CN113454167A

CN113454167A - Coloring composition, compound, color filter and display device

Info

Publication number: CN113454167A
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: 2021-09-28
Anticipated expiration: 2040-02-14
Also published as: WO2020170957A1; CN113454167B; JP2020132878A; TW202035387A; KR20210127754A

Abstract

The present invention aims to provide 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 shoulder wavelength on the longest wavelength side of the absorption spectrum on the longer wavelength side 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 colored composition is used for manufacturing a color filter used in a display device such as a liquid crystal display device and an electroluminescent display device. As a colorant contained in the coloring composition, c.i. pigment yellow 138 is known (patent document 1).

(C.I. pigment yellow 138)

Documents of the prior art

Patent document

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

Disclosure of Invention

In recent years, displays have been developed to expand the displayable color reproduction area, and as one of them, color filters are also required to have darker colors. In order to satisfy this requirement, a coloring composition containing a compound having a maximum absorption wavelength on the longest wavelength side of the absorption spectrum at a wavelength longer than the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of conventionally known c.i. pigment yellow 138 and/or a compound having a wavelength of a shoulder at the longest wavelength side of the absorption spectrum is required.

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

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

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

[ in the formula (I),

R¹～R⁵each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group or-SO₃M、－CO₂M, MM, a C1-valent hydrocarbon group or a C1-valent heterocyclic group having 1-40 carbon atoms,

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

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

the-CH ═ constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by-N ═ or,

-CH constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group₂May 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 by a halogen atom, a cyano group, a nitro group or a-SO group₃M、－CO₂M or MM.

R¹And R²、R²And R³And R³And R⁴May be bonded to each other to form a ring.

M represents a hydrogen atom, an alkali metal atom, a metal atom which may have a ligand, or N (Z)¹)(Z²)(Z³)(Z⁴)。

MM represents an alkali metal atom, a metal atom which may have a ligand, or N (Z)¹)(Z²)(Z³)(Z⁴)。

Z¹～Z⁴Each independently represents a hydrogen atom, a C1-valent hydrocarbon group having 1 to 40 carbon atoms or a C1-valent heterocyclic group having 1 to 40 carbon atoms,

Q¹And Q²Each independently represents a 2-valent hydrocarbon group or a 2-valent heterocyclic group,

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

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

the-CH ═ constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted by-N ═ or,

-CH constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group₂May 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 by a halogen atom, a cyano group, a nitro group or a-SO group₃M、－CO₂M or MM.

Z¹～Z⁴When plural, M and MM are present, respectively, they may be the same as or different from each other.]

[2] The coloring composition according to [1], which comprises a resin.

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

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

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

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

[ in the formula (I),

According to the present invention, there are provided a coloring composition and a compound which can be used for forming a color filter of a darker color than a coloring composition containing c.i. pigment yellow 138.

Detailed Description

[ coloring composition ]

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

[ in the formula (I),

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

The compound (I) can 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, may be referred to as resin (B)).

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

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

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

The coloring composition of the present invention may contain a colorant other than the compound (I) (hereinafter, sometimes referred to as the colorant (a 1); and hereinafter, sometimes referred to as the compound (I) and the colorant (a1) are collectively referred to as the "colorant (a)").

The colorant (a1) may contain 1 or 2 or more colorants.

The colorant (a1) preferably contains 1 or more selected from a yellow colorant, an orange colorant, a red colorant and a green colorant.

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

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

[ Compound (I) ]

Hereinafter, the present invention will be described more specifically by referring to the partial structure of the compound (I), and in each partial structure, even when only the case where a substituent bonded to a ring structure is bonded to a certain portion of the ring structure is exemplified, the following examples include the case where the substituent is bonded to all the portions of the ring structure. When 1 or 2 or more substituents are bonded to the ring structure, and 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, an iodine atom and the like, and a fluorine atom, a chlorine atom and a bromine atom are preferable.

R¹～R⁵And Z¹～Z⁴The 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, and particularly preferably 1 to 12.

R¹～R⁵And Z¹～Z⁴The 1-valent hydrocarbon group having 1 to 40 carbon atoms represented by the formula (I) 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 R¹～R⁵And Z¹～Z⁴Examples of the saturated or unsaturated chain hydrocarbon group 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, hentriacontyl, dotriacontyl, tritriacontyl, tetratriacontyl, pentadecanyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and forty-alkyl groups; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylbutyl group, 3, 3-dimethylbutyl group, 1,3, 3-tetramethylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, 3-methylbutyl group, neopentyl group, 1-dimethylpropyl group, 2-methylpentyl group, 3-ethylpentyl group, 1, 3-dimethylbutyl group, 2-propylpentyl group, 1-ethyl-1, 2-dimethylpropyl group, 1-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylhexyl group, 1-methylhexyl group, 1-ethylpentyl group, 1-propylbutyl group, 3-ethylheptyl group, 2-dimethylheptyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-methyloctyl group, 1-ethylheptyl group, 1-propylhexyl group, 1-butylpentyl group, 1-methylnonyl group, Branched alkyl groups such as 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) Alkenyl groups such as an alkenyl group (e.g., 1-nonenyl group, 8-nonenyl group), a decenyl group (e.g., 1-decenyl group, 9-decenyl group), an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, an eicosenyl group, a 1, 1-dimethyl-2-propenyl group, a 1-ethyl-2-propenyl group, and a 1-methyl-1-butenyl group); ethynyl, propynyl (e.g., 1-propynyl, 2-propynyl), octynyl (e.g., 1-octynyl, 7-octynyl), butynyl, pentynyl, hexynyl, heptynyl, nonynyl, decynyl, undecylynyl, dodecynyl, tridecynyl, and the likeCarbon (C)Alkynyl groups such as alkynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, and eicosynyl; and the like. The number of carbon atoms of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 18, and particularly preferably 1 to 12. Among them, a linear or branched alkyl group having 1 to 12 carbon atoms is particularly preferable.

As R¹～R⁵And Z¹～Z⁴Examples of the saturated or unsaturated alicyclic hydrocarbon group 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, 2,4, 6-trimethylcyclohexyl, 2,6, 6-tetramethylcyclohexyl, 3,5, 5-tetramethylcyclohexyl, 2, 6-tetramethylcyclohexyl, 3,5, 5-tetramethylcyclohexyl, Cycloalkyl groups such as 4-pentylcyclohexyl, 4-octylcyclohexyl and 4-cyclohexylcyclohexyl; cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-1-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl), cycloheptenyl, and cyclooctenyl; norbornyl, norbornenyl, adamantyl and bicyclo [2.2.2 ]Octyl group and the likeA saturated or unsaturated polycyclic hydrocarbon group; and the like. The number of carbon atoms of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, further preferably 3 to 18, and particularly preferably 3 to 12. Among them, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl groups are particularly preferable.

As R¹～R⁵And Z¹～Z⁴The aromatic hydrocarbon group may include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2, 3-dimethylphenyl group, a 2, 4-dimethylphenyl group, a 2, 5-dimethylphenyl group, a 2, 6-dimethylphenyl group, a 3, 4-dimethylphenyl group, a 3, 5-dimethylphenyl group, a 4-vinylphenyl group, an o-isopropylphenyl group, a m-isopropylphenyl group, a p-isopropylphenyl group, an o-tert-butylphenyl group, a m-tert-butylphenyl group, a p-tert-butylphenyl group, a 3, 5-di (tert-butyl) phenyl group, a 3, 5-di (tert-butyl) -4-methylphenyl group, a 4-butylphenyl group, a 4-pentylphenyl group, a 2, 6-bis (1-methylethyl) phenyl group, a 2,4, 6-tris (1-methylethyl) phenyl group, a 4-cyclohexylphenyl group, a 2,4, 6-trimethylphenyl group, a, 4-octylphenyl group, 4- (1,1,3, 3-tetramethylbutyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 6-methyl-2-naphthyl group, 5,6,7, 8-tetrahydro-1-naphthyl group, 5,6,7, 8-tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthracenyl group, 2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group, peryleneyl group, perylene group, etc,

Aromatic hydrocarbon groups such as a pyrenyl group and the like; and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, further preferably 6 to 18, and particularly preferably 6 to 12.

R¹～R⁵And Z¹～Z⁴The hydrocarbon group may be a combination of the hydrocarbon groups (for example, an aromatic hydrocarbon group and at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group) mentioned above, and examples thereof include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, a (4-methylphenyl) methyl group, a (2-ethylphenyl) methyl group, a (3-ethylphenyl) methyl group, a (4-ethylphenyl) methyl group, a (2- (tert-butyl) methyl group, and a (3-d-butyl) alkyl groupAralkyl groups such as 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 group, 2-phenylvinyl group (phenylvinyl group), 2-diphenylvinyl group, and 2-phenyl-2- (1-naphthyl) vinyl group; arylalkynyl groups such as phenylethynyl; a phenyl group having 1 or more phenyl groups bonded thereto, such as a biphenyl group and a terphenyl group; cyclohexylmethylphenyl, benzylphenyl, (dimethyl (phenyl) methyl) phenyl, and the like.

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

R¹～R⁵And Z¹～Z⁴Examples of the group represented by the above-mentioned groups obtained by combining the above-mentioned hydrocarbon groups (for example, a chain hydrocarbon group and an alicyclic hydrocarbon group) include an alkyl group in which 1 or more alicyclic hydrocarbon groups are bonded, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, (2-methylcyclohexyl) methyl group, a cyclohexylethyl group, and an adamantylmethyl group.

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

R¹～R⁵And Z¹～Z⁴The 1-valent heterocyclic group having 1 to 40 carbon atoms represents a group containing a heteroatom as a constituent element of a ring. The 1-valent heterocyclic group having 1 to 40 carbon atoms may be a monocyclic ring or a polycyclic ring. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom and the like.

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

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

Examples of the heterocycle containing an oxygen atom include oxetane, tetrahydrofuran, tetrahydropyran, and 1, 3-bis

Alkanes and 1, 4-bis

Monocyclic saturated heterocycles such as 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 heterocycles such as nonane; lactone heterocycles such as α -caprolactone, β -propiolactone, γ -butyrolactone, γ -valerolactone and δ -valerolactone; 5-membered unsaturated heterocycles such as furan, 2, 3-dimethylfuran, 2, 5-dimethylfuran and the like; 6-membered ring unsaturated heterocycles such as 2H-pyran and 4H-pyran; benzofuran such as 1-benzofuran, benzopyran such as benzopyran and 4-methylbenzopyran, methylenedioxybenzene, 1, 3-methylenedioxybenzene, and benzodi

Fused bicyclic heterocycles such as an alkane, chroman and isochroman; fused tricyclic heterocycles such as xanthene and dibenzofuran; and the like.

Examples of the heterocycle containing a sulfur atom include a 5-membered saturated heterocycle such as dithiolane; 6-membered saturated heterocycles such as thiane, 1, 3-dithiane and 2-methyl-1, 3-dithiane; thiophene such as thiophene, 3-methylthiophene and 2-carboxythiophene, thiopyran such as 2H-thiopyran and 4H-thiopyran, thiochroman such as tetrahydrothiopyran, and 5-membered ring-based unsaturated heterocyclic ring and 6-membered ring-based unsaturated heterocyclic ring; fused bicyclic heterocycles such as thiochromanes and benzothiophenes; fused tricyclic heterocycles such as thianthrene and dibenzothiophene; and the like.

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

Azoles and the like

Azole, 2-methyliso

Azole, 3-methyliso

Azole, 4-methyliso

Azole, 5-methyliso

Azole or the like

Monocyclic unsaturated heterocycles such as oxazole; benzo (b) is

Azole, benzisoh

Azole, benzo

Oxazine and benzodi

Fused bicyclic heterocycles such as an alkane and benzimidazoline; phen

Fused tricyclic heterocycles such as oxazines; and the like.

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

The bonding position of the heterocyclic group is a portion where any hydrogen atom contained in each heterocyclic ring is removed.

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

The heterocyclic group may be a group represented by the following formula. The bonding sites are indicated in the opposite.

-CH constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group₂Can be substituted as-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 by a halogen atom, a cyano group, a nitro group or a-SO group₃M、－CO₂M or MM. Examples of such a group include the following groups.

Examples thereof include trichloromethyl group, trifluoromethyl group, 2,2, 2-trifluoroethyl group, 2, 2-dibromoethyl group, 2,2,3, 3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, diethylaminoethyl group, (4-methoxyphenyl) methyl group, (2-methoxyphenyl) methyl group, (3-methoxyphenyl) methyl group, (4-nitrophenyl) methyl group, (2, 4-dichlorophenyl) methyl group, (4-fluorophenyl) methyl group, (3, 5-difluorophenyl) methyl group, 2,2, 2-trifluoro-1-trifluoromethyl-1-phenylethyl group, (phenoxy) (phenyl) methyl group, (benzyloxy) (phenyl) methyl group, pyrrolylmethyl group, pyrrolylethyl group, (4-aminophenyl) methyl group, (4-cyanophenyl) methyl group, 2-hydroxy-1-methyl-1-phenylethyl group, trichloromethyl group, trifluoromethyl group, 2,2,2, 3, 3-tetrafluoropropyl group, 2-methoxyphenyl) methyl group, 4-methyl group, and the like, 2-chloro-1-methyl-1-phenylethyl; -CH ₂CH₂OCH₂CH₃、－CH₂CH₂O(CH₂)₃CH₃、－(CH₂CH₂O)₂CH₂CH₃、－(CH₂CH₂O)₃CH₂CH₃、－(CH₂CH₂O)₄CH₂CH₃、－(CH₂CH₂O)₅CH₂CH₃、－(CH₂CH₂O)₆CH₂CH₃、－(CH₂CH₂O)₇CH₂CH₃、－(CH₂CH₂O)₈CH₂CH₃、－(CH₂CH₂O)₉CH₂CH₃、－(CH₂CH₂O)₁₀CH₂CH₃、－(CH₂CH₂O)₁₁CH₂CH₃、－(CH₂CH₂O)₁₂CH₂CH₃、－(CH₂CH₂O)₁₃CH₃、－CH₂CH₂OH、－(CH₂CH₂O)₂H、－(CH₂CH₂O)₃H、－(CH₂CH₂O)₄H、－(CH₂CH₂O)₅H、－(CH₂CH₂O)₆H、－(CH₂CH₂O)₇H、－(CH₂CH₂O)₈H、－(CH₂CH₂O)₉H、－(CH₂CH₂O)₁₀H、－(CH₂CH₂O)₁₁H、－(CH₂CH₂O)₁₂H、－(CH₂CH₂O)₁₃H、－CH₂CH₂OCH₃、－(CH₂CH₂O)₂CH₃、－(CH₂CH₂O)₃CH₃、－(CH₂CH₂O)₄CH₃、－(CH₂CH₂O)₅CH₃、－(CH₂CH₂O)₆CH₃、－(CH₂CH₂O)₇CH₃、－(CH₂CH₂O)₈CH₃、－(CH₂CH₂O)₉CH₃、－(CH₂CH₂O)₁₀CH₃、－(CH₂CH₂O)₁₁CH₃、－(CH₂CH₂O)₁₂CH₃、－(CH₂CH₂O)₁₃CH₃-CH having the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group₂-a group substituted with-O-; and the like (hereinafter, they may be referred to as groups of group A).

Examples thereof include aryl groups having a substituent (hereinafter, these may be referred to as groups of group B) 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, 2-aminoanthraquinone group and the like.

For example, a formyl group; acetyl, propionyl, butyryl, 2-dimethylpropionyl, pentanoyl, hexanoyl, 2-ethylhexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, heneicosanoyl, benzoyl, pentanoyl, hexanoyl, decanoyl, undecanoyl, dodecanoyl, hexanoyl, and hexanoyl,

And a carbonyl group to which the group of the above-mentioned group A to group B or the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded,

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

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

More preferably a carbonyl group to which a hydrocarbon group having 1 to 18 carbon atoms, a group of the above-mentioned groups A to B, or a group preferred as the above-mentioned 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-mentioned groups A to B, or a group preferred as the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded.

The bonding sites are indicated in the opposite.

Examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, (2-ethylhexyl) oxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, eicosyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, eicosyloxycarbonyl, ethyloxycarbonyl,

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

the preferred examples of the "oxycarbonyl" group include, but are not limited to, an oxycarbonyl group to which a hydrocarbon group having 1 to 30 carbon atoms, a group from the above-mentioned group A to group B, or a preferred group from the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded, a more preferred oxycarbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms, a group from the above-mentioned group A to group B, or a preferred group from the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded, a further preferred oxycarbonyl group to which a hydrocarbon group having 1 to 18 carbon atoms, a preferred group from the above-mentioned group A to group B, or a preferred group from the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded, and a particularly preferred oxycarbonyl group to which a hydrocarbon group having 1 to 12 carbon atoms, a preferred group from the above-mentioned group A to group B, or a preferred group from the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group. The bonding sites are indicated in the opposite.

For example, formyloxy; acetoxy, propionyloxy, butyryloxy, (2, 2-dimethylpropionyl) oxy, valeryloxy, hexanoyloxy, (2-ethylhexanoyl) oxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, heneicosanoyloxy, benzoyloxy, vinylcarbonyloxy, (2-propenyl) carbonyloxy, (1-methylvinyl) carbonyloxy, and carbonyloxy to which the above group A to group B groups or the above-mentioned hydrocarbon group having a valence of 1 or heterocyclic group having a valence of 1 are bonded, and the like,

the carbonyl group to which a hydrocarbon group having 1 to 30 carbon atoms, a group of the above-mentioned groups A to B, or a group preferred for the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is preferred, the carbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms, a group of the above-mentioned groups A to B, or a group preferred for the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is more preferred, the carbonyl group to which a hydrocarbon group having 1 to 18 carbon atoms, a group of the above-mentioned groups A to B, or a group preferred for the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is further preferred, and the carbonyl group to which a hydrocarbon group having 1 to 12 carbon atoms, a group of the above-mentioned groups A to B, or a group preferred for the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group.

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, dodecyloxy, (2-ethylhexyloxy), dodecyloxy, 1-phenylethoxy, 1-ethylhexyloxy, 1-methyloxy, 2, 3-dimethylphenoxy, 2, 4-dicyanophenoxy, 2, 5-dicyanophenyloxy, 2, 3-dicyanophenyloxy, 3-decylphenoxy, 2, 4-dimethylphenoxy, 2, 4-dicyanophenyloxy, 2, 4-decylphenoxy, 2, 4-dimethylphenoxyl, 2, 4-decylphenoxy, 2, and a, 2-ethoxyphenoxy group, 3-ethoxyphenoxy group; trichloromethoxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, 2,2,3, 3-tetrafluoropropoxy, 3,3, 3-trifluoro-2-trifluoromethyl-2-methylpropoxy, 2-butoxyethoxy, 2-nitropropoxy, -OCH ₂CH₂OH、－O(CH₂CH₂O)₄H、－OCH₂CF₂CF₂H、－OCH₂CH₂O(CH₂)₃CH₃、－OCH₂CH₂OCH₂CH₃、－O(CH₂CH₂O)₂CH₂CH₃、－O(CH₂CH₂O)₄CH₂CH₃、－OCH₂CH₂O(CH₂)₃CH₃、

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

the group preferably has a hydrocarbon group having 1 to 30 carbon atoms, a group A to a group B described above, or an oxo group or a hydroxy group bonded to a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group described above, more preferably a hydrocarbon group having 1 to 20 carbon atoms, a group A to a group B described above, or an oxo group or a hydroxy group bonded to a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group described above, still more preferably a hydrocarbon group having 1 to 18 carbon atoms, a group A to a group B described above, or an oxo group or a hydroxy group bonded to a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group described above, and particularly preferably a hydrocarbon group having 1 to 12 carbon atoms, a group from the group A described above to a group B described above, or an oxo group or a hydroxy group bonded to a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group described above. The bonding sites are indicated in the opposite.

Examples thereof include mercapto groups; methylthio, ethylthio, propylthio, butylthio, t-butylthio, pentylthio, hexylthio, (2-ethylhexyl) thio, heptylthio, octylthio, nonylthio, decylthio, undecylthio, dodecylthio, eicosylthio, phenylthio, o-tolylthio, O-tolylthio, N-tolylthio, S-butylthio, S-substituted or S-tolylthio,

And mercapto groups substituted with hydrogen atoms of the above groups A to B or the above 1-valent hydrocarbon groups or 1-valent heterocyclic groups,

preferably, the hydrogen atom is substituted with a mercapto group or a mercapto group of a hydrocarbon group having 1 to 30 carbon atoms, a group of the groups A to B or a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group, more preferably the hydrogen atom is substituted with a hydrocarbon group having 1 to 20 carbon atoms, a group of the groups A to B or a mercapto group of a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group, still more preferably the hydrogen atom is substituted with a hydrocarbon group having 1 to 18 carbon atoms, a mercapto group or a mercapto group of a group of the groups A to B or a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group, and particularly preferably the hydrogen atom is substituted with a hydrocarbon group having 1 to 12 carbon atoms, a group of the groups A to B or a mercapto group of a group preferred group for the 1-valent hydrocarbon group or the 1-valent heterocyclic group. The bonding sites are indicated in the opposite.

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

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

the sulfonyl group to which a hydrocarbon group having 1 to 30 carbon atoms, a group A to group B described above, or a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group described above is bonded is preferred, the sulfonyl group to which a hydrocarbon group having 1 to 20 carbon atoms, a group of the group A to group B described above, or a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group described above is bonded is more preferred, the sulfonyl group to which a hydrocarbon group having 1 to 18 carbon atoms, a group of the group A to group B described above, or a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group described above is bonded is further preferred, and the sulfonyl group to which a hydrocarbon group having 1 to 12 carbon atoms, a group of the group A to group B described above, or a group preferred for the 1-valent hydrocarbon group or the 1-valent heterocyclic group described above is bonded is particularly preferred. The bonding sites are indicated in the opposite.

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-sulfamoyl ₂NH(CH₂)₂N(CH₂CH₃)₂、－SO₂NHCH₂CH₂CH₂Si(OCH₂CH₃)₃And sulfamoyl groups substituted with 1 of the groups of groups A to B, the 1-valent hydrocarbon group or the 1-valent heterocyclic group;

n, N-dimethylsulfamoyl, N-ethyl-N-methylsulfamoyl, N-diethylsulfamoyl, N-propyl-N-methylsulfamoyl, N-dipropylsulfamoyl, N-isopropyl-N-methylsulfamoyl, N-diisopropylsulfamoyl, N-diisobutylsulfamoyl, N-di (sec-butyl) sulfamoyl, N- (tert-butyl) -N-methylsulfamoyl, 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-dihexylsulfamoyl, N-dihexylsulfamoyl, N- (2-ethylhexyl) -N-methylsulfamoyl, N-bis (2-ethylhexyl) sulfamoyl, N-diheptylsulfamoyl, N-octyl-N-methylsulfamoyl, N-dioctylsulfamoyl, N-dinonylsulfamoyl, N-decyl-N-methylsulfamoyl, N-undecyl-N-methylsulfamoyl, N-dodecyl-N-methylsulfamoyl, N-eicosyl-N-methylsulfamoyl, N-phenyl-N-methylsulfamoyl, N-diphenylsulfamoyl, and sulfamoyl groups substituted with 2 groups selected from the above-mentioned groups A to B, the above-mentioned 1-valent hydrocarbon group and the above-mentioned 1-valent heterocyclic group, and the like,

Preferably 1 or 2 sulfamoyl groups, -SO substituted by a group selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, the groups of the 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 group₂NH(CH₂)₂N(CH₂CH₃)₂Or a sulfamoyl group, more preferably a sulfamoyl group substituted with 1 or 2 members selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, the groups of the above-mentioned 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, -SO₂NH(CH₂)₂N(CH₂CH₃)₂Or a sulfamoyl group, more preferably a sulfamoyl group substituted with 1 or 2 members selected from the group consisting of a hydrocarbon group having 1 to 18 carbon atoms, the groups of the above-mentioned 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, -SO₂NH(CH₂)₂N(CH₂CH₃)₂Or a sulfamoyl group, particularly preferably a sulfamoyl group which is substituted by 1 or 2 members selected from the group consisting of a hydrocarbon group having 1 to 12 carbon atoms, the groups of the above-mentioned 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, -SO₂NH(CH₂)₂N(CH₂CH₃)₂Or a sulfamoyl group.

For example, a carbamoyl group; n-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-isopropylcarbamoyl, N-butylcarbamoyl, N-isobutylcarbamoyl, N- (sec-butyl) carbamoyl, N- (tert-butyl) carbamoyl, 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)₂N(CH₂CH₃)₂、－CONHCH₂CH₂CH₂Si(OCH₂CH₃)₃And a carbamoyl group substituted with 1 of the groups of the above groups A to B or the above-mentioned 1-valent hydrocarbon group or 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-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 group, N- (2-ethylhexyl) -N-methylcarbamoyl group, N-bis (2-ethylhexyl) carbamoyl group, N-diheptylcarbamoyl group, N-octyl-N-methylcarbamoyl group, N-dioctylcarbamoyl group, N-dinonylcarbamoyl group, N-decyl-N-methylcarbamoyl group, N-undecyl-N-methylcarbamoyl group, N-dodecyl-N-methylcarbamoyl group, N-eicosyl-N-methylcarbamoyl group, N-phenyl-N-methylcarbamoyl group, N-diphenylcarbamoyl group, and carbamoyl groups substituted with 2 members selected from the above-mentioned group A to group B, the above-mentioned hydrocarbon group having a valence of 1 and the above-mentioned heterocyclic group having a valence of 1, and the like,

Preferably a carbamoyl group or a carbamoyl group substituted with 1 or 2 members selected from a hydrocarbon group having 1 to 30 carbon atoms, a group selected from the above-mentioned groups A to B, a group preferred to the above-mentioned 1-valent hydrocarbon group and a group preferred to the above-mentioned 1-valent heterocyclic group, more preferably a carbamoyl group or a carbamoyl group substituted with 1 or 2 members selected from a hydrocarbon group having 1 to 20 carbon atoms, a group selected from the above-mentioned groups A to B, a group preferred to the above-mentioned 1-valent hydrocarbon group and a group preferred to the above-mentioned 1-valent heterocyclic group, still more preferably a carbamoyl group or a carbamoyl group substituted with 1 or 2 members selected from a hydrocarbon group having 1 to 18 carbon atoms, a group selected from the above-mentioned groups A to B, a group preferred to the above-mentioned 1-valent hydrocarbon group and a group preferred to the above-mentioned 1-valent heterocyclic group, particularly preferably a carbamoyl group or a carbamoyl group substituted with a group selected from a hydrocarbon group having 1 to 12 carbon atoms, a pharmaceutically acceptable salt, and a pharmaceutically acceptable salt, Carbamoyl group or carbamoyl group of 1 or 2 of the groups of the above-mentioned 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.

For example, an amino group; n-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino, N-isobutylamino, N- (sec-butyl) amino, N- (tert-butyl) amino, 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 of the above groups A to B or the above-mentioned hydrocarbon group having a valence of 1 or heterocyclic group having a valence of 1, etc.;

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-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-dihexylamino, N- (2-ethylhexyl) -N-methylamino, N-bis (2-ethylhexyl) amino, N, 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, amino substituted with 2 groups selected from the above-mentioned group A to group B, the above-mentioned hydrocarbon group having a valence of 1 and the above-mentioned heterocyclic group having a valence of 1, and the like,

Preferably substituted with 1 or 2 amino groups or amino groups selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, the group A to the group B, the group preferred for a hydrocarbon group having 1 valence, and the group preferred for a heterocyclic group having 1 valence, more preferably substituted with 1 or 2 amino groups or amino groups selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, the group A to the group B, the group preferred for a hydrocarbon group having 1 valence, and the group preferred for a heterocyclic group having 1 valence, still more preferably substituted with 1 or 2 amino groups or amino groups selected from the group consisting of a hydrocarbon group having 1 to 18 carbon atoms, the group A to the group B, the group preferred for a hydrocarbon group having 1 valence, and the group preferred for a heterocyclic group having 1 valence, particularly preferably substituted with 1 or 2 amino groups selected from the group consisting of a hydrocarbon group having 1 to 12 carbon atoms, the group A to the group B, the group preferred for a hydrocarbon group having 1 valence, and the group preferred for a heterocyclic group having 1 valence Amino or amino groups.

For example, formylamino; acetylamino, propionylamino, butyrylamino, (2, 2-dimethylpropionyl) amino, pentanoylamino, hexanoylamino, (2-ethylhexanoyl) amino, heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoylamino, dodecanoylamino, heneicosanoylamino, benzoylamino, hexanoylamino, heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoylamino, dodecanoylamino, heneicosanoylamino, benzoylamino, hexanoylamino, amino, hexanoylamino, amino, hexanoylamino, and, amino, and, amino, and its salt, and its derivatives,

And a carbonylamino group to which the group of the above-mentioned group A to group B or the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded,

the preferred carbonylamino group to which a hydrocarbon group having 1 to 30 carbon atoms, a group from the above-mentioned group A to group B, or a preferred group from the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is preferable, the more preferred carbonylamino group to which a hydrocarbon group having 1 to 20 carbon atoms, a group from the above-mentioned group A to group B, or a preferred group from the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is, the more preferred carbonylamino group to which a hydrocarbon group having 1 to 18 carbon atoms, a preferred group from the above-mentioned group A to group B, or a preferred group from the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is, and the most preferred carbonylamino group to which a hydrocarbon group having 1 to 12 carbon atoms, a preferred group from the above-mentioned group A to group B, or a preferred group from the above-mentioned 1-valent hydrocarbon group or 1-valent heterocyclic group is bonded is particularly preferable. The bonding sites are indicated in the opposite.

For example, mention may be made of-SiH₃；－Si(CH₃)₃、－Si(CH₂CH₃)₃、－Si((CH₂)₂CH₃)₃、－Si(CH(CH₃)₂)₃、－Si((CH₂)₃CH₃)₃、－Si((CH₂)₄CH₃)₃、－Si((CH₂)₅CH₃)₃、－Si((CH₂)₆CH₃)₃、－Si((CH₂)₇CH₃)₃、－Si((CH₂)₈CH₃)₃、－Si((CH₂)₉CH₃)₃、－Si((CH₂)₁₀CH₃)₃、－Si((CH₂)₁₁CH₃)₃、－Si((CH₂)₁₂CH₃)₃、－Si(C₆H₅)₃、－Si(C₁₀H₇)₃、－Si(CH₃)₂(CH₂CH₃)、－Si(CH₃)₂((CH₂)₂CH₃)、－Si(CH₃)₂(CH(CH₃)₂)、－Si(CH₃)₂((CH₂)₃CH₃)、－Si(CH₃)₂((CH₂)₅CH₃)、－Si(CH₃)₂((CH₂)₇CH₃)、－Si(CH₃)₂((CH₂)₉CH₃)、－Si(CH₃)₂((CH₂)₁₁CH₃)、－Si(CH₃)₂((CH₂)₁₃CH₃)、－Si(CH₃)₂((CH₂)₁₅CH₃)、－Si(CH₃)₂((CH₂)₁₇CH₃)、－Si(CH₃)₂((CH₂)₁₉CH₃)、－Si(CH₃)₂((CH₂)₂₉CH₃)、－Si(CH₃)₂(C₆H₅)、－Si(CH₃)(C₆H₅)₂、－Si(CH₃)₂(C₁₀H₇) And is substituted with1, 2 or 3-SiH groups selected from the group consisting of the group A to the group B, the 1-valent hydrocarbon group, and the 1-valent heterocyclic group₃Etc.;

－Si(OH)₃；－Si(OCH₃)₃、－Si(OCH₂CH₃)₃、－Si(O(CH₂)₂CH₃)₃、－Si(OCH(CH₃)₂)₃、－Si(O(CH₂)₃CH₃)₃、－Si(O(CH₂)₄CH₃)₃、－Si(O(CH₂)₅CH₃)₃、－Si(O(CH₂)₆CH₃)₃、－Si(O(CH₂)₇CH₃)₃、－Si(O(CH₂)₈CH₃)₃、－Si(O(CH₂)₉CH₃)₃、－Si(O(CH₂)₁₀CH₃)₃、－Si(O(CH₂)₁₁CH₃)₃、－Si(OC₆H₅)₃、－Si(OC₁₀H₇)₃、－Si(OCH₃)₂(OCH₂CH₃)、－Si(OCH₃)₂(O(CH₂)₂CH₃)、－Si(OCH₃)₂(OCH(CH₃)₂)、－Si(OCH₃)₂(O(CH₂)₃CH₃)、－Si(OCH₃)₂(O(CH₂)₅CH₃)、－Si(OCH₃)₂(O(CH₂)₇CH₃)、－Si(OCH₃)₂(O(CH₂)₉CH₃)、－Si(OCH₃)₂(O(CH₂)₁₁CH₃)、－Si(OCH₃)₂(O(CH₂)₁₃CH₃)、－Si(OCH₃)₂(O(CH₂)₁₅CH₃)、－Si(OCH₃)₂(O(CH₂)₁₇CH₃)、－Si(OCH₃)₂(O(CH₂)₁₉CH₃)、－Si(OCH₃)₂(O(CH₂)₂₉CH₃)、－Si(OCH₃)₂(OC₆H₅)、－Si(OCH₃)(OC₆H₅)₂、－Si(OCH₃)₂(OC₁₀H₇) and-Si (OH) substituted with 1, 2 or 3 members selected from the group consisting of the group A to the group B, the 1-valent hydrocarbon group and the 1-valent heterocyclic group ₃Etc.;

－SiH(OH)₂；－Si(CH₃)(OCH₃)₂、－Si((CH₂)₁₁CH₃)(O(CH₂)₁₁CH₃)₂、－Si(C₆H₅)(OC₆H₅)₂、－Si(CH₃)(OH)₂、－Si((CH₂)₃₆CH₃)(OH)₂、－Si(C₆H₅)(OH)₂and-SiH (OH) substituted with 1, 2 or 3 members selected from the group consisting of the group A to the group B, the 1-valent hydrocarbon group and the 1-valent heterocyclic group₂Etc.;

－SiH₂(OH)；－Si(CH₃)₂(OCH₃)、－Si((CH₂)₁₁CH₃)₂(O(CH₂)₁₁CH₃)、－Si(C₆H₅)₂(OC₆H₅)、－Si(CH₃)₂(OH)、－Si((CH₂)₁₇CH₃)₂(OH)、－Si(C₆H₅)₂(OH) and-SiH substituted by 1, 2 or 3 members selected from the group consisting of the group A to the group B, the 1-valent hydrocarbon group and the 1-valent heterocyclic group₂(OH), and the like.

Preferably substituted with 1, 2 or 3-SiH groups selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, the groups of the 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 group₃、－Si(OH)₃、－SiH(OH)₂and-SiH₂(OH), or-Si (OH)₃More preferably, it is substituted with a substituent selected from the group consisting of the number of carbon atoms1 to 20-SiH of 1, 2 or 3 of the hydrocarbon group, the groups of the groups A to B, the group preferred for the 1-valent hydrocarbon group and the group preferred for the 1-valent heterocyclic group₃、－Si(OH)₃、－SiH(OH)₂and-SiH₂(OH), or-Si (OH)₃Further, 1, 2 or 3-SiH groups selected from the group consisting of a hydrocarbon group having 1 to 18 carbon atoms, the groups of the groups A to B, the group preferred for the 1-valent hydrocarbon group and the group preferred for the 1-valent heterocyclic group are substituted₃、－Si(OH)₃、－SiH(OH)₂and-SiH₂(OH), or-Si (OH)₃Particularly preferred is an-SiH group substituted with 1, 2 or 3 members selected from the group consisting of a hydrocarbon group having 1 to 12 carbon atoms, the groups of the above-mentioned 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 ₃、－Si(OH)₃、－SiH(OH)₂and-SiH₂(OH), or-Si (OH)₃。

For example, phthalimidemethyl (C) which may have a substituent₆H₄(CO)₂N－CH₂-) and examples of the substituent include at least 1 selected from the group consisting of the above-mentioned halogen atom, the above-mentioned groups of groups A to B, the above-mentioned 1-valent hydrocarbon group, the above-mentioned 1-valent heterocyclic group and the like.

As other groups, mention may be made of-SCOCH₃、

The bonding sites are indicated in the opposite.

The 1-valent hydrocarbon group or the 1-valent heterocyclic group may be substituted with-SO₃ ^-N⁺(C₁₂H₂₅)(CH₃)₃、－CO₂ ^-N⁺(C₁₂H₂₅)(CH₃)₃、－SO₃ ^-、－CO₂ ^-And the like.

R¹And R²、R²And R³And R³And R⁴Each of which may be bonded to each other to form a ring.

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

Examples of the metal atom which may have a ligand metal atom represented by M and MM include metal atoms belonging to groups IIA to VA of the periodic Table of the 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, further preferably Mg, Ca, Sr, Ba, Ni, Zn, Cu, Fe, Co, Sn, Mn, Al, Cr, 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, NO₃、SO₄、CH₃CO₂And OH, a ligand coordinated to the metal atom, and a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or the like contained in the same ligand may be coordinated to the same metal atom, and a plurality of different ligands may be coordinated to the same metal atom in the 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 may further contain a compound (I) after removing the metal atom which may have a ligand. The compounds (I) according to the invention also contain such oligomers or polymers. Wherein the charge of compound (I) is 0.

Examples of such a compound (I) include metal salts represented by the following formulae (EN1) to (EN 5). In the formulae (EN1) to (EN5), the structure shown in (a) represents a repeating bond as in an oligomer or a polymer. For example, the metal salt represented by the formula (EN1) means that the same ligand is coordinated to the same metal atom. For example, the metal salts represented by the formulae (EN2) to (EN3) represent oligomers in which a plurality of different ligands are coordinated to the same metal atom. For example, the metal salts represented by the formulae (EN4) to (EN5) represent oligomers or polymers formed by coordinating a plurality of different ligands to the same metal atom.

N (Z) as represented by M and MM¹)(Z²)(Z³)(Z⁴) Examples thereof include NH₄；NH₃((CH₂)₇CH₃)、NH₃((CH₂)₁₁CH₃)、NH₃((CH₂)₁₇CH₃) NH being equal₄A group substituted with 1 alkyl group; n (CH)₃)₃((CH₂)₁₅CH₃)、N(CH₃)₃((CH₂)₁₁CH₃)、N(CH₃)₂((CH₂)₁₁CH₃)₂、N(CH₃)₂((CH₂)₁₇CH₃)₂NH being equal₄A group substituted with 4 alkyl groups; and NH substituted by 1, 2, 3 or 4 of the group selected from the group consisting of the above-mentioned group A to group B, the above-mentioned 1-valent hydrocarbon group and the above-mentioned 1-valent heterocyclic group₄And the like.

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；NH₃((CH₂)₇CH₃)、NH₃((CH₂)₁₁CH₃)、NH₃((CH₂)₁₇CH₃) NH being equal₄A group substituted with 1 alkyl group; n (CH)₃)₃((CH₂)₁₅CH₃)、N(CH₃)₃((CH₂)₁₁CH₃)、N(CH₃)₂((CH₂)₁₁CH₃)₂、N(CH₃)₂((CH₂)₁₇CH₃)₂NH being equal₄A group substituted with 4 alkyl groups on the above,

more preferably a hydrogen atom; sodium atom, 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；NH₃((CH₂)₇CH₃)、NH₃((CH₂)₁₁CH₃)、NH₃((CH₂)₁₇CH₃) NH being equal₄A group substituted with 1 alkyl group; n (CH)₃)₃((CH₂)₁₅CH₃)、N(CH₃)₃((CH₂)₁₁CH₃)、N(CH₃)₂((CH₂)₁₁CH₃)₂、N(CH₃)₂((CH₂)₁₇CH₃)₂NH being equal₄A 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；NH₃((CH₂)₇CH₃)、NH₃((CH₂)₁₁CH₃)、NH₃((CH₂)₁₇CH₃) NH being equal₄A group substituted with 1 alkyl group; n (CH)₃)₃((CH₂)₁₅CH₃)、N(CH₃)₃((CH₂)₁₁CH₃)、N(CH₃)₂((CH₂)₁₁CH₃)₂、N(CH₃)₂((CH₂)₁₇CH₃)₂NH being equal₄A group substituted with 4 alkyl groups on the above,

more preferably sodium atom, 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；NH₃((CH₂)₇CH₃)、NH₃((CH₂)₁₁CH₃)、NH₃((CH₂)₁₇CH₃) Etc. NH of₄A group substituted with 1 alkyl group; n (CH)₃)₃((CH₂)₁₅CH₃)、N(CH₃)₃((CH₂)₁₁CH₃)、N(CH₃)₂((CH₂)₁₁CH₃)₂、N(CH₃)₂((CH₂)₁₇CH₃)₂NH being equal₄A group substituted with 4 alkyl groups.

Q¹And Q²Each 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 by-Si (-) -, the-CH (-) -constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted by-N (-), the-CH ═ constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group may be substituted by-N ═ and the-CH constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group ₂May be substituted by-O-, -S-, -S (O)₂-or-CO-, the hydrogen atom constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic groupOptionally substituted by halogen atoms, cyano groups, nitro groups, -SO₃M、－CO₂M or MM. As the group substituting the hydrogen atom constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group, a halogen atom, a cyano group, a nitro group, or-SO is preferable₃H or-CO₂H。

Q¹And Q²May be the same or different, preferably the same. Q¹And Q²Preferred are groups represented by the formulae (QQ1) to (QQ 19).

[ formulae (QQ1) to (QQ19) wherein R is^Q1～R^Q94Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group or-SO₃M、－CO₂M, MM, a 1-valent hydrocarbon group having 1 to 40 carbon atoms or a 1-valent heterocyclic group having 1 to 40 carbon atoms, wherein-C (-) -, which constitutes the 1-valent hydrocarbon group and the 1-valent heterocyclic group, may be substituted by-Si (-) -, wherein-CH (-) -which constitutes the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by-N (-), wherein-CH ═ which constitutes the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by-N ═ and wherein-CH which constitutes the 1-valent hydrocarbon group and the 1-valent heterocyclic group₂May 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, a cyano group, a nitro group, -SO ₃M、－CO₂M or MM. R^Q1～R^Q94Can be respectively selected from R^Q1～R^Q941 or more of them are bonded to form a ring. M and MM represent the same meanings as described above. The bonding sites are indicated in the opposite.]

As R^Q1～R^Q94The C1-valent hydrocarbon group having 1 to 40 carbon atoms or the C1-valent heterocyclic group having 1 to 40 carbon atoms, wherein-C (-) (-) -constituting the C1-valent hydrocarbon group and the C1-valent heterocyclic group may be substituted by-Si (-) - (-) -CH (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by-N (-) -, and-CH ═ constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by-N ═ and-CH constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group₂May 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, -SO₃M、－CO₂Examples of M or MM radicals are the radicals with R¹～R⁵And Z¹～Z⁴A 1-valent hydrocarbon group having 1 to 40 carbon atoms or a 1-valent heterocyclic group having 1 to 40 carbon atoms, wherein-C (-) (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by-Si (-) -, -CH (-) -constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by-N (-), -CH ═ constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by-N ═ and-CH constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by-CH ═ constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group ₂May 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, -SO₃M、－CO₂M or MM are the same groups.

As R^Q1～R^Q94Preferred examples of the group include¹～R⁵And Z¹～Z⁴Preferred groups are the same groups.

Q¹And Q²The group represented by the formula (QQ1) to the formula (QQ12) is preferable, the group represented by the formula (QQ1) to the formula (QQ5) is more preferable, the group represented by the formula (QQ1) to the formula (QQ4) is further preferable, the group represented by the formula (QQ1) and the formula (QQ2) is particularly preferable, and the group represented by the formula (QQ2) is further preferable.

Examples of the expressions (QQ1) to (QQ19) include the following expressions (Qa1) to (Qa 50); formulae (Qb1) to (Qb 27); formulae (Qc1) to (Qc 56); formulae (Qd1) to (Qd 41); formulae (Qe1) to (Qe 16); formulae (Qf1) to (Qf 15); formulae (Qg1) to (Qg 40); formulae (Qh1) to (Qh 40); formulae (Qj1) to (Qj 29); formulae (Qk1) to (Qk 22); formulae (Qm1) to (Qm 20); formulae (Qn1) to (Qn 16); formulae (Qo1) to (Qo 15); formulae (Qp1) to (Qp 83); formulae (Qq1) to (Qq 72); formulae (Qr1) to (Qr 17); formulae (Qs1) to (Qs 26); formulae (Qt1) to (Qt 26); formulas (Qu1) to (Qu 17); formulae (Qv1) to (Qv 26); formulae (Qx1) to (Qx 2); and groups represented by the formulae (Qy1) to (Qy 10). Wherein the bonding sites are indicated in the opposite.

Examples of the compound (I) include compounds represented by the formula (Ia) shown in tables 1 to 14 below and alkali metal salts thereof. In tables 1 to 14, "Q" indicates¹"column and" Q²The symbols in the column "correspond to the groups represented by the above formulae. The bonding sites are indicated in the opposite.

[ 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 and alkali metal salts thereof.

In the formula (Ib), R^Ib1～R^Ib5Any of them is a substituent other than a hydrogen atom (hereinafter, may be referred to as an RR group), and the other 4 are hydrogen atoms. "Q" in tables 15 to 31¹"column and" Q²The symbols in the column "are each a group represented by the above formulaThe clusters correspond. The symbols shown in the column "RR" in tables 15 to 31 represent RR groups, and are respectively associated with the following formulae (a1) to (a 69); formulae (b1) to (b 4); formulae (c1) to (c 4); formulae (d1) to (d 5); formulae (e1) to (e 20); formulae (f1) to (f 5); formulae (g1) to (g 9); formulae (h1) to (h 9); formulae (j1) to (j 9); formulae (k1) to (k 4); formulae (m1) to (m 9); formulae (n1) to (n 3); formulae (o1) to (o 5); formulae (p1) to (p 23); formulae (q1) to (q 26); formulae (r1) to (r 26); the values shown in the columns "No" in tables 15 to 31 correspond to the groups represented by the formulae (s1) to (s26), and the numerical values shown in the columns "No" in tables 15 to 31 indicate the positions at which the RR groups are substituted, and "1" indicates that the RR groups are substituted for R ^Ib1And "2" represents the replacement of an RR group for R^Ib2And "3" represents the replacement of an RR group with R^Ib3And "4" represents the replacement of an RR group with R^Ib4And "5" represents a RR group substituted for R^Ib5. The bonding sites are indicated in the opposite.

[ 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]

Examples of the compound (I) include compounds represented by the formula (If) shown in tables f1 to f44, and alkali metal salts thereof. Note that "Q" in tables f1 to f44¹"column and" Q²The symbols in the column "correspond to the groups represented by the above formulae. The bonding sites are indicated in the opposite.

[ 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, compounds represented by the formula (Iu) shown in tables u1 to u11, and alkali metal salts thereof. In tables t1 to t5 and tables u1 to u11, the column "aq" and the column "Q" are shown ¹"column", "Q²"column and" Q^u+1The symbols in the column "correspond to the groups represented by the above formulae and the groups represented by the following formulae (aq1) to (aq36), respectively. "Q" in tables u1 to u11^u+1The column "Q" in the compound represented by the formula (Iu)¹Group represented by and Q²The group represented is a group of the formula^u+1The symbols in the column indicate the corresponding groups. In the groups represented by the following formulae (aq1) to (aq36), # represents a group represented by formula (aq1) and Q¹The bonding site of (a) to (b),&represents and Q²The bonding site of (3).

[ 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 formulae (Ia1) to (Ia2216) and (Ib1) to (Ib1312), compounds represented by formulae (If1) to (If13090), compounds represented by formulae (It1) to (It900), and compounds represented by formulae (Iu1) to (Iu3238)In which the compound is substituted by a substituent selected from-SO₃H、-CO₂H、-SO₃NH₄、-CO₂NH₄、-SO₂NH₂、－CONH₂Phthalimidomethyl (C)₆H₄(CO)₂N－CH₂－)、－SO₂NH(CH₂)₂N(CH₂CH₃)₂、－N(CH₃)((CH₂)₁₁CH₃) And 1 or more of a fluorine atom, a chlorine atom and a bromine atom.

For example, the compound represented by the formula (Ia1) in Table 1 is substituted with-SO₃The compound of H is shown as the following structure. Wherein, in the formula, - (SO)₃H) represents-SO ₃H replaces all or 1 or more hydrogen atoms of the compound represented by the formula (Ia 1).

Examples of the above compounds include compounds in which all hydrogen atoms of the aromatic rings represented by the formulae (Ic1) to (Ic12) are substituted by 1 or more atoms selected from fluorine atoms, chlorine atoms and bromine atoms.

Examples of the compound (I) include compounds represented by formulae (Ia1) to (Ia2216) and (Ib1) to (Ib1312), compounds represented by formulae (If1) to (If13090), compounds represented by formulae (It1) to (It900), and compounds represented by formulae (Iu1) to (Iu3238) in which 1 to 6 substituents selected from the group consisting of — SO₃H、－CO₂H、－SO₃NH₄、－CO₂NH₄、－SO₂NH₂、－CONH₂O-phthalic anhydrideFormyl imino methyl (C)₆H₄(CO)₂N－CH₂－)、－SO₂NH(CH₂)₂N(CH₂CH₃)₂、－N(CH₃)((CH₂)₁₁CH₃) And 1 or more of a fluorine atom, a chlorine atom and a bromine atom.

For example, the compound represented by the formula (Ia1) in Table 1 is substituted with 1 to 6-SO₃The compound of H is shown as the following structure. Wherein, in the formula, - (SO)₃H)_1～6represents-SO₃H is substituted for any one hydrogen atom of 1 to 6 compounds represented by the formula (Ia 1).

Examples of the compound (I) include compounds represented by the formulae (Ia1) to (Ia2216) and (Ib1) to (Ib1312), compounds represented by the formulae (If1) to (If13090), compounds represented by the formulae (It1) to (It900), and compounds represented by the formulae (Iu1) to (Iu3238) substituted with a substituent selected from the group consisting of-SO ₃ ^-and-CO₂ ^-1 or more anions of (A) and (B) selected from Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺、Ni²⁺、Zn²⁺、Fe²⁺、Co²⁺、Sn²⁺、Mn²⁺、Al³⁺、Fe³⁺、Cr³⁺、Sn⁴⁺、Mn⁴⁺、Cu²⁺、Li⁺、Na⁺And K⁺A metal salt composed of 1 or more cations in (a).

Examples of the compound (I) include anions represented by the formula (Id) and anions represented by the formula (Ih) shown in tables 32 to 33 and tables h1 to h6, and anions selected from Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺、Ni²⁺、Zn²⁺、Fe²⁺、Co²⁺、Sn²⁺、Mn²⁺、Al³⁺、Fe³⁺、Cr³⁺、Sn⁴⁺、Mn⁴⁺、Cu²⁺、Li⁺、Na⁺And K⁺A metal salt composed of 1 or more cations in (a).

"Q" in tables 32 to 33 and tables h1 to h6¹"column and" Q²The symbols in the column "correspond to the groups represented by the above formulae and the groups represented by the following formulae (Qw1) to (Qw11), respectively.

[ Table 32]

[ Table 33]

[ Table h1]

[ Table h2]

[ Table h3]

[ Table h4]

[ Table h5]

[ Table h6]

Examples of the metal salt 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 column "Met" in tables 34 to 38 and tables k1 to k14, Mg2+ represents Mg²⁺And Ca2+ represents Ca²⁺Sr2+ represents Sr²⁺Ba2+ represents Ba²⁺Ni2+ represents Ni²⁺Zn2+ represents Zn²⁺Fe2+ represents Fe²⁺Co2+ represents Co²⁺Sn2+ represents Sn²⁺Mn2+ represents Mn²⁺Al3+ represents Al³⁺Fe3+ represents Fe³⁺Cr3+ represents Cr³⁺Sn4+ represents Sn⁴⁺Mn4+ represents Mn⁴⁺Cu2+ represents Cu²⁺And Li + represents Li ⁺Na + represents Na⁺And K + represents K⁺。

"Q" in tables 34 to 38 and tables k1 to k14¹"column and" Q²The symbols in the column "correspond to the groups represented by the above formulae. In the formulae (Ie) and (Ik), m 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 formulae (Ie) and (Ik), n is an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10. When the compound (I) of the present invention is the oligomer or polymer, the compound (I) is represented by the minimum integer in which m and n represent the ratio of the number of ligands to the number of metal atoms, in which 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]

Preferred compounds (I) are compounds represented by the formulae (Ia1) to (Ia 2216); compounds represented by the formulae (If1) to (If 13090); compounds represented by the formulae (It1) to (It 900); and compounds represented by formulae (Iu1) to (Iu 3238); a compound represented by formula (Ib 8); a compound represented by formula (Ib 14); a compound represented by any one of formulae (Ia1) to (Ia2216), a compound represented by any one of formulae (If1) to (If13090), a compound represented by any one of formulae (It1) to (It900), a compound represented by any one of formulae (Iu1) to (Iu3238), a compound represented by formula (Ib8), or a compound represented by formula (Ib14), the compound being substituted with a substituent selected from the group consisting of-SO ₃H、-CO₂H、-SO₃NH₄、-CO₂NH₄、-SO₂NH₂、-CONH₂Phthalimidomethyl (C)₆H₄(CO)₂N-CH₂-)、-SO₂NH(CH₂)₂N(CH₂CH₃)₂、-N(CH₃)((CH₂)₁₁CH₃) A compound containing 1 or more of a fluorine atom, a chlorine atom and a bromine atom; and compounds represented by the formulae (Ia1) to (Ia2216), compounds represented by the formulae (Ifl) to (If13090), compounds represented by the formulae (It1) to (It900), compounds represented by the formulae (Iu1) to (Iu3238), compounds represented by the formula (Ib8) and compounds represented by the formula (Ib14) substituted with a substituent selected from the group consisting of-SO₃ ^-and-CO₂ ^-1 or more anions of (A) and (B) selected from Mg²⁺、Ca²⁺、Sr²⁺、Ba²⁺、Ni²⁺、Zn²⁺、Fe²⁺、Co²⁺、Sn²⁺、Mn²⁺、Al³⁺、Fe³⁺、Cr³⁺、Sn⁴⁺、Mn⁴⁺、Cu²⁺、Li⁺、Na⁺And K⁺A metal salt composed of 1 or more cations in (A),

more preferably compounds represented by the formulae (Ia1) to (Ia 2216); compounds represented by the formulae (If1) to (If 13090); compounds represented by the formulae (It1) to (It 900); compounds represented by formulae (Iu1) to (Iu 3238); a compound represented by any one of formulae (Ia1) to (Ia2216), a compound represented by any one of formulae (If1) to (If13090), a compound represented by any one of formulae (It1) to (It900), a compound represented by any one of formulae (Iu1) to (Iu3238), a compound represented by formula (Ib8), or a compound represented by formula (Ib14), the compound being substituted with a substituent selected from the group consisting of-SO₃H、－CO₂H、－SO₃NH₄、－CO₂NH₄A compound containing 1 or more of a fluorine atom, a chlorine atom and a bromine atom; and anions represented by the formulae (Id1) to (Id304) and anions represented by the formulae (Ih1) to (Ih1666) with a metal selected from Mg ²⁺、Ca²⁺、Sr²⁺、Ba²⁺、Ni²⁺、Zn²⁺、Fe²⁺、Co²⁺、Sn²⁺、Mn²⁺、Al³⁺、Fe³⁺、Cr³⁺、Sn⁴⁺、Mn⁴⁺、Cu²⁺、Li⁺、Na⁺And K⁺A metal salt composed of 1 or more cations in (A),

further preferred are compounds represented by the formulae (Ia1) to (Ia 2216); compounds represented by the formulae (If1) to (If 13090); compounds represented by the formulae (It1) to (It 900); compounds represented by formulae (Iu1) to (Iu 3238); a compound represented by any one of formulae (Ia1) to (Ia2216), a compound represented by any one of formulae (If1) to (If13090), a compound represented by any one of formulae (It1) to (It900), a compound represented by any one of formulae (Iu1) to (Iu3238), a compound represented by formula (Ib8), or a compound represented by formula (Ib14), the compound being substituted with a substituent selected from the group consisting of-SO₃H、－CO₂H、－SO₃NH₄、－CO₂NH₄1 or more compounds selected from the group consisting of chlorine atom and bromine atom; compounds represented by the formulae (Ie1) to (Ie 76); and compounds represented by the formulae (Ik1) to (Ik 114); compounds represented by the formulae (Ik1615) to (Ik 1633); formula (Ik1822) to formula (Ik)Ik 1983); a compound represented by the formula (Ie 117); a compound represented by the formula (Ie 123); a compound represented by formula (Ik 172); a compound represented by formula (Ik 171); a compound represented by 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 (Ie116),

particularly preferred are compounds represented by the formulae (Ia1) to (Ia 2216); compounds represented by the formulae (If1) to (If 13090); compounds represented by the formulae (It1) to (It 900); compounds represented by formulae (Iu1) to (Iu 3238); a compound represented by formula (Ib 8); and a compound represented by the formula (Ib14),

Further preferred are compounds represented by the formulae (Ia1) to (Ia1241) and compounds represented by the formulae (It1) to (It900),

particularly preferred are a compound represented by the formula (Ia1), a compound represented by the formula (Ia2), a compound represented by the formula (Ia3), a compound represented by the formula (Ia10), a compound represented by the formula (Ia22), a compound represented by the formula (Ia23), a compound represented by the formula (Ia33), a compound represented by the formula (Ia35), a compound represented by the formula (Ia315), a compound represented by the formula (Ia696), a compound represented by the formula (Ia703), a compound represented by the formula (Ia973), a compound represented by the formula (It232), a compound represented by the formula (It242), and a compound represented by the formula (It750),

very preferred are a compound represented by the formula (Ia1), a compound represented by the formula (Ia2), a compound represented by the formula (Ia3), a compound represented by the formula (Ia22), a compound represented by the formula (Ia23), a compound represented by the formula (Ia35), a compound represented by the formula (Ia696), a compound represented by the formula (Ia703), a compound represented by the formula (Ia973), a compound represented by the formula (It232), a compound represented by the formula (It242), and a compound represented by the formula (It750),

the compound represented by the formula (Ia1), the compound represented by the formula (Ia2), the compound represented by the formula (Ia3), the compound represented by the formula (Ia696), the compound represented by the formula (Ia703), the compound represented by the formula (Ia973), the compound represented by the formula (It232), the compound represented by the formula (It242), and the compound represented by the formula (It750) are most preferable.

The compound represented by the formula (I) can be produced by a reaction of the compound represented by the formula (pt1), the compound represented by the formula (pt2) and the compound represented by the formula (pt 3).

In the formulae (pt1) to (pt3), R¹～R⁵、Q¹And Q²The same meanings as described above are indicated.

The amount of the compound represented by the formula (pt2) used in the reaction of the compound represented by the formula (pt1), the compound represented by the formula (pt2) and the compound represented by the formula (pt3) is usually 0.1 to 30 moles, preferably 1 to 20 moles, more preferably 1 to 16 moles, and still more preferably 1 to 10 moles, based on 1 mole of the compound represented by the formula (pt 1).

The amount of the compound represented by the formula (pt3) used in the reaction of the compound represented by the formula (pt1), the compound represented by the formula (pt2) and the compound represented by the formula (pt3) is usually 0.1 to 30 moles, preferably 1 to 20 moles, more preferably 1 to 16 moles, and still more preferably 1 to 10 moles, based on 1 mole 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 ℃, further preferably 100 to 230 ℃, and particularly preferably 150 to 200 ℃.

The reaction time is usually 0.5 to 500 hours.

The reaction of the compound represented by the formula (pt1), the compound represented by the formula (pt2) and the compound represented by the formula (pt3) is usually carried out in the presence of a solvent.

As the solvent, water may 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, diphenyl ether and the like; 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 dichloromethane, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; a nitrated hydrocarbon solvent such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide and the like,

preferred examples thereof include diphenyl ether, methyl benzoate, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decahydronaphthalene, tetrahydronaphthalene, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, 2-chloronaphthalene, nitrobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide,

More preferable examples thereof include diphenyl ether, methyl benzoate, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decahydronaphthalene, tetrahydronaphthalene, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, 2-chloronaphthalene, nitrobenzene, N-methylpyrrolidone,

methyl benzoate is more preferable.

The amount of the solvent used is usually 1 to 1000 parts by mass based on 1 part by mass of the compound represented by formula (pt1) in the reaction of the compound represented by formula (pt1), the compound represented by formula (pt2) and the compound represented by formula (pt 3).

In the reaction of the compound represented by the formula (pt1), the compound represented by the formula (pt2) and the compound represented by the formula (pt3), preferably, 1 or more selected from 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; preferred examples thereof include hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and carboxylic acids, more preferred examples thereof include carboxylic acids, and still more preferred examples thereof include benzoic acid.

The amount of the acid used in the reaction of the compound represented by formula (pt1), the compound represented by formula (pt2), and the compound represented by formula (pt3) is usually 1 to 90 mol, preferably 1 to 70 mol, more preferably 1 to 50 mol, and still more preferably 1 to 30 mol, based on 1 mol of the compound represented by 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 (pt1), the compound represented by the formula (pt2), and the compound represented by the formula (pt3) is usually 0.01 to 30 mol, preferably 0.01 to 20 mol, more preferably 0.01 to 10 mol, and still more preferably 0.01 to 3 mol, based on 1 mol 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 the compound (I) can be extracted by various known methods. For example, after the reaction is completed, the compound (I) can be extracted by thoroughly mixing a solvent such as methanol, which may be difficult to dissolve the compound (I) but easy to dissolve compounds other than the compound (I), in the reaction mixture with the reaction mixture and then filtering the mixture. The compound (I) can be extracted by washing the residue obtained with an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an acidic aqueous solution such as hydrochloric acid using an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide or a mixed solvent thereof, and then with water, a low boiling point alcohol such as methanol or a mixed solvent thereof. Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after the completion of the reaction, the solvent of the reaction mixture may be distilled off, and the obtained 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 reaction is completed, the compound (I) may be extracted by thoroughly mixing a solvent such as methanol, which may be difficult to dissolve the compound (I) but is easy to dissolve compounds other than the compound (I), with the reaction mixture and then filtering the mixture. Further purification may be carried out by column chromatography and/or recrystallization.

The compound represented by the formula (I) can be produced by reacting a compound represented by the formula (pt1) with a compound represented by the formula (pt2) to produce a compound represented by the formula (I ') (hereinafter, sometimes referred to as a compound (I ')), and then hydrolyzing the compound represented by the formula (I ') in the presence of a base to produce a compound represented by the formula (IM1) (hereinafter, sometimes referred to as a compound (IM1)), and further by reacting a compound represented by the formula (IM1) with a compound represented by the formula (pt 3).

R in the formula (pt1), the formula (pt2), the formula (pt3), the formula (I') and the formula (IM1)¹～R⁵、Q¹、Q²The same meanings as described above are indicated.

The amount of the compound represented by the formula (pt2) used in the reaction of the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is usually 0.1 to 60 mol, preferably 1 to 40 mol, more preferably 1 to 32 mol, and still 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 (pt3) used in the reaction of the compound represented by the formula (IM1) and the compound represented by the formula (pt3) is usually 0.1 to 30 moles, preferably 1 to 20 moles, more preferably 1 to 16 moles, and 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 (pt1) with the compound represented by the formula (pt2) or the reaction temperature in the reaction of the compound represented by the formula (IM1) with the compound represented by the formula (pt3) is usually-100 to 300 ℃, preferably 0 to 280 ℃, more preferably 50 to 250 ℃, further preferably 100 to 230 ℃, and particularly preferably 150 to 200 ℃.

The reaction time of the reaction between the compound represented by the formula (pt1) and the compound represented by the formula (pt2) or the reaction time of the reaction between the compound represented by the formula (IM1) and the compound represented by the formula (pt3) is usually 0.5 to 500 hours.

The reaction of the compound represented by formula (pt1) with the compound represented by formula (pt2) or the reaction of the compound represented by formula (IM1) with the compound represented by formula (pt3) is usually carried out in the presence of a solvent.

Examples of the solvent in the reaction of the compound represented by formula (pt1) with the compound represented by formula (pt2) or the reaction of the compound represented by formula (IM1) with the compound represented by formula (pt3) include 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, diphenyl ether and the like; 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 dichloromethane, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; a nitrated hydrocarbon solvent 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 is more preferable.

The amount of the solvent used in the reaction of the compound represented by formula (pt1) and the compound represented by formula (pt2) is usually 1 to 1000 parts by mass based on 1 part by mass of the compound represented by formula (pt 1).

The amount of the solvent used in the reaction of the compound represented by formula (IM1) and the compound represented by formula (pt3) is usually 1 to 1000 parts by mass relative to 1 part by mass of the compound represented by formula (IM 1).

In the reaction of the compound represented by the formula (pt1) with the compound represented by the formula (pt2) or the reaction of the compound represented by the formula (IM1) with the compound represented by the formula (pt3), preferably 1 or more selected from acids and metal salts coexist.

Examples of the acid in the reaction of the compound represented by formula (pt1) with the compound represented by formula (pt2) or the reaction of the compound represented by formula (IM1) with the compound represented by formula (pt3) 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; examples of the carboxylic acid include acetic acid, trifluoroacetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, benzoic acid, tartaric acid, and the like, and examples thereof include preferably hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and carboxylic acid, more preferably carboxylic acid, and even more preferably benzoic acid.

The amount of the acid used in the reaction of the compound represented by formula (pt1) and the compound represented by formula (pt2) is usually 1 to 90 mol, preferably 1 to 70 mol, more preferably 1 to 50 mol, and still more preferably 1 to 30 mol, based on 1 mol of the compound represented by formula (pt 1).

The amount of the acid used in the reaction of the compound represented by formula (IM1) and the compound represented by formula (pt3) is usually 1 to 90 mol, preferably 1 to 70 mol, more preferably 1 to 50 mol, and still more preferably 1 to 30 mol, based on 1 mol of the compound represented by formula (IM 1).

Examples of the metal salt in the reaction of the compound represented by formula (pt1) with the compound represented by formula (pt2) or the reaction of the compound represented by formula (IM1) with the compound represented by formula (pt3) include zinc chloride and aluminum chloride.

The amount of the metal salt used in the reaction of the compound represented by formula (pt1) and the compound represented by formula (pt2) is usually 0.01 to 30 mol, preferably 0.01 to 20 mol, more preferably 0.01 to 10 mol, and still more preferably 0.01 to 3 mol, based on 1 mol of the compound represented by formula (pt 1).

The amount of the metal salt used in the reaction of the compound represented by the formula (IM1) and the compound represented by the formula (pt3) is usually 0.01 to 30 mol, preferably 0.01 to 20 mol, more preferably 0.01 to 10 mol, and still more preferably 0.01 to 3 mol, based on 1 mol 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 (pt1) with the compound represented by the formula (pt2) is not particularly limited, and the extraction can be carried out by various known methods. For example, after completion of the reaction, a solvent such as methanol, in which the compound (I ') in the reaction mixture is not easily dissolved but the compound other than the compound (I ') is easily dissolved, may be thoroughly mixed with the reaction mixture, and then the mixture may be filtered to extract (I '). The compound (I') can be extracted by washing the residue obtained with an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an acidic aqueous solution such as hydrochloric acid using an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide or a mixed solvent thereof, and then washing with water, a low boiling point alcohol such as methanol or a mixed solvent thereof. Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after the completion of the reaction, the solvent of the reaction mixture may be distilled off, and the obtained 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 reaction is completed, the compound (I ') may be extracted by thoroughly mixing a solvent such as methanol, which may be difficult to dissolve the compound (I ') in the reaction mixture and may be easy to dissolve compounds other than the compound (I '), with the reaction mixture and then filtering. Further purification may be carried out by column chromatography and/or recrystallization.

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 (IM1) and the compound represented by the formula (pt3) is not particularly limited, and the extraction can be carried out by various known methods. For example, after the reaction is completed, the compound (I) can be extracted by thoroughly mixing a solvent such as methanol, which may be difficult to dissolve the compound (I) but easy to dissolve compounds other than the compound (I), in the reaction mixture with the reaction mixture and then filtering the mixture. The compound (I) can be extracted by washing the residue obtained with an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an acidic aqueous solution such as hydrochloric acid using an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide or a mixed solvent thereof, and then with water, a low boiling point alcohol such as methanol or a mixed solvent thereof. Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after the completion of the reaction, the solvent of the reaction mixture may be distilled off, and the obtained 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 reaction is completed, the compound (I) may be extracted by thoroughly mixing a solvent such as methanol, which may be difficult to dissolve the compound (I) but is easy to dissolve compounds other than the compound (I), with the reaction mixture and then filtering the mixture. Further purification may be carried out by column chromatography and/or recrystallization.

Examples of the base used in the hydrolysis reaction in which the compound represented by the following formula (I') is present as a 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, metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, organometallic compounds such as methyllithium, butyllithium, tert-butyllithium, and phenyllithium, and inorganic bases such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, and potassium hydroxide, and preferably inorganic bases, more preferably lithium hydroxide, sodium hydroxide and potassium hydroxide, even more preferably sodium hydroxide and potassium hydroxide, and particularly preferably potassium hydroxide.

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

The amount of water used in the hydrolysis reaction of the compound represented by the formula (I ') in the presence of a base is usually 1 to 1000 parts by mass, preferably 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and 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 ℃, further preferably 40 to 100 ℃, and particularly preferably 60 to 100 ℃.

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

The method for extracting the compound represented by the formula (IM1) 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 the extraction can be carried out by various known methods. For example, after completion of the reaction, the compound (IM1) can be extracted by adding an acidic aqueous solution such as hydrochloric acid to the reaction mixture to neutralize the reaction mixture and then filtering the neutralized product. The compound (IM1) can be extracted by washing the obtained residue with a basic aqueous solution such as an aqueous sodium hydroxide solution and/or an acidic aqueous solution such as hydrochloric acid using an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, or 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, or water or a mixed solvent thereof. Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after the completion of the reaction, the solvent of the reaction mixture may be distilled off, and the obtained 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 a compound represented by the formula (pt1) with a compound represented by the formula (pt3) to produce a compound represented by the formula (IM2) (hereinafter, may be referred to as a compound (IM2)), and then reacting the compound represented by the formula (IM2) with a compound represented by the formula (pt 2).

R in the formula (pt1), the formula (pt2), the formula (pt3) and the formula (IM2)¹～R⁵、Q¹、Q²The same meanings as described above are indicated.

The amount of the compound represented by the formula (pt3) used in the reaction of the compound represented by the formula (pt1) and the compound represented by the formula (pt3) is usually 0.1 to 10 mol, preferably 0.1 to 5 mol, more preferably 0.5 to 2 mol, and still 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 (pt1) with the compound represented by the formula (pt3) is usually-100 to 300 ℃, preferably 0 to 280 ℃, more preferably 50 to 250 ℃, further preferably 100 to 230 ℃, and particularly preferably 120 to 200 ℃.

The reaction time in the reaction of the compound represented by the formula (pt1) with the compound represented by the formula (pt3) is usually 0.5 to 500 hours.

The reaction of the compound represented by the formula (pt1) with the compound represented by the formula (pt3) is usually carried out in the presence of a solvent.

Examples of the solvent used in the reaction of the compound represented by formula (pt1) and the compound represented by formula (pt3) include 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, diphenyl ether and the like; 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 dichloromethane, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; a nitrated hydrocarbon solvent such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide, etc.,

preferred examples thereof include phenol, diphenyl ether, methyl benzoate, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decahydronaphthalene, tetrahydronaphthalene, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, 2-chloronaphthalene, nitrobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide,

More preferable examples thereof include phenol, diphenyl ether, methyl benzoate, trimethylbenzene (e.g., 1,3, 5-trimethylbenzene), decahydronaphthalene, tetrahydronaphthalene, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, 2-chloronaphthalene, nitrobenzene, N-methylpyrrolidone,

further preferred are phenol, methyl benzoate,

phenol is particularly preferred.

The amount of the solvent used in the reaction of the compound represented by formula (pt1) and the compound represented by formula (pt3) is usually 1 to 1000 parts by mass, preferably 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and still more preferably 1 to 50 parts by mass, based on 1 part by mass of the compound represented by formula (pt 1).

The method for extracting compound (IM2) from the reaction mixture in the reaction of compound represented by formula (pt1) and compound represented by formula (pt3) is not particularly limited, and extraction can be carried out by various known methods. For example, after the reaction is completed, a solvent such as methanol, in which the compound (IM2) in the reaction mixture is not easily dissolved but the compound other than the compound (IM2) is easily dissolved, may be thoroughly mixed with the reaction mixture, followed by filtration to extract (IM 2). The compound (IM2) can be extracted by washing the obtained residue with a basic aqueous solution such as an aqueous sodium hydroxide solution and/or an acidic aqueous solution such as hydrochloric acid using an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, or 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, or water or a mixed solvent thereof. Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after the completion of the reaction, the solvent of the reaction mixture may be distilled off, and the obtained 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 reaction, the reaction mixture may be added to a solvent such as methanol in which the compound (IM2) in the reaction mixture is not easily dissolved but the compound other than the compound (IM2) is easily dissolved, followed by thorough mixing and filtration to extract (IM 2). Further purification may be carried out by column chromatography and/or recrystallization.

The amount of the compound represented by the formula (pt2) used in the reaction of the compound represented by the formula (IM2) and the compound represented by the formula (pt2) is usually 0.1 to 30 moles, preferably 1 to 20 moles, more preferably 1 to 16 moles, and 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 (IM2) and the compound represented by the formula (pt2) is usually-100 to 300 ℃, preferably 0 to 280 ℃, more preferably 50 to 250 ℃, further preferably 100 to 230 ℃, and particularly preferably 150 to 200 ℃.

The reaction time of the reaction of the compound represented by the formula (IM2) with the compound represented by the formula (pt2) is usually 0.5 to 500 hours.

The reaction of the compound represented by the formula (IM2) with the compound represented by the formula (pt2) is usually carried out in the presence of a solvent.

Examples of the solvent in the reaction of the compound represented by the formula (IM2) with the compound represented by the formula (pt2) include 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, diphenyl ether and the like; 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 dichloromethane, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; a nitrated hydrocarbon solvent 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 is more preferable.

The amount of the solvent used in the reaction of the compound represented by formula (IM2) and the compound represented by formula (pt2) is usually 1 to 1000 parts by mass relative to 1 part by mass of the compound represented by formula (IM 2).

In the reaction of the compound represented by the formula (IM2) with the compound represented by the formula (pt2), preferably 1 or more selected from acids and metal salts coexist.

Examples of the acid in the reaction between the compound represented by the formula (IM2) and the compound represented by the formula (pt2) 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; examples of the carboxylic acid include acetic acid, trifluoroacetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, benzoic acid, tartaric acid, and the like, and examples thereof include preferably hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and carboxylic acid, more preferably carboxylic acid, and even more preferably benzoic acid.

The amount of the acid used in the reaction of the compound represented by formula (IM2) and the compound represented by formula (pt2) is usually 1 to 90 mol, preferably 1 to 70 mol, more preferably 1 to 50 mol, and still more preferably 1 to 30 mol, based on 1 mol of the compound represented by formula (IM 2).

Examples of the metal salt in the reaction between the compound represented by the formula (IM2) and the compound represented by the formula (pt2) include zinc chloride and aluminum chloride.

The amount of the metal salt used in the reaction of the compound represented by the formula (IM2) and the compound represented by the formula (pt2) is usually 0.01 to 30 mol, preferably 0.01 to 20 mol, more preferably 0.01 to 10 mol, and still more preferably 0.01 to 3 mol, based on 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 (IM2) and the compound represented by the formula (pt2) is not particularly limited, and the extraction can be carried out by various known methods. For example, after the reaction is completed, the compound (I) can be extracted by thoroughly mixing a solvent such as methanol, which may be difficult to dissolve the compound (I) but easy to dissolve compounds other than the compound (I), in the reaction mixture with the reaction mixture and then filtering the mixture. The compound (I) can be extracted by washing the residue obtained with an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an acidic aqueous solution such as hydrochloric acid using an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide or a mixed solvent thereof, and then with water, a low boiling point alcohol such as methanol or a mixed solvent thereof. Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after the completion of the reaction, the solvent of the reaction mixture may be distilled off, and the obtained 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 reaction is completed, the compound (I) may be extracted by thoroughly mixing a solvent such as methanol, which may be difficult to dissolve the compound (I) but is easy to dissolve compounds other than the compound (I), with the reaction mixture and then filtering the mixture. Further purification may be carried out by column chromatography and/or recrystallization.

The reaction time of the reaction of the compound represented by the formula (pt1) with the compound represented by the formula (pt3) is usually 0.5 to 500 hours.

Examples of the solvent used in the reaction of the compound represented by formula (pt1) and the compound represented by formula (pt3) include 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, diphenyl ether and the like; 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 dichloromethane, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; a nitrated hydrocarbon solvent such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide and the like,

further preferred are phenol, methyl benzoate,

phenol is particularly preferred.

The method for extracting compound (IM2) from the reaction mixture in the reaction of compound represented by formula (pt1) and compound represented by formula (pt3) is not particularly limited, and extraction can be carried out by various known methods. For example, after the reaction is completed, a solvent such as methanol, in which the compound (IM2) in the reaction mixture is not easily dissolved but the compound other than the compound (IM2) is easily dissolved, may be thoroughly mixed with the reaction mixture, followed by filtration to extract (IM 2). The compound (IM2) can be extracted by washing the obtained residue with a basic aqueous solution such as an aqueous sodium hydroxide solution and/or an acidic aqueous solution such as hydrochloric acid using an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, or 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, or water or a mixed solvent thereof. Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after the completion of the reaction, the solvent of the reaction mixture may be distilled off, and the obtained 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 reaction, a solvent such as methanol, in which the compound (IM2) in the reaction mixture is not easily soluble but the compound other than the compound (IM2) is easily soluble, may be thoroughly mixed with the reaction mixture and then filtered to extract the compound (IM 2). Further purification may be carried out by column chromatography and/or recrystallization.

methyl benzoate is more preferable.

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 (IM2) and the compound represented by the formula (pt2) is not particularly limited, and the extraction can be carried out by various known methods. For example, after the reaction is completed, the compound (I) can be extracted by thoroughly mixing a solvent such as methanol, which may be difficult to dissolve the compound (I) but easy to dissolve compounds other than the compound (I), in the reaction mixture with the reaction mixture and then filtering the mixture. The residue obtained is washed with an alkaline aqueous solution such as an aqueous sodium hydroxide solution and/or an acidic aqueous solution such as hydrochloric acid using an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, or N-methylpyrrolidone, a sulfoxide solvent such as dimethylsulfoxide, or a mixed solvent thereof, and then washed with water, a low-boiling alcohol such as methanol, or a mixed solvent thereof, to extract the compound (I). Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after the completion of the reaction, the solvent of the reaction mixture may be distilled off, and the obtained 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 reaction is completed, the compound (I) may be extracted by thoroughly mixing a solvent such as methanol, which may be difficult to dissolve the compound (I) but is easy to dissolve compounds other than the compound (I), with the reaction mixture and then filtering the mixture. Further purification may be carried out by column chromatography and/or recrystallization.

The compound (I) may be subjected to a reaction with a sulfonating agent such as fuming sulfuric acid or chlorosulfonic acid to introduce a sulfo group or-SO into the compound (I)₃And M. Introduction of sulfo group or-SO into Compound (I)₃The compound of M (hereinafter, sometimes referred to as "sulfonated compound (I)") is also a compound of the present invention.

SO in oleum₃The amount of (b) to be used is usually 1 to 200 mol, preferably 2 to 150 mol, more preferably 3 to 100 mol, and further preferably 5 to 80 mol based on 1 mol of the compound (I).

SO in oleum₃The amount of 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, per 100 parts by mass of the fuming sulfuric acid.

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

Introduction of sulfo or-SO into Compound (I) Using Chlorosulfonic acid₃When M is used, 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 (for example, 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene.

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

The reaction temperature of sulfonation is usually-20 to 200 ℃, preferably-10 to 150 ℃, and 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 the extraction can be carried out by various known methods. For example, after the reaction is completed, the reaction mixture may be added dropwise to ice, and the resulting mixture may be filtered to extract the sulfonated compound (I). Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after the completion of the reaction, the reaction mixture is dropped into ice, and the resulting mixture is mixed with an alcohol solvent such as methanol, in which the sulfonated compound (I) is not easily dissolved but the compound other than the sulfonated compound (I) is easily dissolved, a nitrile solvent such as acetonitrile, and a hydrophilic organic solvent such as a mixed solvent thereof, and the mixture is filtered to extract the sulfonated compound (I). Further purification may be carried out by column chromatography and/or recrystallization. Alternatively, after completion of the reaction, the reaction mixture may be dropped into ice, the resulting mixture may be neutralized with an aqueous solution such as ammonia, a water-soluble amine or a mixture thereof, the mixture may be mixed with an alcohol solvent such as methanol, a nitrile solvent such as acetonitrile or a mixed solvent thereof, and a hydrophilic organic solvent such as a mixed solvent thereof, followed by filtration, and the solvent of the obtained filtrate may be distilled off, whereby the sulfonated compound (I) may be extracted. Further purification may be carried out by column chromatography and/or recrystallization.

Can be prepared by reacting with-SO₃H and/or-CO₂Production of compound (I) having-SO by reacting Compound (I) having H (hereinafter, sometimes referred to as "acid group-containing Compound (I)") with MM salt₃(MM) and/or-CO₂Compound (I) (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, and 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 ℃, and further 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. Examples of the solvent include 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, diphenyl ether and the like; 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 dichloromethane, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; a nitrated hydrocarbon solvent 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 a mixed solvent thereof, more preferably water.

The amount of the solvent used is usually 1 to 1000 parts by mass, preferably 10 to 500 parts by mass, and 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 the salt having MM may be carried out in the presence of a base.

Examples of the base include 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 and other organic bases, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide and other metal alkoxides, methyllithium, butyllithium, tert-butyllithium, phenyllithium and other organic compounds, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide and other inorganic bases, preferably inorganic bases, more preferably lithium hydroxide, sodium hydroxide and potassium hydroxide, still more preferably sodium hydroxide and potassium hydroxide, and particularly preferably sodium hydroxide.

The amount of the base used is usually 1 to 100 moles, preferably 1 to 50 moles, more preferably 1 to 20 moles, and 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 various known methods can be used for extraction. For example, the reaction mixture can be filtered after the reaction is completed to extract the compound having-SO₃(MM) and/or-CO₂(MM) Compound (I). The obtained residue may be washed with an amide solvent such as N, N-dimethylformamide, N-dimethylacetamide, or 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, or water or a mixed solvent thereof, and then washed with water, a low-boiling alcohol such as methanol, or a mixed solvent thereof to purify the residue.

[ 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 color filter of a darker color can be formed as compared with a coloring composition containing c.i. pigment yellow 138. The color filter formed from the colored 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 content in the coloring composition is less than 100% by mass, preferably 0.01% by mass or more and less than 100% by mass, more preferably 0.1% by mass to 99.9% by mass, even more preferably 0.1% by mass to 99% by mass, particularly preferably 1% by mass to 90% by mass, even more preferably 1% by mass to 80% by mass, particularly preferably 1% by mass to 70% by mass, very preferably 1% by mass to 60% by mass, and most preferably 1% by mass to 50% by mass, based on 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 contents of the respective components 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 in the total amount of solid components, preferably 0.0001 to 99.9999% by mass, more preferably 0.0001 to 99% by mass, still more preferably 0.0001 to 90% by mass, particularly preferably 0.0001 to 80% by mass, further preferably 0.0001 to 70% by mass, particularly preferably 0.0001 to 60% by mass, very preferably 0.0001 to 55% by mass, and most preferably 0.1 to 55% by mass.

[ solvent (E) ]

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. Examples of the solvent (E) include an ester solvent (a solvent containing-CO-O-and not containing-O-in the molecule), an ether solvent (a solvent containing-O-and not containing-CO-O-in the molecule), an ether ester solvent (a solvent containing-CO-O-and not containing-O-in the molecule), a ketone solvent (a solvent containing-CO-and not containing-CO-O-in the molecule), an alcohol solvent (a solvent containing OH in the molecule and not containing-O-, -CO-, and-CO-O-, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -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, 1, 4-di-n

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

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

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, and isophorone.

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

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

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

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

Among the above solvents, organic solvents having a boiling point of 120 to 180 ℃ at 1atm are preferable from the viewpoint of coatability and drying property. Preferred examples of the solvent include 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 more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4-hydroxy-4-methyl-2-pentanone.

The content of the solvent (E) is less than 100% by mass, preferably 99.99% by mass or less, 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, very preferably 40% by mass to 99% by mass, and most preferably 50% by mass to 99% by mass, based on 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 an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

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 another structural unit.

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

In the present specification, "(meth) acrylic acid" means at least 1 selected from acrylic acid and methacrylic acid. The same meanings are also given to "(meth) acryloyl group" 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; carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene; unsaturated dicarboxylic acid 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-dicarboxybicyclo [2.2.1] hept-2-ene anhydride; unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [ 2- (meth) acryloyloxyethyl ] ester; unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid; and the like.

Among them, acrylic acid, methacrylic acid, o-, m-, p-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 an oxirane 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 ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 3)"), and the like.

Examples of the monomer (b1) include a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "monomer (b 1-1)") and a monomer having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes 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 -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α -methyl-m-vinylbenzyl glycidyl ether, α -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (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, 2,4, 6-tris (glycidoxymethyl) styrene and the like.

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

[ formula (BI) and formula (BII) wherein R^aAnd R^bIndependently represent 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^aAnd X^bIndependently of one another, represent a single bond, or-R^c－、＊－R^c－O－、＊－R^c-S-or (II)－R^c－NH－。R^cRepresents an alkanediyl group having 1 to 6 carbon atoms. Represents a bonding site with O.]

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

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

As R^aAnd R^bPreferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

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

As X^aAnd X^bPreferable examples thereof include a single bond, methylene, ethylene and perylene-CH₂-O-and-CH₂CH₂O-is more preferably a single bond or O-CH₂CH₂-O- (. ANGSTROM.) represents a bonding site to O).

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

The compound represented by the formula (BII) includes compounds represented by any one of the formulae (BII-1) to (BII-15), and the like, and among them, compounds represented by the formulae (BII-1), (BII-3), (BII-5), (BII-7), the formula (BII-9), and the formulae (BII-11) to (BII-15) are preferable, and compounds represented by the formulae (BII-1), (BII-7), the formula (BII-9), and the formula (BII-15) are more preferable.

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

As the monomer (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of the monomer (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, and 3-ethyl-3-acryloxyethyloxetane.

As the monomer (b3), a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group is more preferable. Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V #150, manufactured by Osaka Organischen chemical industries, Ltd.), tetrahydrofurfuryl methacrylate, and the like.

The monomer (b) is preferably the monomer (b1) in view of enabling the obtained color filter to have higher reliability such as heat resistance, chemical resistance and the like. Further, the monomer (b 1-2) is more preferable in terms 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, and tricyclo [5.2.1.0 ] meth) acrylate² ^,6]Decan-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decen-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6](meth) acrylic esters such as decen-9-yl ester, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; halogen atom-containing (meth) acrylates such as 2,2,3,3,4,4,5, 5-octafluoropentyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; bicyclo [2.2.1 ]Hept-2-ene, 5-methylbicyclo [2.2.1 ]]Hept-2-ene, 5-ethylbicyclo [2.2.1 ]]Hept-2-ene, 5-hydroxybicyclo [2.2.1 ]]Hept-2-ene, 5-hydroxymethylbicyclo [2.2.1 ]]Hept-2-ene, 5- (2' -hydroxyethyl) bicyclo [2.2.1]Hept-2-ene, 5-methoxybicyclo [2.2.1 ]]Hept-2-ene,5-ethoxy-bicyclo [2.2.1 ]]Hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1 ]]Hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1]Hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1]Hept-2-ene, 5, 6-dimethoxybicyclo [2.2.1]Hept-2-ene, 5, 6-diethoxybicyclo [2.2.1 ]]Hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1 ]]Hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1 ]]Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1]Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1]Hept-2-ene, 5-cyclohexyloxycarbonyl-bicyclo [2.2.1 ]]Hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1 ]]Hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1]Hept-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1]Bicyclic unsaturated compounds such as hept-2-ene; dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide; vinyl group-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, 9-vinylcarbazole and p-methoxystyrene; vinyl group-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-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; and the like.

Among them, styrene, vinyltoluene and tricyclo [5.2.1.0 ] are preferable from the viewpoint of copolymerization reactivity and heat resistance^2,6]Decan-8-yl (meth) acrylates, tricyclo [5.2.1.0^2,6]Decan-9-yl (meth) acrylates, 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, 2,3,3,4,4,5, 5-octafluoropentyl (meth) acrylate, 9-vinylcarbazole, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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 [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/9-vinylcarbazole/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6]Decyl ester/(phenyl (meth) acrylate/o-vinylbenzoic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(phenyl (meth) acrylate/m-vinylbenzoic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(phenyl (meth) acrylate/p-vinylbenzoic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(phenyl (meth) acrylate/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid 2,2,3,3,4,4,5, 5-octafluoropentyl ester/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/(meth) acrylic acid benzyl ester/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid) ^2,6]Decyl ester/(meth) acrylic acid 2-ethyl esterCopolymers of ethylhexyl esters and 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic) acid^2,6]Decyl ester/(meth) acrylic acid tricyclo [5.2.1.0^2,6]Decenyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer, benzyl (meth) acrylate/(meth) acrylic acid copolymer, styrene/(meth) acrylic acid copolymer, and resins described in each of Japanese patent application laid-open Nos. 9-106071, 2004-29518 and 2004-361455.

Among these, 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 species, in which case the resin (B) preferably contains at least 1 copolymer comprising a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B), more preferably contains at least 1 copolymer comprising a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B1), further preferably contains at least 1 copolymer comprising a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B1-2), and particularly preferably contains a structural unit selected from the group consisting of 3, 4-epoxytricyclo [5.2.1.0 ] of (meth) acrylic acid ^2,6]Decyl ester/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]1 or more of decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer.

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

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

The acid value (solid content equivalent value) of the resin (B) is preferably 10 to 500 mg-KOH/g, more preferably 20 to 450 mg-KOH/g, still more preferably 20 to 400 mg-KOH/g, yet more preferably 20 to 370 mg-KOH/g, yet more preferably 30 to 350 mg-KOH/g, particularly preferably 30 to 340 mg-KOH/g, most preferably 30 to 335 mg-KOH/g. Here, 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, for example, by titration using an aqueous potassium hydroxide solution.

In the coloring composition, the content of the resin (B) 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 very 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) and the solvent (E) in advance 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 in 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, very preferably 1% by mass to 60% by mass, and most preferably 1% by mass to 50% by mass, based on 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 to 99.9999% by mass, more preferably 0.0001 to 99% by mass, even more preferably 1 to 99% by mass, particularly preferably 3 to 99% by mass, and even more preferably 5 to 99% by mass, based on the total amount of solid content in the solution containing the compound (I).

The compound (I) may be subjected to, if necessary, rosin treatment, surface treatment using a derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment on the surface of the compound (I) with a polymer compound or the like, micronization treatment by a sulfuric acid micronization method, a salt milling method or the like, cleaning treatment by an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like.

Further, the compound (I) may be subjected to the following treatment as required:

crystal structure conversion, particle shaping and/or substantial 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 the compound (I) with a changed crystal structure;

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

treatment in which compound (I) is mixed with water, sulfuric acid or an organic solvent, stirred and/or heated with stirring to obtain a solution or a suspension, the solution or the suspension is mixed with a poor solvent for compound (I) to obtain a suspension, and the suspension is filtered to obtain compound (I) having a modified crystal structure;

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

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

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

When a plurality of compounds (I) or derivatives are used, these treatments may be carried out individually 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, diphenyl ether and the like; 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 dichloromethane, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; a nitrated hydrocarbon solvent such as nitrobenzene; amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and the like.

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, diphenyl ether and the like; 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 dichloromethane, chloroform, 1, 2-dichlorobenzene, trichlorobenzene (e.g., 1,3, 5-trichlorobenzene), 1-chloronaphthalene, and 2-chloronaphthalene; a nitrated hydrocarbon solvent such as nitrobenzene; and the like.

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

When the solution containing the compound (I) contains the 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, based on 100 parts by mass of the compound (I).

The compound (I) can 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 carried out individually or in combination.

The dispersant may be any of cationic, anionic, nonionic and amphoteric surfactants. Specifically, there may be mentioned polyester, polyamide, acrylic and other surfactants. These dispersants may be used alone or in combination of 2 or more. Examples of the dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by AJIAOSU Fine chemical Co., Ltd.), DISPERBYK (registered trademark) (manufactured by BYK-Chemie), BYK (registered trademark) (manufactured by BYK-Chemie).

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, based on 100 parts by mass of the compound (I). When the amount of the dispersant used is within the above range, a solution containing the compound (I) in a more uniformly dispersed state tends to be obtained.

When the coloring composition of the present invention contains the resin (B) and the compound (I) -containing solution containing the compound (I) and the solvent (E) is prepared in advance and then the coloring composition of the present invention is prepared using the compound (I) -containing solution, 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 containing the resin (B) in advance, 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, further preferably 0.1 to 500 parts by mass, and particularly preferably 0.1 to 300 parts by mass, based on 100 parts by mass of the compound (I).

[ polymerizable Compound (C) ]

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

Examples of the polymerizable compound having 1 ethylenically unsaturated bond include nonylphenylcarbinol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 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 Esters and the like are preferably dipentaerythritol penta (meth) acrylate and 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, further preferably 1% by mass to 90% by mass, particularly preferably 2% by mass to 80% by mass, and very preferably 3% by mass to 70% by mass, relative to 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 an active radical, an acid, or the like under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator (D) include oxime compounds such as O-acyloxime compounds, alkylphenone compounds, bisimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-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-dioxopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, etc. Further, as the O-acyloxime compound, commercially available products such as Irgacure OXE01, OXE02 (both of which are manufactured by BASF) and N-1919 (manufactured by ADEKA Co., Ltd.) 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 alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholino) phenyl ] butan-1-one. As the alkylphenone compound, commercially available products such as Irgacure 369, 907 and 379 (all of which are manufactured by BASF) can be used.

Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone and benzildimethylketal.

Examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5' -tetraphenylbiimidazole (see, for example, japanese patent application laid-open No. 6-75372, japanese patent application laid-open No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (alkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (dialkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (trialkoxyphenyl) biimidazole (see, for example, japanese patent publication No. 48-38403, japanese patent publication No. 62-174204, etc.), and 4, 4', and biimidazole compounds in which the phenyl group at the 5, 5' -position is substituted with a carbonylalkoxy group (see, for example, Japanese patent laid-open No. 7-10913).

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, and the like.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure (registered trademark) 819 (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 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiation aid (hereinafter, sometimes referred to as a polymerization initiation 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 alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound and a bisimidazole 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, and more preferably 0.01 to 50% by mass, based on the total amount of the resin (B) and the polymerizable compound (C).

[ polymerization initiation assistant (D1) ]

The coloring composition of the present invention may contain a polymerization initiation aid (D1). The polymerization initiation aid (D1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound (C) whose polymerization is 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 initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson), 4' -bis (diethylamino) benzophenone, and 4,4 '-bis (ethylmethylamino) benzophenone, and 4, 4' -bis (diethylamino) benzophenone is preferable. As the amine compound, a commercially available compound such as EAB-F (manufactured by UK 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 phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylsulfanylacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

When these polymerization initiation aids (D1) are used, the content thereof is preferably 0.00001 to 60% by mass, more preferably 0.0001 to 50% by 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, sometimes referred to as a colorant (a 1)). The colorant (a1) may contain 1 or 2 or more colorants. The colorant (a1) preferably contains 1 or more selected from a yellow colorant, an orange colorant, a red colorant and a green colorant, and more preferably contains 1 or more selected from a yellow colorant and a green colorant.

The colorant (a1) may be a dye or a pigment. As The dye, known dyes can be used, and for example, known dyes described in The color index (published by The Society of Dyers and Colourists) and dyeing guidelines (chromo). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, isoindoline dyes, and the like can be given. These dyes may be used alone or in combination of 2 or more.

Specific examples thereof include the following color index (c.i.) numbered dyes.

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. solvent 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, 59:1, 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. solvent dyes such as c.i. solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35,

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, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

c.i. acid violet 6B, 7, 9, 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, 90:1, 91, 92, 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, 243, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 267, 296, 278, 285, 340, 285, 340;

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

c.i. direct yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

c.i. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

c.i. direct blue 1, 2, 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, 256, 236, 229, 237, 242, 244, 245, 247, 238, 248, 250, 257, 275, 260, 251, 293, 268, 274, 251, 268;

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

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

c.i. disperse violet 26, 27;

c.i. disperse dyes such as 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. alkaline green 1; and the like, the basic dye is added,

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

c.i. reactive orange 16;

c.i. reactive red 36; and the like, the C.I. reactive dye,

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

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

c.i. media 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. mordant dyes such as c.i. mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53,

C.I. vat dyes such as C.I. vat Green 1, and the like

Further, Lumogen (registered trademark) which is a product of BASF may be mentioned, and 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) may be mentioned.

Further, a compound represented by the formula (z), a compound represented by the formula (z1), and the like can be given.

As The pigment, known pigments can be used, and for example, pigments classified as pigments (pigments) in The color index (published by The Society of Dyers and Colourists) can be cited. They may be used alone or in combination of 2 or more.

Specifically, there may be mentioned 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 and the like;

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

red pigments such as 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 and the like;

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

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

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

c.i. brown pigments such as pigment brown 23, 25;

c.i. pigment black 1, 7, 31, 32 and the like.

As the colorant (a1), a yellow dye and a yellow pigment (hereinafter, they may be collectively referred to as "yellow colorant"), an orange dye and an orange pigment (hereinafter, they may be collectively referred to as "orange colorant"), a red dye and a red pigment (hereinafter, they may be collectively referred to as "red colorant"), a green dye and a green pigment (hereinafter, they may be collectively referred to as "green colorant") are preferable, a yellow colorant and a green colorant are more preferable, a yellow pigment and a green pigment are further preferable, and a green pigment is particularly preferable.

Examples of the yellow dye include dyes of which hue is classified as yellow among the dyes, and examples of the yellow pigment include pigments of which hue is classified as yellow among the pigments. 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, and further preferably c.i. pigment yellow 138, 139, 150, 185, 231.

Examples of the orange dye include dyes of the above dyes classified into orange in hue, and examples of the orange pigment include pigments of the above pigments classified into orange in hue. As the orange colorant, an orange dye and an orange pigment are preferable, an 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.

Examples of the red dye include dyes of the above dyes classified into red in hue, and examples of the red pigment include pigments of the above pigments classified into red in hue. As the red colorant, a red dye and a red pigment are preferable, more preferable are 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, and further preferable are c.i. acid red 52, c.i. pigment red 144, 177, 179, 242, 254 and 269.

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

Examples of the green dye include dyes of the above dyes classified into green in hue, and examples of the green pigment include pigments of the above pigments classified into green in hue. As the green colorant, a green dye and a green pigment are preferable, a green pigment is more preferable, a phthalocyanine pigment is further preferable, a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment and a halogenated aluminum zinc phthalocyanine pigment are particularly preferable, and c.i. pigment green 7, 36, 58, 59, 62 and 63 are further preferable.

[ preparation of a solution containing colorant (A1) ]

When the coloring composition of the present invention contains the colorant (a1), a solution containing the colorant (a1) containing the colorant (a1) and the solvent (E) may be prepared in advance, and then the coloring composition may be prepared using the solution containing the colorant (a 1). 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 content 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, very preferably 1% by mass to 60% by mass, and most preferably 1% by mass to 50% by mass, based on the total amount of the solution containing the colorant (a 1).

The content of the colorant (a1) in the solution containing the colorant (a1) is 100% by mass or less, preferably 0.0001 to 99.9999% by mass, more preferably 0.0001 to 99% by mass, even more preferably 1 to 99% by mass, particularly preferably 3 to 99% by mass, and even more preferably 5 to 99% by mass, of the total amount of solid components in the solution containing the colorant (a 1).

The colorant (a1) may be subjected to, if necessary, rosin treatment, surface treatment using a derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment on the surface of the colorant (a1) with a polymer compound or the like, sulfuric acid microparticulation, microparticulation with a salt milling method or the like, cleaning treatment with an organic solvent, water or the like for removing impurities, removal treatment with an ion exchange method or the like for ionic impurities, crystal structure conversion similar to that of the compound (I), shaping of particles, substantial homogenization of particle diameter, or the like. The particle diameter of the colorant (a1) is preferably substantially uniform.

The colorant (a1) can be brought into a state where the colorant (a1) is uniformly dispersed in the solution containing the colorant (a1) by performing a dispersion treatment with a dispersant. 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, there may be mentioned polyester, polyamide, acrylic and other surfactants. These dispersants may be used alone or in combination of two or more. Examples of the dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by AJIAOSU Fine chemical Co., Ltd.), DISPERBYK (registered trademark) (manufactured by BYK-Chemie), BYK (registered trademark) (manufactured by BYK-Chemie).

When the solution containing the colorant (a1) contains a dispersant, the amount of the dispersant (solid content) 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 (a 1). When the amount of the dispersant used is within the above range, a more uniformly dispersed solution containing the colorant (a1) tends to be obtained.

When the coloring composition of the present invention is prepared by using the solution containing the colorant (a1) after the coloring composition of the present invention contains the resin (B) and preparing the solution containing the colorant (a1) 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 containing the resin (B) in advance, the dispersion stability of the solution containing the colorant (a1) can be further improved.

When the solution containing the colorant (a1) 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, based on 100 parts by mass of the colorant (a 1).

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 0.0001 to 99.9999% by mass, more preferably 0.0001 to 99% by mass, further preferably 0.0001 to 90% by mass, particularly preferably 0.0001 to 80% by mass, further preferably 0.0001 to 70% by mass, particularly preferably 0.0001 to 60% by mass, very preferably 0.0001 to 55% by mass, and most preferably 0.1 to 55% by mass, based on 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% by mass or more, preferably 0.0003% by mass or more, more preferably 0.0005% by mass or more, further preferably 0.001% by mass or more, and the upper limit is less than 100% by mass, preferably 99.9999% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, and particularly preferably 97% by mass or less, of the total amount of the colorant (a).

[ leveling agent (F) ]

Examples of the leveling agent (F) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These 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 DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Toray Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF 46, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan contract Co., Ltd.) may be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F183, MEGAFACE F554, MEGAFACE R30, MEGAFACE RS-718-K (manufactured by DIC Co., Ltd.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Material electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Nitro Co., Ltd.), and E5844 (manufactured by King Korea research Co., Ltd.).

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, and MEGAFACE F443 (manufactured by DIC corporation) and the like can be mentioned.

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 still more preferably 0.0001 to 1% by mass, based on 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, the antioxidant is preferably used alone or in combination of 2 or more. The antioxidant is not particularly limited as long as it is an industrially commonly used antioxidant, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.

Examples of the above-mentioned phenol-based antioxidant include Irganox 1010(Irganox 1010: pentaerythritol tetrakis [ 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF), Irganox 1076(Irganox 1076: octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by BASF), Irganox 1330(Irganox 1330: 3,3 ', 5,5 ' -hexa-t-butyl-a, a ' - (mesitylene-2, 4, 6-triyl) tri-p-cresol, manufactured by BASF), Irganox 3114(Irganox 3114: 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1, 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione, manufactured by BASF), Irganox 3790(Irganox 3790: 1,3, 5-t-butyl-4-hydroxybenzyl) -1, 3, 5-triazine-2, 4,6(1H, 5H) -trione, manufactured by BASF), 3, 5-triazine-2, 4,6(1H, 3H, 5H) -trione, manufactured by BASF), Irganox 1035(Irganox 1035: thiodiethylene bis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF), Irganox1135 (Irganox 1135: phenylpropanoic acid, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF), Irganox 1520L (Irganox 1520L: 4, 6-bis (octylthiomethyl) -o-cresol, manufactured by BASF), Irganox 3125(Irganox 3125, manufactured by BASF), Irganox 565(Irganox 565: 2, 4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5' -di-tert-butylanilino) -1, 3, 5-triazine manufactured by 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), Sumilizer BHT (Sumilizer BHT, manufactured by Sumilizer Chemicals Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumilizer Chemicals Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumilizer Chemicals Co., Ltd.), Cyanox 1790(Cyanox 1790, (manufactured by Sitech) and vitamin E (manufactured by Eisai Co., Ltd.), etc.

Examples of the phosphorus-based antioxidant include Irgafos 168(Irgafos 168: tris (2, 4-di-t-butylphenyl) phosphite, manufactured by BASF), Irgafos 12(Irgafos 12: tris [ 2- [ [2,4,8, 10-tetra-t-butylbenzo [ d, f ] [1,3,2] dioxaphosphin-6-yl ] oxy ] ethyl ] amine, manufactured by BASF), Irgafos 38(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), ADSTAB PEP-8 ((manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston618 (GE, manufactured by Weston618, manufactured by Wemilstin), Wemilstin 626 (manufactured by Westin G619, manufactured by Westin 626, manufactured by Westin GK-6-hydroxy propoxy 3- (GP-3, manufactured by Westin) (manufactured by Westin) and U.3- (3-butyl) propoxy G, manufactured by BASF) -2, 4,8, 10-tetra-tert-butyldibenzo [ d, f ] [1.3.2] dioxaphosphepin) (manufactured by Sumitomo chemical Co., Ltd.), and the like.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and β -alkylmercaptopropionate compounds of polyhydric alcohols such as tetrakis [ methylene (3-dodecylthio) propionate ] methane.

[ other ingredients ]

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

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-thioalkylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-glycidyloxy-3-epoxysilane, and the like, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane, etc.

[ 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 initiation aid (D1), the colorant (a1), the leveling agent (F), the antioxidant (G), and/or other components. The mixing can be carried out by using a known or customary apparatus and conditions.

The compound (I) is preferably used in the form of a solution containing the compound (I) dispersed in a bead mill or the like until the average particle size of the compound (I) is about 0.2 μm or less after being mixed with a part or all of the solvent (E). In this case, a part or all of the above-mentioned dispersant and 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 colorant (a1) -containing solution having an average particle diameter of the colorant (a1) of about 0.2 μm or less. In this case, a part or all of the above-mentioned dispersant and resin (B) may be blended as necessary.

The compound (I) is preferably used in the state of a solution (the solution is included in a solution containing the compound (I)) obtained by dissolving a part or all of the solvent (E) in advance. Preferably, the solution containing the compound (I) is further filtered through a filter having a pore size of about 0.01 to 1 μm.

The colorant (a1) is preferably used in the form of a solution (the solution is contained in a solution containing the colorant (a 1)) prepared by dissolving a part or all of the solvent (E) in advance. Preferably, the solution containing the colorant (A1) is further filtered through a filter having a pore size of about 0.01 to 1 μm.

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

[ color Filter ]

A color filter can be formed from the colored composition of the present invention.

The colored composition is applied to a substrate, and a volatile component such as a solvent is removed and dried, thereby forming a colored coating film. The colored coating film thus formed is included in the color filter of the present invention.

Examples of a method for forming a colored pattern include a photolithography method, an ink jet method, a printing method, and the like. Among them, photolithography is preferable. The photolithography method is a method in which the colored composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and/or without performing development at the time of exposure. The colored pattern and the colored coating film formed in this way are the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and can be suitably adjusted according to the purpose, application, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate of silicon, a substrate having a thin film of aluminum, silver/copper/palladium alloy 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 following can be used.

First, a substrate is coated with the coloring composition, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and dry the composition, 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 for heating and drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃. The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

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

The pattern on the photomask is not particularly limited, and a pattern 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 less than 350nm may be cut off using a filter that cuts off the wavelength region, or light near 436nm, near 408nm, or near 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 parallel light rays to the entire exposure surface and perform precise alignment of the photomask and the substrate on which the colored composition layer is formed, an exposure apparatus such as a mask aligner and a stepper is preferably used.

The exposed colored composition layer is brought into contact with a developer to develop the layer, thereby forming a colored pattern on the substrate. The unexposed portion of the colored 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, or 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 a paddle method, a dipping method, a spraying method, and the like. Further, the substrate is tilted at an arbitrary angle during development.

The developed substrate is preferably washed with water.

Further preferably, the obtained colored pattern is subjected to post-baking.

The post-drying temperature is preferably 150-250 ℃, and more preferably 160-235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes. The color filter as a colored pattern or a colored coating film obtained by the above-mentioned method 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 (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) or a solid-state imaging device, particularly a color filter used in a liquid crystal display device.

The present application claims benefits based on priority of japanese patent application No. 2019-026911, filed on 18/2/2019. The entire contents of the specification of japanese patent application No. 2019-026911, filed on 18.2.2019, are incorporated herein by reference.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples, and it is needless to say that the present invention can be carried out with appropriate modifications within the scope suitable for the above and the gist described later, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

In the following synthesis examples, the structure of the compound was confirmed by MASS analysis (LC; model 1200 by Agilent, MASS; 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-8120 GPC (manufactured by Tosoh corporation)

The column is TSK-GELG 2000HXL

Column temperature 40 deg.C

Solvent tetrahydrofuran

Flow rate 1.0 mL/min

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

Sample size 50 μ L

Detector RI

The calibration standard substance is TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh corporation)

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

Example 1

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

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

To the mixture were added 13.6 parts of 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 22.9 parts of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 66.4 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

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

To the mixture were added 8.32 parts of 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 11.7 parts of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 43.5 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

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.

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

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

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

The mixture was stirred at room temperature, filtered, and the resulting residue was washed 3 times with the same volume of N, N-dimethylformamide as the resulting residue.

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

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

< identification of Compound represented by the formula (Ia2) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺519

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^-517

Exact molecular weight 518

Example 2

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

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

To the mixture were added 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.).

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

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

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

To the mixture were added 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.).

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.

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

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

< identification of Compound represented by the formula (Ia23) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺691

(Mass analysis) 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 Kasei Kogyo Co., Ltd.), 3.49 parts of 4-phenylethynylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 3.95 parts of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 28.7 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed.

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

To the mixture were added 0.476 parts of 4-phenylethynylphthalic 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.).

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

0.801 parts of 4-phenylethynylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2.90 parts of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 9.13 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to the mixture.

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

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

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

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

< identification of Compound represented by the formula (Ia22) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺619

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^-617

Exact molecular weight 618

Example 4

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

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

To the mixture was added 40.2 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

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

To the mixture was added 28.0 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

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 was added 173 parts of methanol.

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 formula (Ia10), the compound represented by formula (Ia2143), the compound represented by formula (Ia850), and the compound represented by formula (Ia 315).

< identification of Compound represented by the formula (Ia10) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺507

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^-505

Exact molecular weight 506

< identification of Compound represented by formula (Ia2143) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺521

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^-519

Exact molecular weight 520

< identification of Compound represented by formula (Ia850) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H ]⁺521

(Mass analysis) ionization mode＝ESI－:m/z＝[M－H]^-519

Exact molecular weight 520

< identification of Compound represented by formula (Ia315) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺535

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^-533

Exact molecular weight 534

Example 5

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

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

To the mixture were added 7.12 parts of 3-nitrophthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 10.3 parts of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 16.0 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

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 obtained residue was washed 5 times with 400 parts of methanol.

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

< identification of Compound represented by the formula (Ia35) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺509

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^-507

Exact molecular weight 508

Example 6

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

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

To the mixture were added 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.).

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

To the mixture was added 9 parts of methyl benzoate (manufactured by tokyo chemical industries, ltd.).

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

To the mixture were added 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.).

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

To the mixture were added 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.).

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

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

< identification of Compound represented by the formula (Ia1) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺419

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^-417

Exact molecular weight 418

Example 7

1.05 parts of a mixture of the compound represented by the formula (Ia10), the compound represented by the formula (Ia2143), the compound represented by the formula (Ia850), and the compound represented by the formula (Ia315) 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 resulting mixture was added 8.19 parts of a mixture of 3.23 parts of iron (III) nitrate nonahydrate (manufactured by wako pure chemical industries, ltd.) and 29.1 parts of water 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 at 60 ℃ under reduced pressure 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 Kasei Kogyo Co., Ltd.), 13.6 parts of 4-nitrophthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 19.5 parts of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 116 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed.

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

To the mixture were added 7.12 parts of 4-nitrophthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 10.5 parts of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 30.1 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

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

To the mixture were added 13.6 parts of 4-nitrophthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 19.9 parts of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 29.1 parts of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

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

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

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

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

< identification of Compound represented by the formula (Ia33) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺509

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^-507

Exact molecular weight 508

Example A-1

1 mol of 4-amino-2-methylquinoline (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 8 mol of 3-methylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 21 mol of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 73 times the weight of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) of 1 mol of 4-amino-2-methylquinoline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed.

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

The mixture was cooled to room temperature, and methanol was added to the mixture in an amount of 13 times the weight of the mixture.

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

The obtained 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 Compound represented by the formula (Ia5) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺447

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－445

Precise molecular weight 446

Example A-2

A compound represented by the formula (Ia3) 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 1, 2-naphthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by the formula (Ia3) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺519

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－517

Exact molecular weight 518

Examples A to 3

A compound represented by the formula (Ia17) 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 Compound represented by the formula (Ia17) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺487

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－485

Exact molecular weight of 486

Examples A to 4

A compound represented by the formula (Ia7) 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 Compound represented by the formula (Ia7) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺487

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－485

Exact molecular weight of 486

Examples A to 5

A compound represented by the formula (Ia36) 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-acetamidophthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by the formula (Ia36) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺533

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－531

Exact molecular weight 532

Examples A to 6

A compound represented by the formula (Ia51) was obtained in the same manner as in example A-1, except that 3-methylphthalic anhydride (manufactured by Tokyo Kasei Co., Ltd.) was replaced with 3-hydroxyphthalic anhydride (manufactured by Sigma-Aldrich Japan).

< identification of Compound represented by the formula (Ia51) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺451

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－449

Exact molecular weight 450

Examples A to 7

A compound represented by the formula (Ia19) was obtained in the same manner as in example A-1, except that 3-methylphthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.) was used instead of 3-fluorophthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by the formula (Ia19) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺455

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－453

Exact molecular weight 454

Examples A to 8

The reaction was carried out in the same manner as in example A-1 except for replacing 3-methylphthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.) with the compound represented by the formula (sm1), thereby obtaining a compound represented by the formula (Ia 248).

< identification of Compound represented by the formula (Ia248) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺507

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－505

Exact molecular weight 506

Examples A to 9

A compound represented by the formula (Ia4) 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 Compound represented by the formula (Ia4) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺447

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－445

Precise molecular weight 446

Examples A to 10

The reaction was carried out in the same manner as in example A-1 except for replacing 4-amino-2-methylquinoline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) with 4-amino-6-fluoro-2-methylquinoline (manufactured by Sigma-Aldrich Japan K.K.) and replacing 3-methylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) with 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), thereby obtaining a compound represented by the formula (It 242).

< identification of Compound represented by formula (It242) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺537

(Mass analysis) ionization mode ESI-M/z [ M-H ] ]^－535

Exact molecular weight 536

Examples A to 11

The reaction was carried out in the same manner as in example A-1 except for replacing 4-amino-2-methylquinoline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) with 4-amino-6-methoxy-2-methylquinoline (manufactured by Sigma-Aldrich Japan) and replacing 3-methylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) with 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), thereby obtaining a compound represented by the formula (It 232).

< identification of Compound represented by formula (It232) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺549

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－547

Exact molecular weight 548

Examples A to 12

A compound represented by the formula (It750) was obtained in the same manner as in example A-1, except that 4-amino-2-methylquinoline (manufactured by Tokyo Kasei Co., Ltd.) was replaced with 4-amino-6-bromo-2-methylquinoline (manufactured by Sigma-Aldrich Japan Co., Ltd.).

< identification of Compound represented by formula (It750) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺525

(mass fraction)Chromatography) ionization mode-ESI-M/z-M-H]^－523

Exact molecular weight 524

Synthesis example B-1

1 mol of the compound represented by the formula (Ia2) was mixed with a mixture of 20 mol of potassium hydroxide and 10 times by weight of water as much as the weight of 1 mol of the compound represented by the formula (Ia 2). The mixture was kept at 90 ℃ and stirred until the compound represented by formula (Ia2) disappeared. 36% hydrochloric acid was mixed with the mixture to perform neutralization. The mixture was filtered. The obtained residue was washed with water. The residue was purified by column chromatography to give a compound represented by the formula (IM 1-1).

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

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺339

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－337

Exact molecular weight 338

Synthesis example B-2

A compound represented by the formula (IM 1-2) was obtained in the same manner as in Synthesis example B-1, except that the compound represented by the formula (Ia2) was replaced with the compound represented by the formula (Ia 23).

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

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺425

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－423

Exact molecular weight 424

Synthesis example B-3

A compound represented by the formula (IM 1-3) was obtained in the same manner as in Synthesis example B-1, except that the compound represented by the formula (Ia2) was replaced with the compound represented by the formula (Ia 5).

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

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺303

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－301

Exact molecular weight 302

Synthesis example B-4

A compound represented by the formula (IM 1-4) was obtained in the same manner as in Synthesis example B-1, except that the compound represented by the formula (Ia2) was replaced with the compound represented by the formula (Ia 4).

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

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺303

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－301

Exact molecular weight 302

Synthesis example B-5

A compound represented by the formula (IM 1-5) was obtained in the same manner as in Synthesis example B-1, except that the compound represented by the formula (Ia2) was replaced with the compound represented by the formula (Ia 36).

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

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺346

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－344

Exact molecular weight 345

Synthesis example B-6

A compound represented by the formula (IM 1-6) was obtained in the same manner as in Synthesis example B-1, except that the compound represented by the formula (Ia2) was replaced with the compound represented by the formula (Ia 1).

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

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺289

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－287

Exact 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 Kasei Kogyo Co., Ltd.), 21 mol of benzoic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 73 times by weight of methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) based on 1 mol of the compound represented by the formula (IM 1-1) were mixed. The mixture was kept at 170 ℃ and stirred for 120 hours. The mixture was cooled to room temperature, and methanol was added to the mixture in an amount of 13 times the weight of the mixture. The resulting mixture was stirred at room temperature and then filtered. The obtained 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 Compound represented by formula (Ia699) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺513

(Mass analysis) ionization mode [ ESI ] - [ m/z ] ] [ [ m/z ] ]M－H]^－511

Exact molecular weight 512

Example C-2

A compound represented by the formula (Ia970) 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 Kasei Kogyo Co., Ltd.) was replaced with 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of Compound represented by formula (Ia970) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺605

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－603

Exact molecular weight 604

Example C-3

A compound represented by the formula (Ia703) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by Tokyo chemical industry Co., Ltd.) was used instead of tetrachlorophthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by the formula (Ia703) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺605

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－603

Exact molecular weight 604

Example C-4

A compound represented by the formula (If3796) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by Tokyo chemical industry Co., Ltd.) was used instead of 3-methylphthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by formula (If3796) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺483

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－481

Precise molecular weight 482

Example C-5

A compound represented by the formula (Ia696) was obtained in the same manner as in example C-1, except that phthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.) was used instead of trimellitic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by formula (Ia696) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺469

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－467

Exact molecular weight 468

Example C-6

A compound represented by the formula (Ia969) 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 Kasei Kogyo Co., Ltd.) was replaced with phthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of Compound represented by formula (Ia969) >

(Mass analysis) ionization mode +ESI +:m/z＝[M+H]⁺555

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－553

Exact molecular weight 554

Example C-7

A compound represented by the formula (If2528) 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 Kasei Kogyo Co., Ltd.) was replaced with 3-methylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of the Compound represented by the formula (If2528) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺569

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－567

Exact molecular weight 568

Example C-8

A compound represented by the formula (Ia973) 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).

< identification of Compound represented by the formula (Ia973) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺599

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－597

Exact molecular weight 598

Example C-9

A compound represented by the formula (If1261) 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).

< identification of Compound represented by formula (If1261) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺477

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－475

Exact molecular weight 476

Example C-10

A compound represented by the formula (If5688) 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 Kasei Kogyo Co., Ltd.) was replaced with tetrachlorophthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of the Compound represented by the formula (If5688) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺569

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－567

Exact molecular weight 568

Example C-11

A compound represented by the formula (If636) 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 Kasei Kogyo Co., Ltd.) was replaced with 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of the Compound represented by the formula (If636) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺483

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－481

Precise molecular weight 482

Example C-12

A compound represented by the formula (If5670) 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 Kasei Kogyo Co., Ltd.) was replaced with 1, 2-naphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of Compound represented by formula (If5670) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺483

(Mass analysis) ionization mode ESI-M/z [ M-H ] ]^－481

Precise molecular weight 482

Example C-13

A compound represented by the formula (If5720) 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 Kasei Kogyo Co., Ltd.) was replaced with 1, 8-naphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of Compound represented by formula (If5720) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺483

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－481

Precise molecular weight 482

Examples C to 14

A compound represented by the formula (Ia712) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by Tokyo chemical industry Co., Ltd.) was used instead of 1, 8-naphthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by formula (Ia712) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺519

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－517

Exact molecular weight 518

Examples C to 15

A compound represented by the formula (If635) was obtained in the same manner as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced by the compound represented by the formula (IM 1-4), and trimellitic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was replaced by 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of Compound represented by formula (If635) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺483

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－481

Precise molecular weight 482

Example C to 16

A compound represented by the formula (If1260) was obtained by the same procedures as in example C-1 except that the compound represented by the formula (IM 1-1) was replaced by the compound represented by the formula (IM 1-4).

< identification of the Compound represented by the formula (If1260) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺477

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－475

Exact molecular weight 476

Example C to 17

A compound represented by the formula (If13040) 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 Kasei Kogyo Co., Ltd.) was replaced with pyromellitic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of Compound represented by formula (If13040) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺521

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－519

Exact molecular weight 520

Example C-18

A compound represented by the formula (If8454) 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 Kasei Kogyo Co., Ltd.) was replaced with 4-tert-butylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of the Compound represented by the formula (If8454) >

(Mass analysis) ionization mode＝ESI+:m/z＝[M+H]⁺489

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－487

Precise molecular weight 488

Examples C to 19

A compound represented by the formula (If3795) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by Tokyo chemical industry Co., Ltd.) was used instead of 4-methylphthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by formula (If3795) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺483

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－481

Precise molecular weight 482

Example C-20

A compound represented by the formula (If5671) 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 Kasei Kogyo Co., Ltd.) was replaced with 4-methylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of the Compound represented by the formula (If5671) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺447

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－445

Precise molecular weight 446

Example C-21

A compound represented by the formula (If2511) 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 Kasei Kogyo Co., Ltd.) was replaced with 3-methylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of Compound represented by formula (If2511) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺447

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－445

Precise molecular weight 446

Example C-22

A compound represented by the formula (If3799) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by Tokyo chemical industry Co., Ltd.) was used instead of 4-t-butylphthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by formula (If3799) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺525

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－523

Exact molecular weight 524

Example C-23

A compound represented by the formula (If3814) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by Tokyo chemical industry Co., Ltd.) was used instead of 3-acetamidophthalic anhydride (manufactured by Tokyo chemical industry Co., Ltd.).

< identification of Compound represented by formula (If3814) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺526

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－524

Exact molecular weight: 525

Example C-24

A compound represented by the formula (If654) 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 Kasei Kogyo Co., Ltd.) was replaced with 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of the Compound represented by the formula (If654) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺526

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－524

Exact molecular weight: 525

Example C-25

A compound represented by the formula (If29) 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 Kasei Kogyo Co., Ltd.) was replaced with phthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of the Compound represented by the formula (If29) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺476

(Mass analysis) ionization mode ESI-M/z [. M-H]^－474

Accurate molecular weight: 475

Example C-26

A compound represented by the formula (If1279) 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).

< identification of the Compound represented by the formula (If1279) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺520

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－518

Exact molecular weight 519

Example C-27

The reaction was carried out 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 Kasei Kogyo Co., Ltd.) was replaced with the compound represented by the formula (sm1), to obtain a compound represented by the formula (If 1904).

< identification of Compound represented by formula (If1904) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺520

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－518

Exact molecular weight 519

Example C-28

A compound represented by the formula (Ia728) was obtained in the same manner as in example C-1, except that trimellitic anhydride (manufactured by Tokyo Kasei Co., Ltd.) was used instead of the compound represented by the formula (sm 1).

< identification of Compound represented by formula (Ia728) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺513

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－511

Exact molecular weight 512

Example C to 29

A compound represented by the formula (Ia657) 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 Kasei Kogyo Co., Ltd.) was replaced with 2, 3-naphthalenedicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of Compound represented by the formula (Ia657) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺469

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－467

Exact molecular weight 468

Examples C to 30

A compound represented by the formula (If3171) 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 Kasei Kogyo Co., Ltd.) was replaced with 3-methylphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.).

< identification of the Compound represented by the formula (If3171) >

(Mass analysis) ionization mode＝ESI+:m/z＝[M+H]⁺433

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－431

Exact molecular weight 432

Example C-31

The reaction was carried out in the same manner as in example C-1 except for replacing the compound represented by formula (IM 1-1) with the compound represented by formula (IM 1-6) and replacing trimellitic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) with 3-chlorophthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), thereby obtaining a compound represented by formula (Ia 686).

< identification of Compound represented by formula (Ia686) >

(Mass analysis) ionization mode ESI +: M/z ═ M + H]⁺453

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－451

Exact molecular weight 452

Example E-1

1.61 parts of the compound represented by the formula (Ia5) and 32.7 parts of fuming sulfuric acid (25%) (manufactured by Fuji film and Wako pure chemical industries, Ltd.) were mixed while maintaining the temperature 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. 10% aqueous ammonia was added to the obtained filtrate 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 methanol in an amount of 2 times the volume of the mixture. The mixture was filtered, and the solvent of the resulting filtrate was distilled off. Drying the obtained residue at 60 deg.C under reduced pressure to obtain a mixture containing the compound represented by formula (Ia 5-SA 1) (compound represented by formula (Ia5) wherein any 1 hydrogen atom is replaced by-SO ₃NH₄Compound of (Ia) 5-SA 2) and the compound represented by the formula (Ia 5-SA 2) (the compound represented by the formula (Ia5) wherein any 2 hydrogen atoms are substituted by — SO₃NH₄Compound (b) of0.58 portion.

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

(Mass analysis) ionization mode ESI-M/z [ M-NH ]₄+H－H]^－525

Precise molecular weight 543

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

(Mass analysis) ionization mode ESI-M/z [ M-NH ]₄－NH₄+H+H－H]^－605

Exact molecular weight 640

Example E-2

0.30 part of the compound represented by the formula (Ia1), 3.00 parts of chloroform and 0.55 part of chlorosulfonic acid (manufactured by Tokyo Kasei Kogyo 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. Drying the residue at 60 deg.C under reduced pressure to obtain a mixture containing the compound represented by formula (Ia 1-SA 1) (compound represented by formula (Ia1) wherein any 1 hydrogen atom is replaced by-SO₃H compound) and a compound represented by the formula (Ia 1-SA 2) (compound represented by the formula (Ia1) wherein any 1 hydrogen atom is replaced by-SO₂Compound of Cl) 0.18 part.

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

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－497

Exact molecular weight: 498

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

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－515

Exact molecular weight 516

Example E-3

1.00 part of the compound represented by the formula (Ia2) and 20.6 parts of fuming sulfuric acid (30%) (manufactured by Fuji film 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. Drying the residue at 60 deg.C under reduced pressure to obtain a mixture containing the compound represented by the formula (Ia 2-SA) (formula (Ia2) wherein any 2 hydrogen atoms are replaced by-SO)₃Compound of H) 0.40 part.

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

(Mass analysis) ionization mode ESI-M/z [ M-H ]]^－677

Exact molecular weight 678

Synthesis example 1

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80 ℃ while stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 5 hours ^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0² ^,6]Mixture of decane-9-yl ester (containing 1:1 molar ratio) 289 part, propylene glycol monomethyl ether acetate 125 partAnd (3) solution. On the other hand, a solution prepared 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 held at 80 ℃ for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution containing 35.0% of a solid content. The weight-average molecular weight of the obtained resin B1 was 8800, the degree of dispersion was 2.1, and the acid value in terms of solid content was 80 mg-KOH/g.

Synthesis example 2

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with a nitrogen atmosphere, 340 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80 ℃ while stirring. Subsequently, 57 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 5 hours^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0² ^,6]A mixed solution of 54 parts of a mixture of decan-9-yl esters (containing a molar ratio of 1:1), 239 parts of benzyl methacrylate and 73 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution prepared 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 held at 80 ℃ for 3 hours and then cooled to room temperature to obtain a copolymer (resin B2) solution having a solid content of 36.8%. The weight-average molecular weight of the obtained copolymer was 9400, the degree of dispersion was 1.89, and the acid value in terms of solid content was 114 mg-KOH/g.

Example 9

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

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

The coloring composition 1 was applied onto 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 prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film are shown in table 39. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked 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 (Ia2) was replaced with the compound represented by the formula (Ia23), thereby obtaining a prebaked colored coating film and a postbaked colored coating film. The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film are shown in table 39.

Example 11

A coloring composition was obtained in the same manner as in example 9 except that the compound represented by the formula (Ia2) was replaced with the compound represented by the formula (Ia10), the compound represented by the formula (Ia2143), the compound represented by the formula (Ia850), and the compound represented by the formula (Ia315) which were obtained in example 4, and a prebaked colored coating film and a postbaked colored coating film were obtained. The film thickness of the prebaked colored coating film and the wavelength of the shoulder on the longest side of the absorption spectrum of the prebaked 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 (Ia2) was replaced with the compound represented by the formula (Ia35), thereby obtaining a prebaked colored coating film and a postbaked colored coating film. The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film are shown in table 39.

Example 13

The respective 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 onto 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 prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film are shown in table 39. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

Example 14

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

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

The coloring composition 3 was applied onto 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 prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the wavelength of the shoulder on the longest side of the absorption spectrum of the prebaked colored coating film are shown in Table 39. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

Example 15

A coloring composition was obtained in the same manner as in example 14 except that the compound represented by the formula (Ia10), the compound represented by the formula (Ia2143), the mixture of the compound represented by the formula (Ia850) and the compound represented by the formula (Ia315) obtained in example 4 was replaced with the compound represented by the formula (Ia33), and a prebaked colored coating film and a postbaked colored coating film were obtained. The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film are shown in table 39.

Example 16

The respective components 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 onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film are shown in table 39. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

Comparative example 1

The respective components 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 onto 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 prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film are shown in table 39. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

Comparative example 2

The respective components 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 onto 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 prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film are shown in table 39. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked 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 respective components 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 onto 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 prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film. The film thickness of the obtained post-baking colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the post-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the post-baked colored coating film and the wavelength of the shoulder on the longest side of the absorption spectrum of the post-baked colored coating film are shown in table 40.

Comparative example 3

The respective components 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 onto 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 prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film. The film thickness of the obtained post-baking colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the post-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the post-baked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the post-baked 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 respective components were mixed in the following proportions, and the colorant was dispersed by a bead mill to obtain a coloring composition MH 4.

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

The coloring composition H4 was applied onto 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 prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film. The film thickness of the obtained post-baking colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the post-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the post-baked colored coating film and 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 post-baked colored coating film are shown in table AD 1.

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 coloring composition M6-1.

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

The coloring composition 6-1 was applied onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 2. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

[ Table AD2]

Example 6-2 to example 6-4

A coloring composition was obtained in the same manner as in example 6-1 except that the compound represented by formula (Ia51) was replaced with the compound shown in the column of "colorant AAA" in table AD3, thereby obtaining a pre-baked colored coating film and a post-baked colored coating film. The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 3.

[ 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 coloring composition M7-1.

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

The coloring composition 7-1 was applied onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 4. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

[ Table AD4]

Example 7-2 to example 7-6

A coloring composition was obtained in the same manner as in example 7-1 except that the compound represented by the formula (Ia973) was replaced with the compound described in the column of "colorant AAA" in table AD5, thereby obtaining a pre-baked colored coating film and a post-baked colored coating film. The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 5.

[ 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 coloring composition M7-7.

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

The coloring compositions 7 to 7 were 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 coloring coating film. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film. The film thickness of the obtained post-baking colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the post-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the post-baked colored coating film and 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 post-baked colored coating film are shown in table AD 6.

[ 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 coloring 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 onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 7. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

[ Table AD7]

Example 90-2 to example 90-22

A coloring composition was obtained in the same manner as in example 90-1 except that the compound represented by formula (Ia5) was replaced with the compound shown in the column of "colorant AAA" in table AD8, thereby obtaining a pre-baked colored coating film and a post-baked colored coating film. The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 8.

[ 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 a colored composition M90-23.

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

The coloring compositions 90 to 23 were 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 coloring coating film. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film. The film thickness of the obtained post-baking colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the post-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the post-baked colored coating film and 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 post-baked colored coating film are shown in table AD 9.

[ Table AD9]

Example 91-1

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

Next, the respective components were mixed in the following proportions to obtain a colored composition 91-1.

The coloring composition 91-1 was applied onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 10. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

[ Table AD10]

Example 91-2 to example 91-4

A coloring composition was obtained in the same manner as in example 91-1 except that the compound represented by formula (If3796) was replaced with the compound described in the column "colorant AAA" in table AD11, and a prebaked colored coating film and a postbaked colored coating film were obtained. The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 11.

[ 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 coloring composition M17-1.

Next, the respective components were mixed in the following proportions to obtain coloring composition 17-1.

The coloring composition 17-1 was applied onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 12. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked 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 coloring composition M12-1.

Then, the respective components were mixed in the following proportions to obtain a coloring composition 12-1.

The coloring composition 12-1 was applied onto 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 coloring coating film. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film. The film thickness of the obtained post-baking colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the post-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the post-baked colored coating film and 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 post-baked colored coating film are shown in table AD 13.

[ 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 coloring composition M13-1.

Then, the respective components were mixed in the following proportions to obtain a coloring composition 13-1.

The coloring composition 13-1 was applied onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.).

The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 14.

The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked 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 coloring composition M14-1.

Then, the respective components were mixed in the following proportions to obtain a coloring composition 14-1.

The coloring composition 14-1 was applied onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 15. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked 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 coloring composition M16-1.

Then, the respective components were mixed in the following proportions to obtain a coloring composition 16-1.

The coloring composition 16-1 was applied onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 16. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked 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.

Then, the respective components were mixed in the following proportions to obtain a coloring composition 51-1.

The coloring composition 51-1 was applied onto 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 17. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked 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; manufactured by CORNING) by a spin coating method, and then, prebaked at 100 ℃ for 3 minutes to form a prebaked coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 18. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked 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 colored composition M591-1.

Next, the respective components were mixed in the following proportions to obtain a colored composition 591-1.

The coloring composition 591-1 was coated on 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 19. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

Example 591-2

A coloring composition was obtained in the same manner as in example 591-1, except that in example 591-1, the following amount of colorant (a) was used in place of the compound represented by formula (Ia1) and the compound represented by formula (Ia248), and a prebaked colored coating film and a postbaked colored coating film were obtained.

2.38 parts of a mixture of the compound represented by the formula (Ia10), the compound represented by the formula (Ia2143), the compound represented by the formula (Ia850), and the compound represented by the formula (Ia315) obtained in example 4;

2.12 parts of a compound represented by the formula (Ia 51);

the film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 19.

Example 591-3

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 591-4

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 591-5

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 coloring composition 592-1.

The coloring composition 592-1 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 coloring coating film. The film thickness of the obtained prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 20. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

Example 592-2

A colored composition was obtained in the same manner as in example 592-1 except that in example 592-1, the following colorant (a) was used in the following amount in place of the compound represented by formula (Ia1) and the compound represented by formula (Ia248), and a prebaked colored coating film and a postbaked colored coating film were obtained.

4.00 parts of a compound represented by the formula (Ia 5);

1.00 part of a compound represented by the formula (Ia 248);

the film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 20.

Examples 592 to 3

4.00 parts of a compound represented by the formula (Ia 699);

1.00 part 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 part of a mixture containing the compound represented by the formula (Ia 5-SA 1) and the compound represented by the formula (Ia 5-SA 2) obtained in example E-1;

[ Table AD20]

Example S-1

The respective components were mixed in the following proportions to obtain a colored composition S-1.

The coloring composition S-1 was applied onto 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 prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film. The film thickness of the obtained post-baking colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the post-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the post-baked colored coating film and 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 post-baked colored coating film are shown in table AD 21.

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 onto 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 prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film. The film thickness of the obtained post-baking colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the post-baked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the post-baked colored coating film and 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 post-baked colored coating film are shown in table AD 21.

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 onto 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 prebaked colored coating film was measured by DektakXT (manufactured by BRUKER). The spectrum of the prebaked colored coating film was measured using a colorimeter LVmicroZ (manufactured by Lambda Vision Co., Ltd.). The film thickness of the prebaked colored coating film and the maximum absorption wavelength on the longest wavelength side of the absorption spectrum of the prebaked colored coating film or the wavelength of the shoulder on the longest wavelength side of the absorption spectrum are shown in table AD 21. The prebaked colored coating film was postbaked at 230 ℃ for 30 minutes to obtain a postbaked colored coating film.

[ Table AD21]

From the above results, it was found that 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 for forming a color filter having a darker color than that of a coloring composition containing c.i. pigment yellow 138, and are therefore preferably used for a display device such as a color filter, a liquid crystal display device, or the like.

Claims

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

in the formula (I), the compound is shown in the specification,

R¹～R⁵each independently represents a hydrogen atom or halogenElement atom, cyano group, nitro group, -SO₃M、－CO₂M, MM, a C1-valent hydrocarbon group or a C1-valent heterocyclic group having 1-40 carbon atoms,

the hydrogen atoms constituting the 1-valent hydrocarbon group and the 1-valent heterocyclic group may be substituted by a halogen atom, a cyano group, a nitro group or a-SO group₃M、－CO₂M or MM is selected from the group consisting of,

R¹and R²、R²And R³And R³And R⁴May be bonded to each other to form a ring,

m represents a hydrogen atom, an alkali metal atom, a metal atom which may have a ligand, or N (Z) ¹)(Z²)(Z³)(Z⁴)，

MM represents an alkali metal atom, a metal atom which may have a ligand, or N (Z)¹)(Z²)(Z³)(Z⁴)，

-CH constituting the 2-valent hydrocarbon group and the 2-valent heterocyclic group₂May 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 by a halogen atom, a cyano group, a nitro group or a-SO group₃M、－CO₂M or MM is selected from the group consisting of,

Z¹～Z⁴when plural, M and MM are present, respectively, they may be the same as or different from each other.

2. The coloring composition according to claim 1, comprising a resin.

3. The coloring composition according to any one of claims 1 to 2, comprising a polymerizable compound and a polymerization initiator.

4. A color filter formed from the colored composition according to any one of claims 1 to 3.

5. A display device comprising the color filter of claim 4.

6. A compound represented by the formula (I),

in the formula (I), the compound is shown in the specification,

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

m represents a hydrogen atom, an alkali metal atom, a metal atom which may have a ligand, or N (Z)¹)(Z²)(Z³)(Z⁴)，