium hydroxide, sodium hydroxide, and potassium hydroxide, and even more preferably sodium hydroxide and potassium hydroxide, and particularly preferably sodium hydroxide.

The amount of the base to be used is usually 1 to 100 moles, preferably 1 to 50 moles, more preferably 1 to 20 moles, still more preferably 1 to 10 moles, based on 1 mole of the acid group-containing compound (I).

The method for extracting the MM-containing compound (I) from the reaction mixture is not particularly limited, and extraction can be performed by various known methods. For example, the compounds having-SO can be extracted by filtering the reaction mixture after the reaction has ended ₃ (MM) and/or-CO ₂ Compound (I) of (MM). The residue obtained may be washed with an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide, a ketone solvent such as acetone, an alcohol solvent such as methanol, a nitrile solvent such as acetonitrile, water or a mixed solvent thereof, and then washed with water, a low boiling point alcohol such as methanol or a mixed solvent thereof, and then purified.

[ coloring composition ]

The coloring composition of the present invention comprises a compound (I) and a solvent (E). According to the coloring composition of the present invention, a darker color filter can be formed as compared to a coloring composition containing c.i. pigment yellow 138. The color filter formed from the coloring composition of the present invention is preferably used for a display device such as a liquid crystal display device. The coloring composition of the present invention is preferably a yellow composition, an orange composition, a red composition and a green composition.

The content of the solid component in the coloring composition is preferably not less than 0.01% by mass and not more than 100% by mass, more preferably 0.1% by mass to 99.9% by mass, still more preferably 0.1% by mass to 99% by mass, particularly preferably 1% by mass to 90% by mass, still more preferably 1% by mass to 80% by mass, particularly preferably 1% by mass to 70% by mass, particularly preferably 1% by mass to 60% by mass, and most preferably 1% by mass to 50% by mass, relative to the total amount of the coloring composition.

The "total amount of solid components" in the present specification means the total amount of components other than the solvent (E) in the coloring composition of the present invention. The total amount of the solid components and the content of each component relative to the total amount of the solid components can be measured by a known analytical means such as liquid chromatography or gas chromatography.

The content of the compound (I) in the coloring composition is 100% by mass or less, preferably 0.0001% by mass to 99.9999% by mass, more preferably 0.0001% by mass to 99% by mass, still more preferably 0.0001% by mass to 90% by mass, particularly preferably 0.0001% by mass to 80% by mass, still more preferably 0.0001% by mass to 70% by mass, particularly preferably 0.0001% by mass to 60% by mass, most preferably 0.0001% by mass to 55% by mass, and most preferably 0.1% by mass to 55% by mass, based on the total solid content.

[ solvent (E) ]

The solvent (E) is not particularly limited, and solvents commonly used in the art can be used. Examples of the solvent (E) include ester solvents (solvents containing-CO-O-and not containing-O-in the molecule) an ether solvent (a solvent containing-O-and not-CO-O-in the molecule) ether ester solvents (solvents containing-CO-O-and-O-in the molecule) ketone solvent (solvent containing-CO-in the molecule and no-CO-O-) alcohol solvents (OH-free and-O-free in the molecule) -CO-and-CO-O-, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, 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 gamma-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, and 1, 4-di-n Alkyl, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole and the like.

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

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

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

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

These solvents may be used in combination of 2 or more.

Among the above solvents, from the viewpoint of coatability and drying properties, an organic solvent having a boiling point of 120 to 180℃at 1atm is preferable. The solvent may preferably be propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide, and may more preferably be propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, and the like.

The content of the solvent (E) is preferably less than 100% by mass, more preferably 99.99% by mass or less, still more preferably 0.1% by mass to 99.9% by mass, still more preferably 1% by mass to 99.9% by mass, particularly preferably 10% by mass to 99% by mass, still more preferably 20% by mass to 99% by mass, particularly preferably 30% by mass to 99% by mass, most preferably 40% by mass to 99% by mass, and most preferably 50% by mass to 99% by mass, relative to the total amount of the coloring composition.

[ resin (B) ]

The resin (B) is preferably an alkali-soluble resin, and more preferably a polymer having a structural unit derived from at least 1 monomer (hereinafter, sometimes referred to as "monomer (a)") selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

The resin (B) is preferably a copolymer having a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (B)") and other structural units.

Examples of the other structural unit include a structural unit derived from a monomer copolymerizable with the monomer (a) (wherein the monomer is different from the monomer (a) and the monomer (b): hereinafter, sometimes referred to as "monomer (c)"), a structural unit having an ethylenically unsaturated bond, and the like.

In the present specification, "(meth) acrylic" means at least 1 kind selected from acrylic acid and methacrylic acid. The same meaning applies to the "(meth) acryl" and "(meth) acrylate" and the like.

Examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid; unsaturated dicarboxylic acids such as 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, dimethyltetrahydrophthalic acid and 1, 4-cyclohexene dicarboxylic acid; 2, 3-dicarboxylic acid methyl-5-norbornene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, and other carboxyl group-containing bicyclic unsaturated compounds; unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride; unsaturated mono- [ (meth) acryloyloxyalkyl ] esters of polycarboxylic acids having 2 or more members such as succinic acid mono- [ 2- (meth) acryloyloxyethyl ] ester and phthalic acid mono- [ 2- (meth) acryloyloxyethyl ] ester; unsaturated acrylates having hydroxyl groups and carboxyl groups in the same molecule, such as α - (hydroxymethyl) acrylic acid; etc.

Among them, acrylic acid, methacrylic acid, ortho-, meta-, para-vinylbenzoic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

The monomer (b) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an oxetane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. The monomer (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of the monomer (b) include a monomer having an oxetanyl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "monomer (b 1)"), a monomer having an oxetanyl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "monomer (b 2)"), a monomer having a tetrahydrofuranyl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "monomer (b 3)"), and the like.

Examples of the monomer (b 1) include a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, referred to as "monomer (b 1-1)") and a monomer having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, referred to as "monomer (b 1-2)").

As the monomer (b 1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Examples of the monomer (b 1-1) include glycidyl (meth) acrylate, β -methyl glycidyl (meth) acrylate, β -ethyl glycidyl (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 (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, and 2, 6-tris (glycidoxymethyl) styrene.

Examples of the monomer (b 1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, celloxide (registered trademark) 2000, (product of Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer (registered trademark) A400, (product of Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer (registered trademark) M100, (product of Daicel)), a compound represented by the formula (BI), and a compound represented by the formula (BII).

[ formula (BI) and formula (BII), R ^a And R is ^b Independently of each other, represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X is X ^a And X ^b Independently of one another, represents a single bond, R ^c －、＊－R ^c －O－、＊－R ^c -S-or O-R ^c －NH－。R ^c Represents an alkanediyl group having 1 to 6 carbon atoms. And represents a bonding site to O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and the like.

Examples of the alkyl group having a hydrogen atom substituted with a hydroxyl group include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, and 4-hydroxybutyl group.

As R ^a And R is ^b The hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group are preferable, and the hydrogen atom and methyl group are more preferable.

Examples of the alkanediyl group include methylene, ethylene, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl and hexane-1, 6-diyl.

As X ^a And X ^b The single bond, methylene, ethylene, or-CH can be preferably mentioned ₂ -O-and-CH ₂ CH ₂ O-more preferably represents a single bond or-CH ₂ CH ₂ -O- (. Times. Represents a bonding site to O).

The compound represented by the formula (BI) may be a compound represented by any one of the formulas (BI-1) to (BI-15), or the like. Among them, compounds represented by the formulas (BI-1), (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) and formulas (BI-11) to (BI-15) are preferable, and compounds represented by the formulas (BI-1), formula (BI-7), formula (BI-9) and formula (BI-15) are more preferable.

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The compound represented by the formula (BII) may be a compound represented by any one of the formulas (BII-1) to (BII-15), and among them, the compounds represented by the formulas (BII-1), (BII-3), the formulas (BII-5), the formulas (BII-7), the formulas (BII-9) and the formulas (BII-11) to (BII-15) may be preferable, and the compounds represented by the formulas (BII-1), the formulas (BII-7), the formulas (BII-9) and the formulas (BII-15) may be more preferable.

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The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used singly or in combination of 2 or more. The compound represented by the formula (BI) and the compound represented by the formula (BII) may also be used in combination. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, the content ratio of the compound represented by the formula (BI) to the compound represented by the formula (BII) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, still more preferably 20:80 to 80:20 on a molar basis.

As the monomer (b 2), monomers having an oxetanyl group and a (meth) acryloyloxy group are more preferable. Examples of the monomer (b 2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

As the monomer (b 3), a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group is more preferable. Examples of the monomer (b 3) include tetrahydrofurfuryl acrylate (for example, viscoat V#150, manufactured by Osaka organic chemical industry Co., ltd.), and tetrahydrofurfuryl methacrylate.

The monomer (b) is preferably the monomer (b 1) in order to improve reliability such as heat resistance and chemical resistance of the color filter obtained. Further, the monomer (b 1-2) is more preferable in view of excellent storage stability of the coloring composition.

Examples of the monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo (5.2.1.0) acrylate ² ^,6 ]Decane-8-yl ester, tricyclo [5.2.1.0 (meth) acrylic acid ^2,6 ]Decane-9-yl ester, tri (meth) acrylic acidCyclo [5.2.1.0 ^2,6 ]Decen-8-yl ester, tricyclo (meth) acrylate [5.2.1.0 ^2,6 ](meth) acrylic esters such as decen-9-yl ester, dicyclopentadienyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate; hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (meth) acrylic esters containing a halogen atom such as 2,3, 4, 5-octafluoropentyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; bicyclo [2.2.1 ]Hept-2-ene, 5-methyl-bicyclo [2.2.1]Hept-2-ene, 5-ethylbicyclo [2.2.1]Hept-2-ene, 5-hydroxy bicyclo [2.2.1]Hept-2-ene, 5-hydroxymethyl bicyclo [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-bis (2' -hydroxyethyl) bicyclo [2.2.1]Hept-2-ene, 5, 6-dimethoxy bicyclo [2.2.1]Hept-2-ene, 5, 6-diethoxy bicyclo [2.2.1]Hept-2-ene, 5-hydroxy-5-methyl-bicyclo [2.2.1]Hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1]Hept-2-ene, 5-hydroxymethyl-5-methyl bicyclo [2.2.1]Hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1]Hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1 ]]Hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1]Hept-2-ene, 5, 6-bis (t-butoxycarbonyl) bicyclo [2.2.1]Hept-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1]Bicyclo-unsaturated compounds such as hept-2-ene; n-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaprooate, N-succinimidyl-3-maleimidopropionate and N- (9) -acridinyl) maleimide and other dicarbonyl imide derivatives; vinyl-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, 9-vinylcarbazole, and p-methoxystyrene; vinyl-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl-containing amides such as (meth) acrylamide; esters such as vinyl acetate; dienes such as 1, 3-butadiene, isoprene and 2, 3-dimethyl-1, 3-butadiene; etc.

Among them, styrene, vinyl toluene, tricyclo [5.2.1.0 ] are preferable from the viewpoint of copolymerization reactivity and heat resistance ^2,6 ]Decane-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]Decane-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]Decen-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]Decen-9-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1]Hept-2-ene, phenyl (meth) acrylate, 2,3, 4, 5-octafluoropentyl (meth) acrylate, 9-vinylcarbazole, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

Specific examples of the resin (B) include 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer and 3, 4-epoxytricyclo (meth) acrylate [5.2.1.0 ] ^2,6 ]Decyl ester/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid ^2,6 ]Decyl ester/(meth) acrylic acid benzyl ester/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]Decyl ester/9-vinylcarbazole/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic phenyl ester/o-vinylbenzoic acid copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic phenyl ester/m-vinylbenzoic acid copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]Decyl ester/phenyl (meth) acrylateEster/para-vinyl benzoic acid copolymer, 3, 4-epoxy tricyclo [5.2.1.0 (meth) acrylic acid ^2,6 ]Decyl ester/(meth) acrylic acid phenyl ester/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid 2,3, 4, 5-octafluoropentyl ester/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/(meth) benzyl acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo (meth) acrylic acid 5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid 2-ethylhexyl (meth) acrylate copolymer, 3, 4-epoxytricyclo (meth) acrylate [5.2.1.0 ^2,6 ]Decyl ester/tricyclo (meth) acrylate [5.2.1.0 ^2,6 ]Decenyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyl oxetane/(meth) acrylic acid/styrene copolymer, benzyl (meth) acrylate/(meth) acrylic acid copolymer, styrene/(meth) acrylic acid copolymer, resins described in each of Japanese patent application laid-open No. 9-106071, japanese patent application laid-open No. 2004-29518 and Japanese patent application laid-open No. 2004-361455, and the like.

Among them, the resin (B) is preferably a copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B). The resin (B) may be combined with 2 or more kinds, in which case the resin (B) preferably contains at least 1 copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B), more preferably contains at least 1 copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B1), and still more preferably contains at least 1 copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B) Copolymers containing structural units selected from the group consisting of 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid are particularly preferred as the copolymers of the monomers (b 1-2) ^2,6 ]Decyl ester/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid ^2,6 ]Decyl ester/(meth) acrylic acid benzyl ester/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo (meth) acrylic acid 5.2.1.0 ^2,6 ]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxytricyclo (meth) acrylic acid [5.2.1.0 ^2,6 ]More than 1 kind of decyl ester/(methyl) acrylic acid 2-ethylhexyl ester copolymer.

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (B) is preferably 1000 to 100000, more preferably 1000 to 50000, further preferably 1000 to 30000, particularly preferably 3000 to 30000, and particularly preferably 5000 to 30000.

The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4.

The acid value (solid content conversion value) of the resin (B) is preferably 10 to 500mg-KOH/g, more preferably 20 to 450mg-KOH/g, still more preferably 20 to 400mg-KOH/g, still more preferably 20 to 370mg-KOH/g, still more preferably 30 to 350mg-KOH/g, particularly preferably 30 to 340mg-KOH/g, and most preferably 30 to 335mg-KOH/g. The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin (B) in the coloring composition is less than 100% by mass, preferably 0.00001% by mass to 99.99999% by mass, more preferably 1% by mass to 99% by mass, still more preferably 1% by mass to 97% by mass, particularly preferably 1% by mass to 95% by mass, still more preferably 3% by mass to 95% by mass, particularly preferably 5% by mass to 95% by mass, and most preferably 10% by mass to 95% by mass, based on the total amount of solid components.

[ preparation of solution containing Compound (I) ]

The coloring composition of the present invention may be prepared by preparing a solution containing the compound (I) in advance, which contains the compound (I) and the solvent (E), and then using the solution containing the compound (I) to prepare the coloring composition. When the compound (I) is insoluble in the solvent (E), a solution containing the compound (I) can be prepared by dispersing and mixing the compound (I) in the solvent (E). The solution containing the compound (I) may contain a part or all of the solvent (E) contained in the coloring composition.

The solution containing the compound (I) is contained in the coloring composition of the present invention.

The content of the solid content of the solution containing the compound (I) is less than 100% by mass, preferably 0.01% by mass to 99.99% by mass, more preferably 0.1% by mass to 99.9% by mass, still more preferably 0.1% by mass to 99% by mass, particularly preferably 1% by mass to 90% by mass, still more preferably 1% by mass to 80% by mass, particularly preferably 1% by mass to 70% by mass, most preferably 1% by mass to 60% by mass, and most preferably 1% by mass to 50% by mass, relative to the total amount of the solution containing the compound (I).

The content of the compound (I) in the solution containing the compound (I) is 100% by mass or less, preferably 0.0001% by mass to 99.9999% by mass, more preferably 0.0001% by mass to 99% by mass, still more preferably 1% by mass to 99% by mass, particularly preferably 3% by mass to 99% by mass, and still more preferably 5% by mass to 99% by mass, based on the total amount of solid components in the solution containing the compound (I).

The compound (I) may be subjected to a rosin treatment, a surface treatment using a derivative having an acidic group or a basic group introduced therein, a grafting treatment on the surface of the compound (I) with a polymer compound or the like, a micronization treatment by sulfuric acid micronization, salt milling or the like, a washing treatment by an organic solvent, water or the like for removing impurities, a removal treatment by an ion exchange method or the like for ionic impurities, or the like, as required.

The compound (I) may be subjected to the following treatments as needed:

crystal structure conversion, shaping of particles and/or approximate homogenization of particle size;

mixing the compound (I) with water and/or an organic solvent, stirring and/or heating while stirring to obtain a suspension, and filtering the suspension to obtain a compound (I) with a modified crystal structure;

A treatment for changing the crystal structure of the compound (I) by recrystallization;

mixing the compound (I) with water, sulfuric acid or an organic solvent, stirring and/or heating while stirring to obtain a solution or suspension, mixing the solution or suspension with a lean solvent of the compound (I) to obtain a suspension, and filtering the suspension to obtain a compound (I) with a modified crystal structure;

mixing the compound (I) and the derivative with water and/or an organic solvent, stirring and/or heating while stirring to obtain a suspension, and filtering the suspension to obtain a mixture containing the compound (I) with a modified crystal structure and/or mixing the compound (I) and the derivative;

a treatment for obtaining a mixture containing the compound (I) having a modified crystal structure by subjecting the mixture of the compound (I) and the derivative to recrystallization and/or a treatment for mixing the compound (I) with the derivative;

mixing a compound (I) with a derivative with water, sulfuric acid or an organic solvent, stirring and/or stirring while heating to obtain a solution or a suspension, mixing the solution or the suspension with a poor solvent of the compound (I) to obtain a suspension, and filtering the suspension to obtain a mixture containing the compound (I) with a modified crystal structure and/or a mixture of the compound (I) with the derivative; etc.

When a plurality of compounds (I) or derivatives are used, these treatments may be carried out singly or in combination.

The particle size of the compound (I) is preferably substantially uniform.

Examples of the organic solvent used for the crystal structure conversion include nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; an amine solvent; ether solvents such as diethyl ether, tetrahydrofuran, and diphenyl ether; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and methyl benzoate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, and tetralin; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; nitrohydrocarbon solvents such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; etc.

Examples of the lean solvent include nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol, and phenol; an amine solvent; ether solvents such as diethyl ether, tetrahydrofuran, and diphenyl ether; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and methyl benzoate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decalin, and tetralin; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; nitrohydrocarbon solvents such as nitrobenzene; etc.

Examples of the derivative include a compound represented by the formula (z) and a compound represented by the formula (z 1).

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When the solution containing the compound (I) contains a derivative, the content of the derivative is 0.01 to 100 parts by mass, preferably 0.01 to 70 parts by mass, more preferably 0.1 to 50 parts by mass, still more preferably 0.1 to 30 parts by mass, and particularly preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the compound (I).

The compound (I) may be dispersed by a dispersing treatment with a dispersant to obtain a state in which the compound (I) is uniformly dispersed in a solution containing the compound (I). When a plurality of compounds (I) are used, the dispersion treatment may be performed alone or by mixing a plurality of compounds.

The dispersant may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, examples thereof include surfactants such as polyester-based, polyamine-based and acrylic-based surfactants. These dispersants may be used alone or in combination of 2 or more. Examples of the dispersant include KP (manufactured by Xinyue chemical industry Co., ltd.), FLOWLEN (manufactured by Kyowa chemical Co., ltd.), solsperse (registered trademark) (manufactured by Zeneca Co., ltd.), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by Weisu Fine chemical Co., ltd.), DISERBYK (registered trademark) (manufactured by BYK-Chemie Co., ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Co., ltd.).

When the solution containing the compound (I) contains a dispersant, the amount of the dispersant (solid content) to be used is, for example, 0.01 to 10000 parts by mass, preferably 0.01 to 5000 parts by mass, more preferably 0.01 to 1000 parts by mass, still more preferably 0.1 to 500 parts by mass, particularly preferably 0.1 to 300 parts by mass, still more preferably 1 to 300 parts by mass, and particularly preferably 5 to 260 parts by mass, relative to 100 parts by mass of the compound (I). When the amount of the dispersant is within the above range, there is a tendency that a solution containing the compound (I) in a more uniform dispersion state is obtained.

When the coloring composition of the present invention contains the resin (B), the compound (I) -containing solution containing the compound (I) and the solvent (E) is prepared in advance, and then the compound (I) -containing solution is used to prepare the coloring composition of the present invention, the compound (I) -containing solution may contain a part or all, preferably a part of the resin (B) contained in the coloring composition in advance. By previously containing the resin (B), the dispersion stability of the solution containing the compound (I) can be further improved.

When the solution containing the compound (I) contains the resin (B), the content of the resin (B) is, for example, 0.01 to 10000 parts by mass, preferably 0.01 to 5000 parts by mass, more preferably 0.01 to 1000 parts by mass, still more preferably 0.1 to 500 parts by mass, and particularly preferably 0.1 to 300 parts by mass, relative to 100 parts by mass of the compound (I).

[ polymerizable Compound (C) ]

The polymerizable compound (C) is a compound polymerizable by a living radical and/or an acid generated by the polymerization initiator (D), and is, for example, a compound having a polymerizable ethylenically unsaturated bond, etc., preferably a (meth) acrylate compound.

Examples of the polymerizable compound having 1 ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, and the above-mentioned monomer (a), monomer (b), and monomer (c).

Examples of the polymerizable compound having 2 ethylenically unsaturated bonds include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane 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, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

The weight average molecular weight of the polymerizable compound (C) is preferably 50 to 4000, more preferably 50 to 3500, still more preferably 50 to 3000, particularly preferably 150 to 2900, and particularly preferably 250 to 1500.

The content of the polymerizable compound (C) in the coloring composition is less than 100% by mass, preferably 0.00001% by mass to 99.99999% by mass, more preferably 1% by mass to 99% by mass, still more preferably 1% by mass to 97% by mass, particularly preferably 1% by mass to 95% by mass, still more preferably 1% by mass to 90% by mass, particularly preferably 2% by mass to 80% by mass, and most preferably 3% by mass to 70% by mass, based on the total amount of solid components.

[ polymerization initiator (D) ]

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

As the O-acyl oxime compound, for example, examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-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-dioxacyclopentylmethoxy) 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-cyclopentylpropane-1-one-2-imine, and the like. As the O-acyl oxime compound, commercially available products such as Irgacure OXE01, OXE02 (both of them are manufactured by BASF) and N-1919 (manufactured by ADEKA) can be used. Among them, as the O-acyloxime compound, at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

Examples of the alkylbenzene ketone compound include 2-methyl-2-morpholino-1- (4-methylsulfanyl phenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] butan-1-one. As the alkylbenzene ketone compound, commercially available products such as Irgacure 369, 907 and 379 (all of which are manufactured by BASF) can be used.

Examples of the alkylbenzene ketone compound include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, an oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone and benzildimethyl ketal.

Examples of the bisimidazole compound include 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole and 2,2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenylbisimidazole (for example, reference is made to Japanese patent application laid-open No. 6-75372, japanese patent application laid-open No. 6-75373, etc.), 2' -bis (2-chlorophenyl) -4,4', 5' -tetra (alkoxyphenyl) bisimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese patent publication No. 48-38403, japanese patent application laid-open No. 62-174204, etc.), biimidazole compounds in which phenyl groups at the 4,4', 5' -positions are substituted with carboalkoxy groups (for example, refer to Japanese patent application laid-open No. 7-10913, etc.), and the like.

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-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and the like. Commercial products such as Irgacure 819 (registered trademark) manufactured by BASF can be used.

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 compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, a titanocene compound, and the like. These are preferably used in combination with a polymerization initiator aid (hereinafter, may be referred to as a polymerization initiator aid (D1)), particularly an amine, which will be described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least 1 selected from the group consisting of an alkylbenzene compound, a triazine compound, an acylphosphine oxide compound, an oxime compound and a biimidazole compound, more preferably a polymerization initiator containing an oxime compound, and still more preferably a polymerization initiator containing an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.001 to 60% by mass, more preferably 0.01 to 50% by mass, based on the total amount of the resin (B) and the polymerizable compound (C).

[ polymerization initiator auxiliary (D1) ]

The coloring composition of the present invention may contain a polymerization initiator aid (D1). The polymerization initiator aid (D1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound (C) initiated by the polymerization initiator (D). When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiator aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone (known as Michaelis ' ketone), 4' -bis (diethylamino) benzophenone, and 4,4' -bis (ethylmethylamino) benzophenone, and 4,4' -bis (diethylamino) benzophenone may be preferably used. As the amine compound, commercially available products such as EAB-F (manufactured by Baogu chemical Co., ltd.) can 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-dibutoxyanthracene, and 2-ethyl-9, 10-dibutoxyanthracene.

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

Examples of the carboxylic acid compound include phenylthioalkyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylthioalkyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylthioalkyl acetic acid, dimethoxyphenylthioalkyl acetic acid, chlorophenyl thioalkyl acetic acid, dichlorophenylthioalkyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

When these polymerization initiator additives (D1) are used, the content thereof is preferably 0.00001 to 60 mass%, more preferably 0.0001 to 50 mass%, based on the total amount of the resin (B) and the polymerizable compound (C).

[ colorant (A1) ]

The coloring composition of the present invention may contain a colorant other than the compound (I) (hereinafter, may be referred to as a colorant (A1)). The colorant (A1) may contain 1 or 2 or more colorants. The colorant (A1) preferably contains 1 or more selected from yellow colorant, orange colorant, red colorant and green colorant, and more preferably contains 1 or more selected from yellow colorant and green colorant.

The colorant (A1) may be a dye or a pigment. As the dye, a known dye can be used, and examples thereof include a known dye described in color index (The Society of Dyers and Colourists publication) and dyeing guide (color dyeing company). Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitrodyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, isoindoline dyes, and the like can be exemplified. These dyes may be used singly or in combination of 2 or more.

Specifically, the following color index (c.i.) numbered dyes are exemplified.

C.i. solvent yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;

c.i. solvent red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

c.i. solvents orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

c.i. solvent blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

c.i. solvents green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.,

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, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 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, 401, 412, 417, 418, 422, 426;

c.i. acid oranges 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, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

c.i. acid blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 280, 290, 296, 278, 315, 340.

C.i. acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109, etc.,

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 oranges 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, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274.

C.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82, etc.,

c.i. disperse yellow 51, 54, 76;

c.i. disperse violet 26, 27;

c.i. disperse blue 1, 14, 56, 60, etc.,

c.i. basic red 1, 10;

c.i. basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;

c.i. basic violet 2;

c.i. basic red 9;

c.i. basic green 1; an equivalent c.i. basic dye,

c.i. active yellow 2, 76, 116;

c.i. active orange 16;

c.i. reactive red 36; the same amount of c.i. reactive dye,

c.i. medium yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. media red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

c.i. medium oranges 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

c.i. vehicle violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

C.i. medium blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

c.i. mediator dyes of c.i. mediator green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc.,

C.I. vat dyes such as C.I. vat green 1 and the like

Further, as products of BASF, lumogen (registered trademark) may be mentioned Lumogen (registered trademark) F Yellow 083 (manufactured by BASF), lumogen (registered trademark) F Yellow 170 (manufactured by BASF), lumogen (registered trademark) F Orange 240 (manufactured by BASF), and Lumogen (registered trademark) F Red 305 (manufactured by BASF).

Further, the compound represented by the formula (z) and the compound represented by the formula (z 1) may be mentioned.

/>

As the pigment, a known pigment can be used, and examples thereof include pigments classified as pigments (pigment) in the color index (The Society of Dyers and Colourists publication). They may be used singly or in combination of 2 or more.

Specifically, examples thereof include yellow pigments such as c.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, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231;

Orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273;

c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, etc. blue pigments;

violet pigments such as c.i. pigment violet 1, 19, 23, 29, 32, 36, 38;

green pigments such as c.i. pigment green 7, 36, 58, 59, 62, 63;

brown pigments such as pigment brown 23, 25;

black pigments such as c.i. pigment black 1, 7, 31, 32.

As the colorant (A1), a yellow dye and a yellow pigment (hereinafter, they are sometimes referred to as "yellow colorant"), an orange dye and an orange pigment (hereinafter, they are sometimes referred to as "orange colorant"), a red dye and a red pigment (hereinafter, they are sometimes referred to as "red colorant"), a green dye and a green pigment (hereinafter, they are sometimes referred to as "green colorant"), more preferably a yellow colorant and a green colorant, further preferably a yellow pigment and a green pigment, and particularly preferably a green pigment, are preferable.

The yellow dye may be a dye whose hue is classified into yellow, and the yellow pigment may be a pigment whose hue is classified into yellow. The yellow colorant is preferably a yellow dye or a yellow pigment, more preferably a yellow pigment, further preferably a quinophthalone pigment, a metal-containing pigment or an isoindoline pigment, particularly preferably c.i. pigment yellow 129, 138, 139, 150, 185, 231, further preferably c.i. pigment yellow 138, 139, 150, 185, 231.

Examples of the orange dye include dyes whose hues are classified into orange, and examples of the orange pigment include pigments whose hues are classified into orange. As the orange colorant, orange dye and orange pigment are preferable, orange pigment is more preferable, and c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 is further preferable.

The red dye may be a dye whose hue is classified into red, and the red pigment may be a pigment whose hue is classified into red. As the red colorant, a red dye and a red pigment are preferable, an azo dye, an anthraquinone dye, a triphenylmethane dye, a xanthene dye, a perylene dye, an azo pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, a triphenylmethane dye, a xanthene pigment, and a perylene pigment are more preferable, and c.i. acid red 52, c.i. pigment red 144, 177, 179, 242, 254, and 269 are more preferable.

Further, as the yellow colorant, orange colorant, or red colorant, a xanthene compound described in japanese patent application laid-open No. 2013-235257, or the like can be used.

The green dye may be a dye whose hue is classified into green, and the green pigment may be a pigment whose hue is classified into green. As the green colorant, green dyes and green pigments are preferable, green pigments are more preferable, phthalocyanine pigments are further preferable, halogenated copper phthalocyanine pigments, halogenated zinc phthalocyanine pigments and halogenated aluminum zinc phthalocyanine pigments are particularly preferable, and c.i. pigments green 7, 36, 58, 59, 62 and 63 are further preferable.

[ preparation of solution containing colorant (A1) ]

When the coloring composition of the present invention contains the colorant (A1), the coloring composition may be prepared by preparing a solution containing the colorant (A1) and the solvent (E) in advance, and then using the solution containing the colorant (A1). When the colorant (A1) is insoluble in the solvent (E), a solution containing the colorant (A1) can be prepared by dispersing and mixing the colorant (A1) in the solvent (E). The solution containing the colorant (A1) may contain a part or all of the solvent (E) contained in the coloring composition.

The content of the solid component in the solution containing the colorant (A1) is less than 100% by mass, preferably 0.01% by mass to 99.99% by mass, more preferably 0.1% by mass to 99.9% by mass, still more preferably 0.1% by mass to 99% by mass, particularly preferably 1% by mass to 90% by mass, still more preferably 1% by mass to 80% by mass, particularly preferably 1% by mass to 70% by mass, most preferably 1% by mass to 60% by mass, and most preferably 1% by mass to 50% by mass, relative to the total amount of the solution containing the colorant (A1).

The content of the colorant (A1) in the solution containing the colorant (A1) is 100% by mass or less, preferably 0.0001% by mass to 99.9999% by mass, more preferably 0.0001% by mass to 99% by mass, still more preferably 1% by mass to 99% by mass, particularly preferably 3% by mass to 99% by mass, and still more preferably 5% by mass to 99% by mass, based on the total amount of solid components in the solution containing the colorant (A1).

The colorant (A1) may be subjected to a rosin treatment, a surface treatment using a derivative having an acidic group or a basic group introduced therein, a grafting treatment to the surface of the colorant (A1) by a polymer compound or the like, a sulfuric acid micronization method, a micronization treatment by a salt milling method or the like, a washing treatment by an organic solvent or water or the like for removing impurities, a removal treatment by an ion exchange method or the like of ionic impurities, a crystal structure conversion similar to that of the compound (I), shaping of particles, a rough homogenization treatment of particle diameters, or the like, as required. The particle diameter of the colorant (A1) is preferably substantially uniform.

The colorant (A1) can be dispersed by a dispersing treatment with a dispersant to achieve a state in which the colorant (A1) is uniformly dispersed in a solution containing the colorant (A1). The colorant (A1) may be dispersed alone or in combination of two or more.

The dispersant may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, examples thereof include surfactants such as polyester-based, polyamine-based and acrylic-based surfactants. These dispersants may be used singly or in combination of two or more. Examples of the dispersant include KP (manufactured by Xinyue chemical industry Co., ltd.), FLOWLEN (manufactured by Kyowa chemical Co., ltd.), solsperse (registered trademark) (manufactured by Zeneca Co., ltd.), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by Weisu Fine chemical Co., ltd.), DISERBYK (registered trademark) (manufactured by BYK-Chemie Co., ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Co., ltd.).

When the solution containing the colorant (A1) contains a dispersant, the amount of the dispersant (solid content) to be used is, for example, 0.01 to 10000 parts by mass, preferably 0.01 to 5000 parts by mass, more preferably 0.01 to 1000 parts by mass, still more preferably 0.1 to 500 parts by mass, particularly preferably 0.1 to 300 parts by mass, still more preferably 1 to 300 parts by mass, and particularly preferably 5 to 260 parts by mass, based on 100 parts by mass of the colorant (A1). When the amount of the dispersant is within the above range, a more uniform dispersion state of the solution containing the colorant (A1) tends to be obtained.

The coloring composition of the present invention contains the resin (B), and when the coloring composition of the present invention is prepared by using the solution containing the colorant (A1) after preparing the solution containing the colorant (A1) and the solvent (E) in advance, the solution containing the colorant (A1) may contain a part or all, preferably a part of the resin (B) contained in the coloring composition in advance. By previously containing the resin (B), the dispersion stability of the solution containing the colorant (A1) can be further improved.

When the resin (B) is contained in the solution containing the colorant (A1), the content of the resin (B) is, for example, 0.01 to 10000 parts by mass, preferably 0.01 to 5000 parts by mass, more preferably 0.01 to 1000 parts by mass, still more preferably 0.1 to 500 parts by mass, and particularly preferably 0.1 to 300 parts by mass, relative to 100 parts by mass of the colorant (A1).

When the coloring composition of the present invention contains the colorant (A1), the content of the colorant (a) in the total of the compound (I) and the colorant (A1) in the coloring composition is less than 100% by mass, preferably from 0.0001% by mass to 99.9999% by mass, more preferably from 0.0001% by mass to 99% by mass, still more preferably from 0.0001% by mass to 90% by mass, particularly preferably from 0.0001% by mass to 80% by mass, still more preferably from 0.0001% by mass to 70% by mass, particularly preferably from 0.0001% by mass to 60% by mass, most preferably from 0.0001% by mass to 55% by mass, and most preferably from 0.1% by mass to 55% by mass, relative to the total amount of solid components.

When the coloring composition of the present invention contains the colorant (A1), the content of the compound (I) is usually 0.0001 mass% or more, preferably 0.0003 mass% or more, more preferably 0.0005 mass% or more, further preferably 0.001 mass% or more, and the upper limit is less than 100 mass%, preferably 99.9999 mass% or less, more preferably 99 mass% or less, further preferably 98 mass% or less, and particularly preferably 97 mass% or less, based on the total amount of the colorant (a).

[ leveling agent (F) ]

Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. They may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC11PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH29PA, toray Silicone SH PA, toray Silicone SH8400 (trade name: dow Corning Toray, manufactured by Mitsui chemical Co., ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Xinyue chemical Co., ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan contract Co., ltd.) and the like are exemplified.

The fluorine-based surfactant may be a surfactant having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD FC430, FLUORAD FC431 (manufactured by Sumitomo 3M (Inc.), MEGAFACE F142D, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F183, MEGAFACE F554, MEGAFACE R30, MEGAFACE RS-718-K (manufactured by DIC (Inc.), F-top EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi material electronics), surflon S381, surflon S382, surflon SC101, surflon SC105 (manufactured by Asahi) and E5844 (manufactured by Surflon chemical research).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, MEGAFACE (registered trademark) R08, MEGAFACE BL20, MEGAFACE F475, MEGAFACE F477, MEGAFACE F443 (DIC Co., ltd.) and the like are exemplified.

When the leveling agent (F) is contained, the content thereof is usually 0.00001 to 5% by mass, preferably 0.00001 to 3% by mass, more preferably 0.0001 to 2% by mass, and even more preferably 0.0001 to 1% by mass relative to the total amount of the coloring composition. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[ antioxidant (G) ]

From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use the antioxidant alone or in combination of 2 or more. The antioxidant is not particularly limited as long as it is an antioxidant generally used in industry, and phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like can be used.

Examples of the phenol-based antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF), irganox 1076 (Irganox 1076: octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, irganox 1330 (Irganox 1330:3,3',3", 5',5" -hexatert-butyl-a, a ', a "- (mesitylene-2, 4, 6-triyl) tri-p-cresol, manufactured by BASF), irganox 3114 (Irganox 3114:1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione, manufactured by BASF), irganox 3790 (Irganox 3790:1,3, 5-tris ((4-tert-butyl-3-hydroxy-2, 6-xylyl) methyl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione, manufactured by BASF), irganox 1035 (Irganox 1035: thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], BASF), irganox1135 (Irganox 1135: phenylpropane acid, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, BASF), irganox 1520L (Irganox 1520L:4, 6-bis (octylthiomethyl) -o-cresol, BASF), irganox 3125 (Irganox 3125, BASF), irganox 565 (Irganox 565:2, 4-bis (n-octylthio) -6- (4-hydroxy 3',5' -di-tert-butylphenylamino) -1,3, 5-triazine, BASF), ADK STAB AO-80 (ADK STAB AO-80:3, 9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro (5, 5) undecane (manufactured by ADEKA), sumizer BHT (manufactured by Sumizer BHT, manufactured by Sumitomo chemical Co., ltd.), sumizer GA-80 (manufactured by Sumizer GA-80, manufactured by Sumitomo chemical Co., ltd.), sumizer GS (manufactured by Sumizer GS, manufactured by Sumizer chemical Co., ltd.), cyanox 1790 (manufactured by Cyanox 1790, manufactured by Sitech), vitamin E (manufactured by Eisai), and the like.

Examples of the phosphorus antioxidant include Irgafos 168 (Irgafos 168: tris (2, 4-di-t-butylphenyl) phosphite, irgafos 12 (manufactured by BASF), irgafos 12: tris [2- [ [2,4,8, 10-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxa-phospha-6-yl ] oxy ] ethyl ] amine, manufactured by BASF), irgafos 38 (manufactured by Irgafos 38: bis (2, 4-bis (1, 1-dimethylethyl) -6-methylphenyl) ethyl phosphite, manufactured by BASF), ADK STAB 329K ((manufactured by ADEKA), ADK STAB PEP36 ((manufactured by ADEKA), ADK STAB-8 ((manufactured by ADEKA), sandstab P-EPQ (manufactured by Clariant Co., ltd.), weston618 (manufactured by Weston618, GE Co., ltd.), weston G619G (manufactured by GE Co., ltd.), ultranox (manufactured by Ultranox, sulzem.) and Suftp-6-methylphenyl) 6- (4-t-butylphospha 6-4-hydroxy-4-propyl) phenyl group (manufactured by Surbridge 2, 6-t-butylphospha) 2, 4-t-butylphospha).

Examples of the above-mentioned sulfur-based antioxidant include a dialkyl thiodipropionate compound such as dilauryl thiodipropionate, dimyristyl thiodipropionate or distearyl thiodipropionate, and a β -alkylmercaptopropionate compound of a polyhydric alcohol such as tetrakis [ methylene (3-dodecylthio) propionate ] methane.

[ other Components ]

The coloring composition of the present invention may contain, if necessary, a filler, other polymer compound, adhesion promoter, light stabilizer, chain transfer agent, and other additives known in the art.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-sulfanylpropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldiethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane and N-phenyl-3-aminopropyl triethoxysilane.

[ method for producing coloring composition ]

The coloring composition of the present invention can be prepared, for example, by mixing the compound (I), the solvent (E), and, if necessary, the resin (B), the polymerizable compound (C), the polymerization initiator (D), the polymerization initiator auxiliary (D1), the colorant (A1), the leveling agent (F), the antioxidant (G), and/or other components. The mixing may be carried out by using known or conventional devices and conditions.

The compound (I) is preferably used in a state of being mixed with a part or the whole of the solvent (E) and dispersed by a bead mill or the like into a solution containing the compound (I) having an average particle diameter of about 0.2 μm or less. In this case, the dispersant and part or all of the resin (B) may be blended as necessary.

The colorant (A1) is preferably used in a state of being mixed with a part or all of the solvent (E) in advance and dispersed by a bead mill into a solution containing the colorant (A1) having an average particle diameter of about 0.2 μm or less of the colorant (A1). In this case, the dispersant and part or all of the resin (B) may be blended as necessary.

The compound (I) is preferably used in the form of a solution (the solution is contained in a solution containing the compound (I)) dissolved in part or all of the solvent (E) in advance. The solution containing the compound (I) is preferably further filtered through a filter having a pore size of about 0.01 μm to 1. Mu.m.

The colorant (A1) is preferably used in a state of a solution (the solution is contained in a solution containing the colorant (A1)) dissolved in part or all of the solvent (E) in advance. The solution containing the colorant (A1) is preferably further filtered by a filter having a pore size of about 0.01 μm to 1. Mu.m.

The mixed coloring composition is preferably filtered through a filter having a pore size of about 0.01 μm to about 10. Mu.m.

[ color Filter ]

Color filters may be formed from the coloring compositions of the present invention.

The colored composition is applied to a substrate, and a colored coating film is formed by removing volatile components such as a solvent and drying the composition. The colored coating film thus formed is included in the color filter of the present invention.

Examples of the method for forming the colored pattern include photolithography, inkjet method, and printing method. Among them, photolithography is preferable. Photolithography is a method of forming a colored composition layer by applying the above-mentioned colored composition to a substrate and drying the same, exposing the colored composition layer to light through a photomask, and developing the same. In the photolithography, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and/or without developing at the time of exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and may be appropriately adjusted depending on the purpose, application, and the like, and is, for example, 0.1 to 30. Mu.m, preferably 0.1 to 20. Mu.m, and more preferably 0.5 to 6. Mu.m.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass coated with silica on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like, silicon, a substrate having aluminum, silver/copper/palladium alloy thin films formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by photolithography can be performed by using a known or conventional apparatus and conditions. For example, the production can be performed as follows.

First, the coloring composition is applied onto a substrate, and then heated and dried (prebaked) and/or dried under reduced pressure, whereby volatile components such as a solvent are removed and dried, thereby obtaining a smooth coloring composition layer.

Examples of the coating method include a spin coating method, a slit coating method, and a slit/spin coating method.

The temperature at which the heat drying is carried out is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. In the case of drying under reduced pressure, it is preferable to carry out the drying under a pressure of 50 to 150Pa at a temperature of 20 to 25 ℃. 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 to light through a photomask for forming a target coloring pattern.

The pattern on the photomask is not particularly limited, and a pattern corresponding 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 of less than 350nm may be cut off using a filter that cuts off this wavelength region, or light of around 436nm, around 408nm, or around 365nm may be selectively extracted using a band-pass filter that extracts these wavelength regions. Specific examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps.

In order to uniformly irradiate the entire exposure surface with parallel light and to precisely align the photomask with the substrate on which the coloring composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

The exposed coloring composition layer is developed by contacting with a developer, thereby forming a coloring pattern on the substrate. The unexposed portion of the coloring composition layer is dissolved in a developer and removed by development.

As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable.

The concentration of the basic compound is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass. The developer may contain a surfactant.

The developing method may be any of paddle method, dipping method, spraying method, and the like. And the substrate is tilted at an arbitrary angle during development.

The substrate after development is preferably washed with water.

It is further preferable to post-bake the resulting colored pattern.

The post-baking temperature is preferably 150 to 250 ℃, more preferably 160 to 235 ℃. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes. The color filter having the colored pattern and the colored coating film thus obtained may be further subjected to a surface coating treatment in order to impart various properties.

The color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state imaging element, particularly a color filter used in a liquid crystal display device.

The present application claims the benefit of priority based on japanese patent application No. 2019-026911 filed on 18 of 2 months in 2019. The entire contents of the specification of japanese patent application No. 2019-026911, filed on 2 months of 2019, is incorporated herein by reference.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples, and can be carried out with appropriate modifications within the scope suitable for the above-described and the following gist, and these are included in the technical scope of the present invention. Hereinafter, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

In the following synthesis examples, the structure of the compound was confirmed by MASS analysis (LC; model 1200 by Agilent; model LC/MSD6130 by Agilent).

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.

HLC-8120GPC (manufactured by Tosoh Co., ltd.)

Column TSK-GELG2000HXL

Column temperature of 40 DEG C

Solvent tetrahydrofuran

Flow Rate 1.0 mL/min

The concentration of the solid content of the analysis sample is 0.001 to 0.01 mass%

Sample injection amount 50. Mu.L

Detector RI

Calibration standard substance: TSK STANDARD PolySTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., ltd.)

The dispersion was defined as the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene obtained above.

Example 1

3.02 parts of 4-amino-2-methylquinoline (manufactured by Tokyo chemical industry Co., ltd.), 8.33 parts of 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 11.7 parts of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.) and 66.7 parts of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) were mixed.

The mixture was kept at 170 ℃ and stirred for 9 hours.

To this mixture, 13.6 parts of 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo chemical industries, ltd.) and 22.9 parts of benzoic acid (manufactured by Tokyo chemical industries, ltd.) were added, and 66.4 parts of methyl benzoate (manufactured by Tokyo chemical industries, ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 49 hours.

To this mixture, 8.32 parts of 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo chemical industries, ltd.) and 11.7 parts of benzoic acid (manufactured by Tokyo chemical industries, ltd.) were added, and 43.5 parts of methyl benzoate (manufactured by Tokyo chemical industries, ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 28 hours.

The mixture was cooled to room temperature, and 1300 parts of methanol was added to the mixture.

After the mixture was stirred at room temperature, the mixture was filtered, and the resulting residue was washed with 400 parts of methanol 7 times.

The resulting residue was dried under reduced pressure at 60 ℃.

To the residue was added 875 parts of N, N-dimethylformamide.

After the mixture was stirred at room temperature, the mixture was filtered, and the obtained residue was washed 3 times with N, N-dimethylformamide having the same volume as the obtained residue.

The residue was washed 3 times with 200 parts of methanol.

The obtained residue was dried under reduced pressure at 60℃to obtain 7.25 parts of a compound represented by the formula (Ia 2).

< identification of Compounds represented by formula (Ia 2) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 519

Ionization mode=esi-: M/z= [ M-H ]] ^- 517

Accurate molecular weight 518

Example 2

2.05 parts of 4-amino-2-methylquinoline (manufactured by Tokyo chemical industry Co., ltd.) and 8.16 parts of tetrachlorophthalic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 8.05 parts of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.) and 58.6 parts of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) were mixed.

The mixture was kept at 170 ℃ and stirred for 5 hours.

To this mixture, 3.72 parts of tetrachlorophthalic anhydride (manufactured by tokyo chemical industry Co., ltd.), 8.00 parts of benzoic acid (manufactured by tokyo chemical industry Co., ltd.), and 18.0 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 6 hours.

To this mixture, 1.89 parts of tetrachlorophthalic anhydride (manufactured by tokyo chemical industry Co., ltd.), 4.09 parts of benzoic acid (manufactured by tokyo chemical industry Co., ltd.), and 54.5 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 6 hours.

To this mixture, 11.4 parts of tetrachlorophthalic anhydride (manufactured by tokyo chemical industry Co., ltd.), 12.6 parts of benzoic acid (manufactured by tokyo chemical industry Co., ltd.), and 18.4 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 16 hours.

The mixture was cooled to room temperature, and 1200 parts of methanol was added to the mixture.

After the mixture was stirred at room temperature, the mixture was filtered, and the resulting residue was washed with 400 parts of methanol 8 times.

The obtained residue was dried under reduced pressure at 60℃to obtain 8.88 parts of a compound represented by the formula (Ia 23).

< identification of Compounds represented by the formula (Ia 23)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 691

Ionization mode=esi-: M/z= [ M-H ]] ^- 689

Exact molecular weight 690

Example 3

1.01 parts of 4-amino-2-methylquinoline (manufactured by Tokyo chemical industry Co., ltd.), 3.49 parts of 4-phenylethynyl phthalic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 3.95 parts of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.), and 28.7 parts of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) were mixed.

The mixture was kept at 170 ℃ and stirred for 20 hours.

To this mixture, 0.476 parts of 4-phenylethynyl phthalic anhydride (manufactured by tokyo chemical industry Co., ltd.), 1.32 parts of benzoic acid (manufactured by tokyo chemical industry Co., ltd.), and 3.3 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 10 hours.

To this mixture were added 0.801 parts of 4-phenylethynyl phthalic anhydride (manufactured by tokyo chemical industry Co., ltd.), 2.90 parts of benzoic acid (manufactured by tokyo chemical industry Co., ltd.), and 9.13 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.).

The mixture was kept at 170 ℃ and stirred for 29 hours.

The mixture was cooled to room temperature, 400 parts of methanol was added to the mixture, and the mixture was stirred for 1 hour.

The mixture was filtered, and the resulting residue was washed 6 times with 140 parts of methanol.

The obtained residue was dried under reduced pressure at 60℃to obtain 3.12 parts of a compound represented by the formula (Ia 22).

< identification of Compounds represented by formula (Ia 22)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 619

Ionization mode=esi-: m/z= [ mass analysis ]M－H] ^- 617

Accurate molecular weight 618

Example 4

4.04 parts of 4-amino-2-methylquinoline (manufactured by Tokyo chemical industry Co., ltd.) 10.8 parts of trimellitic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 15.6 parts of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.) and 92.3 parts of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) were mixed.

The mixture was kept at 167 ℃ and stirred for 5 hours.

To this mixture, 40.2 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) was added.

The mixture was kept at 167 ℃ and stirred for 9 hours.

To this mixture, 28.0 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) was added.

The mixture was kept at 170 ℃ and stirred for 11 hours.

The mixture was cooled to room temperature, and 2000 parts of methanol was added to the mixture.

The mixture was stirred at room temperature.

To the resulting mixture, 173 parts of methanol was added.

The mixture was filtered, and the resulting residue was washed with 124 parts of methanol 1 time, 160 parts of methanol 1 time, and 400 parts of methanol 1 time.

The obtained residue was dried under reduced pressure at 60℃to obtain 9.91 parts of a mixture of the compound represented by the formula (Ia 10), the compound represented by the formula (Ia 2143), the compound represented by the formula (Ia 850) and the compound represented by the formula (Ia 315).

< identification of Compounds represented by formula (Ia 10) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 507

Ionization mode=esi-: M/z= [ M-H ]] ^- 505

Accurate molecular weight 506

< identification of Compounds represented by formula (Ia 2143) >)

Ionization mode=esi +: M/z= [ m+h ] ] ⁺ 521

Ionization mode=esi-: M/z= [ M-H ]] ^- 519

Accurate molecular weight 520

< identification of Compounds represented by formula (Ia 850)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 521

Ionization mode=esi-: M/z= [ M-H ]] ^- 519

Accurate molecular weight 520

< identification of Compounds represented by formula (Ia 315)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 535

Ionization mode=esi-: M/z= [ M-H ]] ^- 533

Accurate molecular weight 534

Example 5

5.23 parts of 4-amino-2-methylquinoline (manufactured by Tokyo chemical industry Co., ltd.), 14.2 parts of 3-nitrophthalic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 20.2 parts of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.), and 119 parts of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) were mixed.

The mixture was kept at 168 ℃ and stirred for 12 hours.

To this mixture, 7.12 parts of 3-nitrophthalic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 10.3 parts of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.), and 16.0 parts of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 26 hours.

The mixture was cooled to room temperature, and 2400 parts of methanol was added to the mixture.

The resulting mixture was stirred at room temperature and then filtered.

The resulting residue was washed with 400 parts of methanol 5 times.

The obtained residue was dried under reduced pressure at 60℃to obtain 13.0 parts of a compound represented by the formula (Ia 35).

< identification of Compounds represented by formula (Ia 35)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 509

Ionization mode=esi-: M/z= [ M-H ]] ^- 507

Accurate molecular weight 508

Example 6

3.67 parts of 4-amino-2-methylquinoline (manufactured by Tokyo chemical industry Co., ltd.), 7.59 parts of phthalic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 14.4 parts of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.), and 84.3 parts of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) were mixed.

The mixture was kept at 170 ℃ and stirred for 10 hours.

To this mixture, 7.92 parts of phthalic anhydride (manufactured by tokyo chemical industry Co., ltd.), 15.5 parts of benzoic acid (manufactured by tokyo chemical industry Co., ltd.), and 45 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 9 hours.

To this mixture, 9 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) was added.

The mixture was kept at 170 ℃ and stirred for 18 hours.

To this mixture, 7.77 parts of phthalic anhydride (manufactured by tokyo chemical industry Co., ltd.), 14.6 parts of benzoic acid (manufactured by tokyo chemical industry Co., ltd.), and 11.1 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 27 hours.

To this mixture, 3.88 parts of phthalic anhydride (manufactured by tokyo chemical industry Co., ltd.), 7.33 parts of benzoic acid (manufactured by tokyo chemical industry Co., ltd.), and 12.3 parts of methyl benzoate (manufactured by tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 8 hours.

The mixture was cooled to room temperature, and 2800 parts of methanol was added to the mixture.

The resulting mixture was stirred at room temperature and then filtered.

The resulting residue was washed 2 times with 400 parts of methanol and 1 time with 800 parts of methanol.

The obtained residue was dried under reduced pressure at 60℃to obtain 7.67 parts of the compound represented by the formula (Ia 1).

< identification of Compounds represented by formula (Ia 1) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 419

Ionization mode=esi-: M/z= [ M-H ]] ^- 417

Accurate molecular weight 418

Example 7

1.05 parts of a mixture of the compound represented by formula (Ia 10), the compound represented by formula (Ia 2143), the compound represented by formula (Ia 850) and the compound represented by formula (Ia 315) obtained in example 4 was mixed with 106 parts of water.

To the mixture was added 22.1 parts of a 1% aqueous sodium hydroxide solution at room temperature.

To the resultant mixture, 3.23 parts of iron (III) nitrate nonahydrate (manufactured by Wako pure chemical industries, ltd.) and 8.19 parts of water in 29.1 parts were added at room temperature.

The resulting mixture was filtered, and the resulting residue was washed 2 times with the same volume of water as the resulting residue.

The obtained residue was dried under reduced pressure at 60℃to obtain 1.17 parts of a mixture containing the compound represented by the formula (Ie 12).

Example 8

5.03 parts of 4-amino-2-methylquinoline (manufactured by Tokyo chemical industry Co., ltd.), 13.6 parts of 4-nitrophthalic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 19.5 parts of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.), and 116 parts of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) were mixed.

The mixture was kept at 170 ℃ and stirred for 4 hours.

To this mixture, 7.12 parts of 4-nitrophthalic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 10.5 parts of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.), and 30.1 parts of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 18 hours.

To this mixture, 13.6 parts of 4-nitrophthalic anhydride (Tokyo chemical industry Co., ltd.), 19.9 parts of benzoic acid (Tokyo chemical industry Co., ltd.), and 29.1 parts of methyl benzoate (Tokyo chemical industry Co., ltd.) were added.

The mixture was kept at 170 ℃ and stirred for 27 hours.

The resulting mixture was stirred at room temperature and then filtered.

The resulting residue was washed with 400 parts of methanol 4 times.

The obtained residue was dried under reduced pressure at 60℃to obtain 14.8 parts of a compound represented by the formula (Ia 33).

< identification of Compounds represented by formula (Ia 33) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 509

Ionization mode=esi-: M/z= [ M-H ]] ^- 507

Accurate molecular weight 508

Example A-1

1 mol of 4-amino-2-methylquinoline (manufactured by Tokyo chemical industry Co., ltd.), 8 mol of 3-methylphthalic anhydride (manufactured by Tokyo chemical industry Co., ltd.), 21 mol of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.), and 73 times by weight of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) as much as 1 mol were mixed.

The mixture was kept at 170 ℃ and stirred for 120 hours.

The mixture was cooled to room temperature, and 13 times by weight of methanol as much as the weight of the mixture was added to the mixture.

The resulting mixture was stirred at room temperature and then filtered.

The resulting residue was washed with methanol.

The obtained residue was purified by column chromatography to obtain a compound represented by the formula (Ia 5).

< identification of Compounds represented by formula (Ia 5) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 447

Ionization mode=esi-: M/z= [ M-H ]] ^－ 445

Accurate molecular weight 446

Example A-2

A compound represented by formula (Ia 3) was obtained in the same manner as in example a-1 except that 3-methylphthalic anhydride (manufactured by tokyo chemical industry co.) was replaced with 1, 2-naphthalic anhydride (manufactured by tokyo chemical industry co.).

< identification of Compounds represented by formula (Ia 3) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 519

Ionization mode=esi-: M/z= [ M-H ]] ^－ 517

Accurate molecular weight 518

Example A-3

A compound represented by formula (Ia 17) was obtained in the same manner as in example a-1, except that 3-methylphthalic anhydride (manufactured by tokyo chemical industry co., ltd.) was replaced with 3-chlorophthalic anhydride (manufactured by tokyo chemical industry co., ltd.).

/>

< identification of Compounds represented by formula (Ia 17) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 487

Ionization mode=esi-: M/z= [ M-H ]] ^－ 485

Accurate molecular weight 486

Examples A to 4

A compound represented by formula (Ia 7) was obtained in the same manner as in example a-1, except that 3-methylphthalic anhydride (manufactured by tokyo chemical industry co., ltd.) was replaced with 4-chlorophthalic anhydride (manufactured by tokyo chemical industry co., ltd.).

< identification of Compounds represented by formula (Ia 7) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 487

Ionization mode=esi-: M/z= [ M-H ]] ^－ 485

Accurate molecular weight 486

Examples A to 5

A compound represented by formula (Ia 36) was obtained in the same manner as in example a-1, except that 3-methylphthalic anhydride (manufactured by tokyo chemical industry co., ltd.) was replaced with 3-acetaminophthalic anhydride (manufactured by tokyo chemical industry co., ltd.).

< identification of Compounds represented by formula (Ia 36)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 533

Ionization mode=esi-: M/z= [ M-H ]] ^－ 531

Accurate molecular weight 532

Examples A to 6

The procedure of example A-1 was repeated except that 3-methylphthalic anhydride (manufactured by Tokyo chemical industry Co., ltd.) was replaced with 3-hydroxyphthalic anhydride (manufactured by Sigma-Aldrich Japan contract Co., ltd.) to obtain a compound represented by the formula (Ia 51).

< identification of Compounds represented by formula (Ia 51)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 451

Ionization mode=esi-: M/z= [ M-H ]] ^－ 449

Accurate molecular weight of 450

Examples A to 7

A compound represented by formula (Ia 19) was obtained in the same manner as in example a-1, except that 3-methylphthalic anhydride (manufactured by tokyo chemical industry co., ltd.) was replaced with 3-fluorophthalic anhydride (manufactured by tokyo chemical industry co., ltd.).

< identification of Compounds represented by formula (Ia 19)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 455

Ionization mode=esi-: M/z= [ M-H ]] ^－ 453

Accurate molecular weight 454

Examples A to 8

A compound represented by formula (Ia 248) was obtained in the same manner as in example a-1, except that 3-methylphthalic anhydride (manufactured by tokyo chemical industry co., ltd.) was replaced with the compound represented by formula (sm 1).

/>

< identification of Compounds represented by the formula (Ia 248) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 507

Ionization mode=esi-: M/z= [ M-H ]] ^－ 505

Accurate molecular weight 506

Examples A to 9

A compound represented by formula (Ia 4) was obtained in the same manner as in example a-1, except that 3-methylphthalic anhydride (manufactured by tokyo chemical industry co., ltd.) was replaced with 4-methylphthalic anhydride (manufactured by tokyo chemical industry co., ltd.).

< identification of Compounds represented by formula (Ia 4) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 447

Ionization mode=esi-: M/z= [ M-H ]] ^－ 445

Accurate molecular weight 446

Examples A to 10

A compound represented by the formula (It 242) was obtained in the same manner as in example a-1 except that 4-amino-2-methylquinoline (manufactured by tokyo chemical industry co.) was replaced with 4-amino-6-fluoro-2-methylquinoline (manufactured by Sigma-Aldrich Japan contract co.) and 3-methylphthalic anhydride (manufactured by tokyo chemical industry co.) was replaced with 2, 3-naphthalenedicarboxylic anhydride (manufactured by tokyo chemical industry co.).

< identification of Compound represented by formula (It 242) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 537

Ionization mode=esi-: M/z= [ M-H ]] ^－ 535

Exact molecular weight 536

Examples A to 11

A compound represented by the formula (It 232) was obtained in the same manner as in example a-1 except that 4-amino-2-methylquinoline (manufactured by tokyo chemical industry co.) was replaced with 4-amino-6-methoxy-2-methylquinoline (manufactured by Sigma-Aldrich Japan contract co.) and 3-methylphthalic anhydride (manufactured by tokyo chemical industry co.) was replaced with 2, 3-naphthalenedicarboxylic anhydride (manufactured by tokyo chemical industry co.).

< identification of Compound represented by formula (It 232 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 549

Ionization mode=esi-: M/z= [ M-H ]] ^－ 547

Accurate molecular weight of 548

Examples A to 12

A compound represented by the formula (It 750) was obtained in the same manner as in example a-1, except that 4-amino-2-methylquinoline (manufactured by tokyo chemical industry co., ltd.) was replaced with 4-amino-6-bromo-2-methylquinoline (manufactured by Sigma-Aldrich Japan contract co.).

< identification of Compound represented by formula (It 750 >)

Ionization mode=esi +: M/z= [ m+h ] ] ⁺ 525

Ionization mode=esi-: M/z= [ M-H ]] ^－ 523

Accurate molecular weight 524

Synthesis example B-1

A mixture of 1 mole of the compound represented by formula (Ia 2) and 20 moles of potassium hydroxide and 10 times by weight of water based on the weight of 1 mole of the compound represented by formula (Ia 2) was mixed. The mixture was kept at 90℃and stirred until the compound represented by formula (Ia 2) disappeared. 36% hydrochloric acid was mixed with the mixture and neutralized. The mixture was filtered. The resulting residue was washed with water. The residue was purified by column chromatography to obtain a compound represented by the formula (IM 1-1).

< identification of Compounds represented by the formula (IM 1-1) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 339

Ionization mode=esi-: M/z= [ M-H ]] ^－ 337

Accurate molecular weight 338

Synthesis example B-2

The procedure of Synthesis example B-1 was carried out in the same manner as in Synthesis example B-1 except that the compound represented by formula (Ia 2) was replaced with the compound represented by formula (Ia 23), to obtain a compound represented by formula (IM 1-2).

< identification of Compounds represented by the formula (IM 1-2) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 425

Ionization mode=esi-: M/z= [ M-H ]] ^－ 423

Accurate molecular weight 424

Synthesis example B-3

The procedure of Synthesis example B-1 was carried out in the same manner as in Synthesis example B-1 except that the compound represented by formula (Ia 2) was replaced with the compound represented by formula (Ia 5), to obtain a compound represented by formula (IM 1-3).

< identification of Compounds represented by the formula (IM 1-3) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 303

Ionization mode=esi-: M/z= [ M-H ]] ^－ 301

Accurate molecular weight 302

Synthesis example B-4

The procedure of Synthesis example B-1 was carried out in the same manner as in Synthesis example B-1 except that the compound represented by formula (Ia 2) was replaced with the compound represented by formula (Ia 4), to obtain a compound represented by formula (IM 1-4).

< identification of Compounds represented by the formula (IM 1-4) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 303

Ionization mode=esi-: M/z= [ M-H ]] ^－ 301

Accurate molecular weight 302

Synthesis example B-5

The procedure of Synthesis example B-1 was carried out in the same manner as in Synthesis example B-1 except that the compound represented by formula (Ia 2) was replaced with the compound represented by formula (Ia 36), to obtain a compound represented by formula (IM 1-5).

< identification of Compounds represented by the formula (IM 1-5) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 346

Ionization mode=esi-: M/z= [ M-H ]] ^－ 344

Accurate molecular weight 345

Synthesis example B-6

The procedure of Synthesis example B-1 was repeated except that the compound represented by formula (Ia 2) was replaced with the compound represented by formula (Ia 1), to obtain a compound represented by formula (IM 1-6).

Identification of Compounds represented by the formula (IM 1-6)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 289

Ionization mode=esi-: M/z= [ M-H ]] ^－ 287

Accurate molecular weight 288

Example C-1

1 mol of the compound represented by the formula (IM 1-1), 8 mol of trimellitic anhydride (manufactured by Tokyo chemical industry Co., ltd.) and 21 mol of benzoic acid (manufactured by Tokyo chemical industry Co., ltd.) were mixed with 73 times by weight of methyl benzoate (manufactured by Tokyo chemical industry Co., ltd.) based on the weight of 1 mol of the compound represented by the formula (IM 1-1). The mixture was kept at 170 ℃ and stirred for 120 hours. The mixture was cooled to room temperature, and 13 times by weight of methanol as much as the weight of the mixture was added to the mixture. The resulting mixture was stirred at room temperature and then filtered. The resulting residue was washed with methanol. The obtained residue was purified by column chromatography to obtain a compound represented by the formula (Ia 699).

< identification of Compounds represented by the formula (Ia 699) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 513

Ionization mode=esi-: M/z= [ M-H ]] ^－ 511

Accurate molecular weight 512

Example C-2

A compound represented by the formula (Ia 970) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-2), and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 2, 3-naphthalene dicarboxylic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compounds represented by the formula (Ia 970)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 605

Ionization mode=esi-: m/z=[M－H] ^－ 603

Accurate molecular weight 604

Example C-3

A compound represented by formula (Ia 703) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by tokyo chemical industry co.) was replaced with tetrachlorophthalic anhydride (manufactured by tokyo chemical industry co.).

< identification of Compounds represented by formula (Ia 703)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 605

Ionization mode=esi-: M/z= [ M-H ]] ^－ 603

Accurate molecular weight 604

Example C-4

A compound represented by the formula (If 3796) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by tokyo chemical industry co.) was replaced with 3-methylphthalic anhydride (manufactured by tokyo chemical industry co.).

< identification of Compound represented by formula (If 3796 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 483

Ionization mode=esi-: M/z= [ M-H ]] ^－ 481

Precise molecular weight 482

Example C-5

A compound represented by formula (Ia 696) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by tokyo chemical industry co.) was replaced with phthalic anhydride (manufactured by tokyo chemical industry co.).

< identification of Compounds represented by the formula (Ia 696) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 469

Ionization mode=esi-: M/z= [ M-H ]] ^－ 467

Accurate molecular weight 468

Example C-6

A compound represented by the formula (Ia 969) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-2), and trimellitic anhydride (manufactured by tokyo chemical industry (ltd.) was replaced with phthalic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compounds represented by formula (Ia 969) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 555

Ionization mode=esi-: M/z= [ M-H ]] ^－ 553

Accurate molecular weight 554

Example C-7

A compound represented by the formula (If 2528) was obtained in the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-2) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 3-methylphthalic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 2528 >)

Ionization mould (mass analysis)ESI +: M/z = [ M+H ]] ⁺ 569

Ionization mode=esi-: M/z= [ M-H ] ] ^－ 567

Accurate molecular weight 568

Example C-8

A compound represented by formula (Ia 973) was obtained in the same manner as in example C-1 except that the compound represented by formula (IM 1-1) was replaced with the compound represented by formula (IM 1-2).

< identification of Compounds represented by formula (Ia 973) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 599

Ionization mode=esi-: M/z= [ M-H ]] ^－ 597

Accurate molecular weight 598

Example C-9

In the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-3), a compound represented by the formula (If 1261) was obtained.

< identification of Compound represented by formula (If 1261 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 477

Ionization mode=esi-: M/z= [ M-H ]] ^－ 475

Exact molecular weight 476

Example C-10

A compound represented by the formula (If 5688) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-3) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd.) was replaced with tetrachlorophthalic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 5688 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 569

Ionization mode=esi-: M/z= [ M-H ]] ^－ 567

Accurate molecular weight 568

Example C-11

A compound represented by the formula (If 636) was obtained in the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-3) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 2, 3-naphthalene dicarboxylic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 636) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 483

Ionization mode=esi-: M/z= [ M-H ]] ^－ 481

Precise molecular weight 482

Example C-12

A compound represented by the formula (If 5670) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-3) and the trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 1, 2-naphthalene anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 5670 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 483

Ionization mode=esi-: M/z= [ M-H ]] ^－ 481

Precise molecular weight 482

Example C-13

A compound represented by the formula (If 5720) was obtained in the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-3) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 1, 8-naphthalene anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 5720 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 483

Ionization mode=esi-: M/z= [ M-H ]] ^－ 481

Precise molecular weight 482

Examples C to 14

A compound represented by formula (Ia 712) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by tokyo chemical industry co.) was replaced with 1, 8-naphthalene anhydride (manufactured by tokyo chemical industry co.).

< identification of Compounds represented by formula (Ia 712) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 519

Ionization mode=esi-: M/z= [ M-H ]] ^－ 517

Accurate molecular weight 518

Example C-15

A compound represented by the formula (If 635) was obtained in the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-4) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 2, 3-naphthalene dicarboxylic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 635 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 483

Ionization mode=esi-: M/z= [ M-H ]] ^－ 481

Precise molecular weight 482

Examples C-16

In the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-4), a compound represented by the formula (If 1260) was obtained.

< identification of Compound represented by formula (If 1260) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 477

Ionization mode=esi-: M/z= [ M-H ]] ^－ 475

Exact molecular weight 476

Examples C to 17

A compound represented by the formula (If 13040) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-4) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with pyromellitic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 13040 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 521

Ionization mode=esi-: M/z= [ M-H ]] ^－ 519

Accurate molecular weight 520

Examples C-18

A compound represented by the formula (If 8454) was obtained in the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-4) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd.) was replaced with 4-tert-butylphthalic anhydride (manufactured by tokyo chemical industry (ltd.).

< identification of Compound represented by formula (If 8454) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 489

Ionization mode=esi-: M/z= [ M-H ]] ^－ 487

Accurate molecular weight 488

Examples C to 19

A compound represented by the formula (If 3795) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by tokyo chemical industry co.) was replaced with 4-methylphthalic anhydride (manufactured by tokyo chemical industry co.).

< identification of Compound represented by formula (If 3795) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 483

Ionization mode=esi-: M/z= [ M-H ]] ^－ 481

Precise molecular weight 482

Example C-20

A compound represented by the formula (If 5671) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-3) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 4-methylphthalic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 5671) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 447

Ionization mode=esi-: M/z= [ M-H ]] ^－ 445

Accurate molecular weight 446

Example C-21

A compound represented by the formula (If 2511) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-4) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 3-methylphthalic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 2511 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 447

Ionization mode=esi-: M/z= [ M-H ]] ^－ 445

Accurate molecular weight 446

Examples C to 22

A compound represented by the formula (If 3799) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by tokyo chemical industry co.) was replaced with 4-tert-butylphthalic anhydride (manufactured by tokyo chemical industry co.).

< identification of Compound represented by formula (If 3799 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 525

Ionization mode=esi-: M/z= [ M-H ]] ^－ 523

Accurate molecular weight 524

Example C-23

A compound represented by the formula (If 3814) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by tokyo chemical industry co.) was replaced with 3-acetamidophthalic anhydride (manufactured by tokyo chemical industry co.).

< identification of Compound represented by formula (If 3814 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 526

Ionization mode=esi-: M/z= [ M-H ]] ^－ 524

Accurate molecular weight 525

Example C-24

A compound represented by the formula (If 654) was obtained in the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-5) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 2, 3-naphthalene dicarboxylic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 654) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 526

Ionization mode=esi-: M/z= [ M-H ]] ^－ 524

Accurate molecular weight 525

Example C-25

A compound represented by the formula (If 29) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-5) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with phthalic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 29 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 476

Ionization mode=esi-: M/z= [ M-H ]] ^－ 474

Exact molecular weight 475

Examples C to 26

In the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-5), a compound represented by the formula (If 1279) was obtained.

< identification of Compound represented by formula (If 1279 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 520

Ionization mode=esi-: M/z= [ M-H ]] ^－ 518

Accurate molecular weight 519

Examples C to 27

A compound represented by the formula (If 1904) was obtained in the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-5) and trimellitic anhydride (manufactured by tokyo chemical industry co.) was replaced with the compound represented by the formula (sm 1).

< identification of Compound represented by formula (If 1904 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 520

Ionization mode=esi-: M/z= [ M-H ]] ^－ 518

Accurate molecular weight 519

Examples C to 28

A compound represented by formula (Ia 728) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by tokyo chemical industry co., ltd.) was replaced with the compound represented by formula (sm 1).

< identification of Compounds represented by formula (Ia 728) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 513

Ionization mode=esi-: M/z= [ M-H ]] ^－ 511

Accurate molecular weight 512

Examples C to 29

A compound represented by the formula (Ia 657) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-6), and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 2, 3-naphthalene dicarboxylic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compounds represented by the formula (Ia 657) >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 469

Ionization mode=esi-: M/z= [ M-H ]] ^－ 467

Accurate molecular weight 468

Example C-30

A compound represented by the formula (If 3171) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-6) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 3-methylphthalic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compound represented by formula (If 3171 >)

Ionization mode=esi +: M/z= [ m+h ]] ⁺ 433

Ionization mode=esi-: M/z= [ M-H ]] ^－ 431

Accurate molecular weight 432

Example C-31

A compound represented by the formula (Ia 686) was obtained in the same manner as in example C-1, except that the compound represented by the formula (IM 1-1) was replaced with the compound represented by the formula (IM 1-6) and trimellitic anhydride (manufactured by tokyo chemical industry (ltd)) was replaced with 3-chlorophthalic anhydride (manufactured by tokyo chemical industry (ltd)).

< identification of Compounds represented by the formula (Ia 686) >)

Ionization mode (Mass analysis)＝ESI+:m/z＝[M+H] ⁺ 453

Ionization mode=esi-: M/z= [ M-H ]] ^－ 451

Accurate molecular weight 452

Example E-1

1.61 parts of the compound represented by the formula (Ia 5) and 32.7 parts of fuming sulfuric acid (25%) (Fuji film and Wako pure chemical industries, ltd.) were mixed at 10℃to 20 ℃. The mixture was kept at 5-20 ℃ and stirred for 3 hours. The mixture was added dropwise to 62.2 parts of ice. The resulting mixture was filtered. To the obtained filtrate, 10% aqueous ammonia was added to neutralize the obtained filtrate. The solvent of the mixture was distilled off until the volume of the mixture became half. To the resulting mixture was added 2 times the volume of methanol as the volume of the mixture. The mixture was filtered, and the solvent of the resulting filtrate was distilled off. Drying the obtained residue at 60deg.C under reduced pressure to obtain a compound represented by formula (Ia 5-SA 1) (wherein any 1 hydrogen atom in the compound represented by formula (Ia 5) is replaced with-SO) ₃ NH ₄ Compounds represented by the formula (Ia 5-SA 2) (substitution of any 2 hydrogen atoms of the compound represented by the formula (Ia 5) to-SO) ₃ NH ₄ Compound of (c) 0.58 parts.

< identification of Compounds represented by the formula (Ia 5-SA 1) >)

Ionization mode=esi-: M/z= [ M-NH ] ₄ +H－H] ^－ 525

Accurate molecular weight 543

< identification of Compounds represented by the formula (Ia 5-SA 2) >)

Ionization mode=esi-: M/z= [ M-NH ] ₄ －NH ₄ +H+H－H] ^－ 605

Accurate molecular weight 640

Example E-2

0.30 part of the compound represented by the formula (Ia 1), 3.00 parts of chloroform and 0.55 part of chlorosulfonic acid (Tokyo chemical industry Co., ltd.) were mixed. The mixture was kept at 60 ℃ and stirred for 3 hours. The mixture was added dropwise to 3.64 parts of ice. The resulting mixture was filtered, and the resulting residue was washed with water. The residue was washed with methanol. The residue was dried under reduced pressure at 60℃to obtain a compound represented by the formula (Ia 1-SA 1) (wherein any 1 hydrogen atom in the compound represented by the formula (Ia 1) was replaced with-SO) ₃ H) and compounds represented by the formulae (Ia 1-SA 2) (wherein any 1 hydrogen atom in the compounds represented by the formula (Ia 1) is substituted by-SO) ₂ Cl compound) 0.18 parts.

< identification of Compounds represented by the formula (Ia 1-SA 1) >)

Ionization mode=esi-: M/z= [ M-H ]] ^－ 497

Accurate molecular weight of 498

< identification of Compounds represented by the formula (Ia 1-SA 2) >)

Ionization mode=esi-: M/z= [ M-H ]] ^－ 515

Accurate molecular weight 516

Example E-3

1.00 parts of the compound represented by the formula (Ia 2) and 20.6 parts of fuming sulfuric acid (30%) (Fuji film and Wako pure chemical industries, ltd.) were mixed at room temperature. The mixture was stirred at room temperature for 3 hours. The mixture was added dropwise to 208 parts of ice. The resulting mixture was mixed with 110 parts of acetonitrile. The mixture was filtered, and the resulting residue was washed with acetonitrile. The residue is treated at 60deg.CDrying under reduced pressure to obtain a compound represented by formula (Ia 2-SA) (wherein any 2 hydrogen atoms of the compound represented by formula (Ia 2) are replaced with-SO) ₃ Compounds of H) 0.40 parts.

< identification of Compounds represented by the formula (Ia 2-SA) >)

Ionization mode=esi-: M/z= [ M-H ]] ^－ 677

Accurate molecular weight 678

Synthesis example 1

A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen to replace the nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80℃while stirring. Next, 38 parts of acrylic acid, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise over 5 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ² ^,6 ]Decane-9-yl ester (molar ratio 1:1) 289 parts, propylene glycol monomethyl ether acetate 125 parts. On the other hand, a solution obtained by dissolving 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at 80℃for 4 hours and then cooled to room temperature to obtain a solution of the copolymer (resin B1) having a solid content of 35.0%. The weight average molecular weight of the obtained resin B1 was 8800, the dispersity was 2.1, and the acid value in terms of solid content was 80mg-KOH/g.

Synthesis example 2

A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen to replace the nitrogen atmosphere, 340 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80℃while stirring. Next, 57 parts of acrylic acid, 3, 4-epoxytricyclo [5.2.1.0 ] was added dropwise over 5 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ² ^,6 ]54 parts of a mixture of decane-9-yl esters (molar ratio 1:1),239 parts of benzyl methacrylate and 73 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution obtained by dissolving 40 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at 80℃for 3 hours and then cooled to room temperature to obtain a solution of the copolymer (resin B2) having a solid content of 36.8%. The weight average molecular weight of the obtained copolymer was 9400, the dispersity was 1.89, and the acid value in terms of solid content was 114mg-KOH/g.

Example 9

The following components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 1.

The coloring composition 1 was applied onto a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). Table 39 shows the film thickness of the pre-baked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

Example 10

A colored composition was obtained in the same manner as in example 9 except that the compound represented by the formula (Ia 2) was replaced with the compound represented by the formula (Ia 23), and a pre-baked colored coating film and a post-baked colored coating film were obtained. Table 39 shows the film thickness of the pre-baked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film.

Example 11

A colored composition was obtained in the same manner as in example 9 except that the compound represented by the formula (Ia 2) was replaced with a mixture of the compound represented by the formula (Ia 10), the compound represented by the formula (Ia 2143), the compound represented by the formula (Ia 850) and the compound represented by the formula (Ia 315) obtained in example 4, and a pre-baked colored coating film and a post-baked colored coating film were obtained. The film thickness of the pre-baked colored coating film and the wavelength of the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table 39.

Example 12

A colored composition was obtained in the same manner as in example 9 except that the compound represented by the formula (Ia 2) was replaced with the compound represented by the formula (Ia 35), and a pre-baked colored coating film and a post-baked colored coating film were obtained. Table 39 shows the film thickness of the pre-baked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film.

Example 13

The following components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M2.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 2.

The coloring composition 2 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). Table 39 shows the film thickness of the pre-baked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

Example 14

The following components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M3.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 3.

The coloring composition 3 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table 39. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

Example 15

A colored composition was obtained in the same manner as in example 14 except that the compound represented by formula (Ia 10), the compound represented by formula (Ia 2143), the compound represented by formula (Ia 850), and the compound represented by formula (Ia 315) obtained in example 4 were replaced with the compound represented by formula (Ia 33), and a pre-baked colored coating film and a post-baked colored coating film were obtained. Table 39 shows the film thickness of the pre-baked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film.

Example 16

The following ingredients were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M4.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 4.

The coloring composition 4 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). Table 39 shows the film thickness of the pre-baked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

Comparative example 1

The following ingredients were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M5.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 5.

The coloring composition 5 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). Table 39 shows the film thickness of the pre-baked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

Comparative example 2

The following ingredients were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M6.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 6.

The coloring composition 6 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). Table 39 shows the film thickness of the pre-baked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

In table 39, the column "AAA" shows the maximum absorption wavelength on the longest wavelength side of the absorption spectrum, and the column "BBB" shows the wavelength of the shoulder on the longest wavelength side of the absorption spectrum.

TABLE 39

Example 17

The following ingredients were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M7.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 7.

The coloring composition 7 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film. The film thickness of the resulting post-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the post-baking colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the post-baking colored coating film and the wavelength of the shoulder on the longest wavelength side of the absorption spectrum of the post-baking colored coating film are shown in table 40.

Comparative example 3

The following ingredients were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M8.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 8.

The coloring composition 8 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film. The film thickness of the resulting post-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the post-baking colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the post-baking colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the post-baking colored coating film are shown in table 40.

In table 40, the column "CCC" shows the maximum absorption wavelength on the longest wavelength side of the absorption spectrum, and the column "DDD" shows the wavelength of the shoulder on the longest wavelength side of the absorption spectrum.

TABLE 40

Comparative example 4

The following ingredients were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition MH4.

Next, the respective components were mixed in the following proportions to obtain a coloring composition H4.

The coloring composition H4 was applied to a 2-inch square glass substrate (EAGLE XG; manufactured by CORNING) by a spin coating method, and then prebaked at 100℃for 3 minutes to form a prebaked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film. The film thickness of the resulting post-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the post-baking colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the post-baking colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the post-baking colored coating film are shown in table AD1.

In tables AD1 to AD21, the column "EEE" shows the maximum absorption wavelength on the longest wavelength side of the absorption spectrum, and the column "FFF" shows the wavelength of the shoulder on the longest wavelength side of the absorption spectrum.

[ Table AD1]

Example 6-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M6-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 6-1.

The coloring composition 6-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD2. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD2]

Examples 6-2 to 6-4

A colored composition was obtained in the same manner as in example 6-1 except that the compound represented by the formula (Ia 51) was replaced with the compound described in the "colorant AAA" column in table AD3, and a pre-baked colored coating film and a post-baked colored coating film were obtained. The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD3.

[ Table AD3]

Example 7-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M7-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 7-1.

The coloring composition 7-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD4. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD4]

Examples 7-2 to 7-6

A colored composition was obtained in the same manner as in example 7-1 except that the compound represented by the formula (Ia 973) was replaced with the compound described in the "colorant AAA" column in table AD5, and a pre-baked colored coating film and a post-baked colored coating film were obtained. The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD5.

[ Table AD5]

Examples 7 to 7

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M7-7.

Next, the respective components were mixed in the following proportions to obtain coloring compositions 7 to 7.

The coloring compositions 7 to 7 were applied onto a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film. The film thickness of the resulting post-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the post-baking colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the post-baking colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the post-baking colored coating film are shown in table AD6.

[ Table AD6]

Example 90-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M90-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 90-1.

The coloring composition 90-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD7. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD7]

Examples 90-2 to 90-22

A colored composition was obtained in the same manner as in example 90-1 except that the compound represented by the formula (Ia 5) was replaced with the compound described in the "colorant AAA" column in table AD8, and a pre-baked colored coating film and a post-baked colored coating film were obtained. The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD8.

[ Table AD8]

Examples 90 to 23

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain coloring compositions M90 to 23.

Next, the respective components were mixed in the following proportions to obtain coloring compositions 90 to 23.

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The coloring composition 90-23 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film. The film thickness of the resulting post-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the post-baking colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the post-baking colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the post-baking colored coating film are shown in table AD9.

[ Table AD9]

Example 91-1

The following ingredients were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M91-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 91-1.

The coloring composition 91-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD10. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD10]

Examples 91-2 to 91-4

A colored composition was obtained in the same manner as in example 91-1 except that the compound represented by the formula (If 3796) was replaced with the compound described in the "colorant AAA" column in table AD11, and a pre-baked colored coating film and a post-baked colored coating film were obtained. The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD11.

[ Table AD11]

Example 17-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M17-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 17-1.

The coloring composition 17-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD12. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD12]

Example 12-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M12-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 12-1.

The coloring composition 12-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film. The film thickness of the resulting post-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the post-baking colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the post-baking colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the post-baking colored coating film are shown in table AD13.

[ Table AD13]

Example 13-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M13-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 13-1.

The coloring composition 13-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.).

The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD14.

The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD14]

Example 14-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M14-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 14-1.

The coloring composition 14-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD15. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD15]

Example 16-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a colored composition M16-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 16-1.

The coloring composition 16-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD16. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD16]

Example 51-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M51-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 51-1.

The coloring composition 51-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD17. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD17]

Example 571-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M571-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 571-1.

The coloring composition 571-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD18. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

Table AD18

Example 591-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M591-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 591-1.

The coloring composition 591-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD19. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

Examples 591-2

A colored composition was obtained in the same manner as in example 591-1 except that the following colorant (A) was used in place of the compound represented by the formula (Ia 1) and the compound represented by the formula (Ia 248) in the following amounts in example 591-1, to obtain a pre-baked colored coating film and a post-baked colored coating film.

2.38 parts of a mixture of the compound represented by the formula (Ia 10), the compound represented by the formula (Ia 2143), the compound represented by the formula (Ia 850) and the compound represented by the formula (Ia 315) obtained in example 4;

2.12 parts of a compound represented by the formula (Ia 51);

the film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD19.

Examples 591 to 3

2.38 parts of a compound represented by the formula (Ia 248);

2.12 parts of a compound represented by the formula (Ia 51);

Examples 591 to 4

2.64 parts of a compound represented by the formula (Ia 23);

1.86 parts of a compound represented by the formula (Ia 17);

Examples 591 to 5

2.17 parts of a compound represented by the formula (Ia 19);

2.33 parts of a compound represented by the formula (Ia 17);

[ Table AD19]

Example 592-1

The respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition M592-1.

Next, the respective components were mixed in the following proportions to obtain a coloring composition 592-1.

The coloring composition 592-1 was applied to a 2-inch square glass substrate (EAGLE XG; made by CORNING) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD20. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

Example 592-2

A colored composition was obtained in the same manner as in example 592-1 except that the following colorant (A) was used in place of the compound represented by the formula (Ia 1) and the compound represented by the formula (Ia 248) in the following amounts in example 592-1, and a pre-baked colored coating film and a post-baked colored coating film were obtained.

4.00 parts of a compound represented by the formula (Ia 5);

1.00 parts of a compound represented by the formula (Ia 248);

the film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD20.

Example 592-3

4.00 parts of a compound represented by the formula (Ia 699);

1.00 parts of a compound represented by the formula (Ia 248);

Examples 592 to 4

4.00 parts of a compound represented by the formula (Ia 5);

1.00 parts of the mixture obtained in example E-1 and containing the compound represented by the formula (Ia 5-SA 1) and the compound represented by the formula (Ia 5-SA 2);

[ Table AD20]

Example S-1

The respective components were mixed in the following proportions to obtain a coloring composition S-1.

The coloring composition S-1 was applied to a 2-inch square glass substrate (EAGLE XG; manufactured by CORNING) by a spin coating method, and then prebaked at 100℃for 3 minutes to form a prebaked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film. The film thickness of the resulting post-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the post-baking colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the post-baking colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the post-baking colored coating film are shown in table AD21.

Example S-2

The respective components were mixed in the following proportions to obtain a coloring composition S-2.

The coloring composition S-2 was applied to a 2-inch square glass substrate (EAGLE XG; manufactured by CORNING) by a spin coating method, and then prebaked at 100℃for 3 minutes to form a prebaked colored coating film. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film. The film thickness of the resulting post-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the post-baking colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the post-baking colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the post-baking colored coating film are shown in table AD21.

Example S-3

The respective components were mixed in the following proportions to obtain a coloring composition S-3.

The coloring composition S-3 was applied to a 2-inch square glass substrate (EAGLE XG; manufactured by CORNING) by a spin coating method, and then prebaked at 100℃for 3 minutes to form a prebaked colored coating film. The film thickness of the obtained pre-baked colored coating film was measured using DektakXT (manufactured by BRUKER). The spectrum of the pre-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by LambdaVision, inc.). The film thickness of the pre-baked colored coating film and the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the shoulder on the longest wavelength side of the absorption spectrum of the pre-baked colored coating film are shown in table AD21. The pre-baked colored coating film was post-baked at 230℃for 30 minutes, thereby obtaining a post-baked colored coating film.

[ Table AD21]

From the above results, it is understood that the wavelength of the maximum absorption wavelength on the longest wavelength side of the absorption spectrum or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum of the colored coating film formed from the colored composition containing the compound of the present invention is a longer wavelength than the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the colored coating film formed from the colored composition containing c.i. pigment yellow 138.

Industrial applicability

The coloring composition and the compound of the present invention can be used to form a color filter having a darker color than a coloring composition containing c.i. pigment yellow 138, and thus are preferably used for display devices such as color filters, liquid crystal display devices, and the like.

Claims

1. A coloring composition comprising a compound represented by the following formula (I) and a solvent,

in the formula (I) of the present invention,

R ¹ ～R ⁵ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, or-OCH ₃ ，

Q ¹ And Q ² Each independently represents a group represented by the formulae (QQ 1) to (QQ 5) as a 2-valent aromatic hydrocarbon group,

wherein R is ^Q1 ～R ^Q30 Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -CO ₂ H、－CO ₂ CH ₃ -OH, or-NHCOCH ₃ The symbol indicates the binding site.

2. The coloring composition according to claim 1, wherein a resin is contained.

3. The coloring composition according to claim 1 or 2, wherein a polymerizable compound and a polymerization initiator are contained.

4. A color filter formed from the coloring composition according to claim 1 or 2.

5. A display device comprising the color filter of claim 4.

6. A compound represented by the formula (I),

in the formula (I) of the present invention,