TWI619771B - Pyridone complex compound - Google Patents

Abstract

The present invention is a pyridone complex compound, a dye using the pyridone complex compound as an active ingredient, and a colored resin composition containing a dye, a resin, and a solvent using the pyridone complex compound as an active ingredient.

Description

Pyridone complex compound

The present invention relates to a compound useful as a dye.

Since the past, pigments of metal salt compounds have been used in various fields (for example, fiber materials, liquid crystal display devices, etc.) for color display using reflected light or transmitted light. As such a dye, for example, a dye of a chromium complex containing an azo compound as a ligand is known as C.I. Solvent Yellow 21 represented by the following formula.

[Non-Patent Document 1] Industrial Dyes Chemistry, Properties, Applications, WILEY-VCH, 2003.

Among the above-mentioned compounds known previously, the molar absorption coefficient is small, and the spectroscopic concentration sometimes cannot fully meet the requirements.

The present invention provides the following [1] to [7].

[1] A compound represented by the formula (0):

[In the formula (0), R ¹ represents a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be -OR ⁸ , -COOR ⁸ , -OCOR ⁸ , -CONR ⁸ R ⁹ , carbon one having 6 to 10 or a divalent aromatic hydrocarbon group substituted with a halogen atom, a saturated hydrocarbon group which contains the -CH ₂ - and -CH -O- is not bonded to the ₂ - may be substituted with -CO-; R ² represents hydrogen Atom, -CN or -CONH ₂ group; R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom; R ^4a to R ^7a each independently represent -R ⁸ , -OR ⁸ , -COOR ⁸ ,- COR ⁸ , -OCOOR ⁸ , -OCOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, -SO ₂ NR ⁸ R ⁹ or -NR ¹¹ R ¹² ; R ^4a and R ^5a , R ^5a and R ^6a, and R ^6a and R ^7a may also be bonded to each other to form a 6 to 7 member ring containing a benzene ring carbon; R ⁸ and R ⁹ represent a hydrogen atom and a carbon number of 1 to 8 A monovalent aliphatic hydrocarbon group, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group, and the aromatic hydrocarbon group is also Can be substituted by -OR ¹⁰ ; R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R ¹¹ and R ¹² are respectively Independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a fluorenyl group or tetrahydrofurfuryl group having 2 to 8 carbon atoms; R ¹¹ and R ¹² may also be bonded to each other to form a ring containing a nitrogen atom; A ⁺ represents a hydrogen cation, a sodium cation, a potassium cation, or a tetraalkylammonium cation having a carbon number of 1 to 4].

[2] A compound represented by the formula (I):

[In the formula (I), R ¹ represents a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be -OR ⁸ , -COOR ⁸ , -OCOR ⁸ , -CONR ⁸ R ⁹ , carbon one having 6 to 10 or a divalent aromatic hydrocarbon group substituted with a halogen atom, a saturated hydrocarbon group which contains the -CH ₂ - and -CH -O- is not bonded to the ₂ - may be substituted with -CO-; R ² represents hydrogen Atom, -CN or -CONH ₂ ; R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom; R ⁴ to R ⁷ each independently represent -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, or -SO ₂ NR ⁸ R ⁹ ; R ⁸ and R ⁹ represent a hydrogen atom and one of carbon numbers 1 to 8 Valence aliphatic hydrocarbon group, aralkyl group having 7 to 12 carbon atoms, or monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may also pass through -OR ¹⁰ substitution; R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; A ⁺ represents a hydrogen cation, sodium cation, potassium cation, or carbon number 1 to Tetraalkylammonium cation 4].

[3] The compound according to the above [1] or [2], wherein R ¹ is a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted by -OH or -OCOR ⁸ .

[4] The compound according to any one of the above [1] to [3], wherein at least three of R ⁴ to R ⁷ are hydrogen atoms.

[5] The compound according to any one of [1] to [4] above, wherein R ² is -CN.

[6] A dye containing the compound according to any one of the above [1] to [5] as an active ingredient.

[7] A colored resin composition containing the dye, resin, and solvent as described in [6] above.

The compound of the present invention has a high molar absorption coefficient and a high spectral concentration.

The compound of the present invention is a compound represented by formula (0) (hereinafter sometimes referred to as "compound (0)"). The compounds of the present invention also include their tautomers.

[In the formula (0), R ¹ represents a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be -OR ⁸ , -COOR ⁸ , -OCOR ⁸ , -CONR ⁸ R ⁹ , carbon one having 6 to 10 or a divalent aromatic hydrocarbon group substituted with a halogen atom, a saturated hydrocarbon group which contains the -CH ₂ - and -CH -O- is not bonded to the ₂ - may be substituted with -CO-; R ² represents hydrogen Atom, -CN or -CONH ₂ group; R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom; R ^4a to R ^7a each independently represent -R ⁸ , -OR ⁸ , -COOR ⁸ ,- COR ⁸ , -OCOOR ⁸ , -OCOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, -SO ₂ NR ⁸ R ⁹ or -NR ¹¹ R ¹² ; R ^4a and R ^5a , R ^5a and R ^6a, and R ^6a and R ^7a may also be bonded to each other to form a 6 to 7 member ring containing a benzene ring carbon; R ⁸ and R ⁹ represent a hydrogen atom and a carbon number of 1 to 8 A monovalent aliphatic hydrocarbon group, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group, and the aromatic hydrocarbon group is also Can be substituted by -OR ¹⁰ ; R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R ¹¹ and R ¹² are respectively Independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a fluorenyl group or tetrahydrofurfuryl group having 2 to 8 carbon atoms; R ¹¹ and R ¹² may also be bonded to each other to form a ring containing a nitrogen atom; A ⁺ represents a hydrogen cation, a sodium cation, a potassium cation, or a tetraalkylammonium cation having a carbon number of 1 to 4].

The compound of the present invention is preferably a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)").

[In the formula (I), R ¹ represents a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be -OR ⁸ , -COOR ⁸ , -OCOR ⁸ , -CONR ⁸ R ⁹ , carbon one having 6 to 10 or a divalent aromatic hydrocarbon group substituted with a halogen atom, a saturated hydrocarbon group which contains the -CH ₂ - and -O- is not adjacent to the -CH ₂ - may be substituted with -CO-; R ² represents a hydrogen atom , -CN or -CONH ₂ ; R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom; R ⁴ to R ⁷ each independently represent -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, or -SO ₂ NR ⁸ R ⁹ ; R ⁸ and R ⁹ represent a hydrogen atom and a carbon number of 1 to 8 An aliphatic hydrocarbon group, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group, and the aromatic hydrocarbon group may also be- OR ¹⁰ substitution; R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; A ⁺ represents a hydrogen cation, sodium cation, potassium cation, or carbon number 1 to 4 Tetraalkylammonium cation].

R ¹ is a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, preferably a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and further preferably 2 to carbon atoms. A monovalent saturated hydrocarbon group of 4 is particularly preferably a monovalent saturated hydrocarbon group having 2 or 4 carbon atoms.

In the case where the hydrogen atom contained in the saturated hydrocarbon group is substituted, it is preferably substituted with -OR ⁸ , -OCOR ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and in the case of substitution with -OR ⁸ In this case, R ^{8 is} preferably a hydrogen atom. When substituted with -OCOR ⁸ , R ^{8 is} preferably a monovalent aliphatic hydrocarbon group having 6 to 8 carbon atoms or a phenyl group.

Examples of the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms in R ¹ and R ¹⁰ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Linear saturated hydrocarbon groups such as isopropyl; isopropyl, isobutyl, second butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl Amyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethyl Pentyl, 2-ethylpentyl, 3-ethylpentyl, 1-propylbutyl, 1- (1-methylethyl) butyl, 1- (1-methylethyl) -2 -Methylpropyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1- Ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-n-propylpentyl, 2-propylpentyl, 1- (1-methylethyl) pentyl, 1-butylbutyl, 1-butyl-2-methylbutyl, 1-butyl-3-methylbutyl, 1- (1,1-dimethylethyl) butylbutyl, Tributyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethyl-2-methylpropyl, 1,1-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl Group, 1,4-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl Methyl, 3,4-dimethylpentyl, 1-ethyl-1-methylbutyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 2- Ethyl-1-methylbutyl, 2-ethyl-3-methylbutyl, 1,1-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1 , 4-dimethylhexyl, 1,5-dimethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethyl Hexyl, 3,3-dimethylhexyl, 3,4-dimethylhexyl, 3,5-dimethylhexyl, 4,4-dimethylhexyl, 4,5-dimethylhexyl, 1- Ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 2-ethyl 2-methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-1-methylpentyl, 3-ethyl-2 -Methylpentyl, 3-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 1-propyl-1-methylbutyl, 1- 2-methylbutyl, 1-propyl-3-methylbutyl, 1- (1-methylethyl) -1-methylbutyl, 1- (1-methylethyl)- Branched chain saturated hydrocarbon groups such as 2-methylbutyl, 1- (1-methylethyl) -3-methylbutyl, 1,1-diethylbutyl, 1,2-diethylbutyl ; Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and other cyclic saturated hydrocarbon groups.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ⁸ and R ⁹ include the vinyl, propenyl, isopropyl, and isocyanate groups in addition to the groups listed in the above-mentioned linear saturated hydrocarbon group and branched saturated hydrocarbon group. Propenyl, butenyl, 2-methacryl and the like.

Examples of the aralkyl group having 7 to 12 carbon atoms in R ⁸ and R ⁹ include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, and naphthylethyl.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ⁸ , R ^9, and R ¹⁰ include a phenyl group, a tolylmethyl group, a xylyl group, a naphthyl group, and the like.

Examples of the saturated hydrocarbon group in which -CH ₂ -is substituted with -CO- include acetone, 3-oxobutyl, 2-oxobutyl, 3-oxopentyl, 2-oxopentyl, Saturated hydrocarbon groups containing oxo groups such as 3-oxohexyl; benzamidinemethyl, 2-oxo-2-naphthylethyl, 2-oxo-2-hydroxyphenylethyl, 2-oxo- 2-hydroxynaphthylethyl, 2-oxo-2-methoxyphenylethyl, 2-oxo-2-methoxynaphthylethyl, 2-oxo-3-phenylpropyl, 2-oxo-3-naphthylpropyl and other saturated hydrocarbon groups containing aromatic hydrocarbon groups and oxo groups.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with a halogen atom include fluoromethyl, trifluoromethyl, fluoromethyl, fluoropropyl, fluorobutyl, chloromethyl, chloroethyl, chloropropyl, and chlorobutyl Methyl, bromomethyl, bromoethyl, bromopropyl, bromobutyl, iodomethyl, iodoethyl, iodopropyl, iodobutyl, and the like.

Examples of -OR ⁸ include hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, and 2-ethylhexyloxy. , Phenoxy, benzyloxy, benzamyloxy and the like.

Examples of -OR ⁸ substituted with -OR ¹⁰ include methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, and 1-ethoxy. Propyl, 2-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methyl-2-ethoxyethyl, 1- (1-methylethoxy) propyl , 2- (1-methylethoxy) propyl, 1- (1-methylethoxy) -1-methylethyl, 2- (1-methylethoxy) -1-methyl Ethyl, 3-ethoxypropyl and the like.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with -OR ⁸ include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxymethoxymethyl, 2-hydroxyethoxymethyl, 2- Hydroxyl-containing saturated hydrocarbon groups such as hydroxymethoxyethyl, 2- (2-hydroxyethoxy) ethyl, 2-oxo-4-hydroxybutyl; methoxymethyl, ethoxymethyl, and propane Oxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, 2-oxo-4-methoxy Alkoxy-containing saturated hydrocarbon groups such as butylbutyl; methoxymethoxymethyl, 2-methoxyethoxymethyl, ethoxymethoxymethyl, 2-ethoxyethoxymethyl Methyl, propoxymethoxymethyl, 2-propoxyethoxymethyl, 2-methoxymethoxyethyl, 2- (2-methoxyethoxy) ethyl, 2- Ethoxymethoxyethyl, 2- (2-ethoxyethoxy) ethyl, 2-propoxymethoxyethyl, 2- (2-propoxyethoxy) ethyl, etc. Alkoxyalkyl-containing saturated hydrocarbon groups; phenoxymethyl, 1-naphthyloxymethyl, 2-naphthyloxymethyl, hydroxyphenoxymethyl, hydroxynaphthyloxymethyl Aryloxy-containing saturated hydrocarbon groups such as methoxyphenoxymethyl, methoxynaphthyloxymethyl, 3-phenoxy-2-oxopropyl; benzyloxymethyl, naphthylmethoxy Methyl, hydroxybenzyloxymethyl, hydroxynaphthylmethoxymethyl, methoxybenzyloxymethyl, methoxynaphthylmethoxymethyl, phenoxyethoxymethyl, naphthyloxy Arylalkoxy-containing saturated hydrocarbon groups such as ethoxymethyl and the like.

Examples of -COOR ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with -COOR ⁸ include a carboxyl-containing saturated hydrocarbon group such as carboxymethyl, carboxyethyl, carboxypropyl, and carboxybutyl; methoxycarbonylmethyl, and methoxycarbonylethyl Methyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, propoxycarbonylethyl, butoxycarbonylmethyl, butoxycarbonylethyl, phenoxymethoxy Alkoxycarbonyl-containing saturated hydrocarbon groups such as carbonylmethyl, 2-hydroxyethoxycarbonylmethyl, and 2-methoxyethoxycarbonylmethyl; phenoxycarbonylmethyl, naphthyloxycarbonylmethyl, etc. Aryloxycarbonyl saturated hydrocarbon groups; benzyloxycarbonylmethyl, naphthylmethoxycarbonylmethyl and other saturated hydrocarbon groups containing arylalkoxycarbonyl groups; 2-oxopropoxycarbonylmethyl, 2- (2- Oxopropoxycarbonyl) ethyl, 3- (2-oxopropoxycarbonyl) propyl, 2-oxobutoxycarbonylmethyl, 2- (2-oxobutoxycarbonyl) ethyl , 3- (2-oxobutoxycarbonyl) propyl, 2-oxopentyloxycarbonylmethyl, 2- (2-oxopentyloxycarbonyl) ethyl, 3- (2-oxopentyl) Oxycarbonyl) propyl, 3-oxobutoxycarbonylmethyl, 2- (3-oxo Butoxycarbonyl) ethyl, 3- (3-oxobutoxycarbonyl) propyl, 3-oxopentyloxycarbonylmethyl, 2- (3-oxopentyloxycarbonyl) ethyl, 3 -(3-oxopentyloxycarbonyl) propyl, 2-oxohexyloxycarbonylmethyl, 2- (2-oxohexyloxycarbonyl) ethyl, 3- (2-oxohexyloxy) Carbonyl) propyl and other saturated hydrocarbon groups containing -CH ₂ -alkoxycarbonyl substituted with -CO-; 3-methoxycarbonyl-2-oxopropyl, 4-methoxycarbonyl-3-oxo Butyl, 5-methoxycarbonyl-4-oxopentyl, 3-ethoxycarbonyl-2-oxopropyl, 4-ethoxycarbonyl-3-oxobutyl, 5-ethoxy Carbonyl-4-oxopentyl, 3-propoxycarbonyl-2-oxopropyl, 4-propoxycarbonyl-3-oxobutyl, 5-propoxycarbonyl-4-oxopentyl 4-methoxycarbonyl-2-oxobutyl, 4-methoxycarbonyl-3-oxopentyl, 5-methoxycarbonyl-4-oxohexyl, 4-ethoxycarbonyl-2 -Oxobutyl, 4-ethoxycarbonyl-3-oxopentyl, 5-ethoxycarbonyl-4-oxohexyl, 4-propoxycarbonyl-2-oxobutyl, 4-prop Alkoxycarbonyl groups such as oxycarbonyl-3-oxopentyl, 5-propoxycarbonyl-4-oxohexyl and -CH _2- Substituted for -CO- saturated hydrocarbon group.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with -CONR ⁸ R ⁹ include N-methylaminocarbonylmethyl, N-methylaminocarbonylethyl, and N, N-dimethylaminocarbonylmethyl. , N, N-dimethylaminocarbonylethyl, N, N-ethylmethylaminocarbonylmethyl, N, N-ethylmethylcarbonylethyl, etc. Saturated hydrocarbon; N-phenylaminocarbonylmethyl, N, N-phenylmethylcarbonylmethyl, N, N-diphenylcarbonylmethyl, N, N-phenylbenzylcarbonylmethyl, etc. Saturated hydrocarbyl groups of amidomethyl substituted with aryl groups; N-benzylaminocarbonylmethyl, N, N-dibenzylcarbonylmethyl, N, N-bis (2-phenylethyl) carbonylmethyl Saturated hydrocarbyl groups containing carbamoyl substituted with aralkyl and the like.

Examples of -OCOR ⁸ include ethoxyl, pentamyloxy, and benzyloxy.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with -OCOR ⁸ include ethoxymethyl, ethoxyethyl, ethylcarbonyloxymethyl, ethylcarbonyloxyethyl, and propylcarbonyloxy. Methyl, propylcarbonyloxyethyl, butylcarbonyloxymethyl, butylcarbonyloxyethyl, hexamethyleneoxyethyl, 2-ethylbutoxymethyl, 2-ethyl Saturated alkyl groups containing alkylcarbonyloxy groups, such as hexamethyleneoxyethyl, 2-propylhexamethyleneoxyethyl, p-pentamyloxyethyl, 2-methylpropionyloxyethyl; benzamyloxy Methyl, benzamyloxyethyl, naphthyloxycarbonylmethyl, benzylcarbonyloxymethyl, naphthylmethylcarbonyloxymethyl, methylbenzyloxymethyl, 2-methyl Benzylbenzyloxyethyl, 4-methylbenzyloxyethyl, 3,4-dimethylbenzyloxyethyl, hydroxybenzyloxymethyl, methoxybenzyl Aromatic hydrocarbon groups such as methoxymethyl, 4-methoxybenzyloxyethyl, 3,4-dimethoxybenzyloxyethyl, and saturated hydrocarbon groups containing carbonyloxy and the like.

Examples of -COR ⁸ include ethenyl, propionyl, isobutyridyl, pentamyl, and isopentyl.

Examples of -OCOOR ⁸ include methoxycarbonyloxy, ethoxycarbonyloxy, n-propoxycarbonyloxy, isopropoxycarbonyloxy, n-butoxycarbonyloxy, and isobutoxy Carbonyloxy, second butoxycarbonyloxy, n-pentyloxycarbonyloxy, phenoxycarbonyloxy and the like.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms include a benzyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, and a group represented by the following formula.

R ^{1 is} preferably a saturated hydrocarbon group in which a hydrogen atom is substituted with -COOR ⁸ and a saturated hydrocarbon group in which a hydrogen atom is substituted with -OCOR ⁸ , and more preferably a group represented by formula (f-1) to formula (f-14). When R ¹ is the above-mentioned group, the compound of the present invention tends to exhibit high solubility in an organic solvent. In the formulae (f-1) to (f-14), * represents a bonding position with a nitrogen atom on a pyridone ring.

R ² is a hydrogen atom, -CN, or -CONH ₂ . Among these, -CN is preferable in terms of easy availability of raw materials.

R ³ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.

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

Examples of the alkyl group having 1 to 4 carbon atoms substituted with a halogen atom include a trifluoromethyl group and a pentafluoroethyl group.

R ^{3 is} preferably a methyl group or a trifluoromethyl group, and particularly preferably a methyl group.

R ^4a to R ^{7a are} preferably independently -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K,- SO ₂ NR ⁸ R ⁹ or -NR ¹¹ R ¹² .

R ⁴ ~ R ⁷ are each independently _{^{-R 8, -OR 8, - COOR}} 8, -CN, -NO 2, a halogen _{atom, -SO 3 H, -SO 3 Na} , -SO 3 K or -SO ₂ NR ⁸ R ⁹ .

Examples of -NR ¹¹ R ¹² among R ^4a to R ^7a include N-methylamino, N, N-dimethylamino, N-ethylamino, and N, N-diethylamine. Group, N-propylamino group, N, N-dipropylamino group, N-butylamino group, N, N-dibutylamino group, N-pentylamino group, N-ethenylamino group Wait.

Examples of -NR ¹¹ R ^{12 in} which R ¹¹ and R ¹² are bonded to each other to form a ring containing a nitrogen atom include 1-pyrazolyl, pyrrolidinyl, piperidinyl, Phenyl and so on.

Among these, in terms of solubility in an organic solvent, an N-ethylamidoamino group is preferred.

Examples of -SO ₂ NR ⁸ R ^{9 in} R ^4a to R ^7a and R ⁴ to R ⁷ include unsubstituted aminesulfonyl, N-monosubstituted aminesulfonyl, and N, N-disubstituted aminesulfonyl.醯 基.

Examples of the N-monosubstituted aminesulfonyl group include N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylaminesulfonyl , N-butylaminosulfonyl, N-isobutylaminesulfonyl, N-second butylaminesulfonyl, N-third butylaminesulfonyl, N-pentylaminesulfonyl , N- (1-ethylpropyl) sulfamidino, N- (1,1-dimethylpropyl) sulfamidino, N- (1,2-dimethylpropyl) sulfamidino Group, N- (2,2-dimethylpropyl) aminosulfonyl group, N- (1-methylbutyl) aminosulfonyl group, N- (2-methylbutyl) aminesulfonyl group, N- (3-methylbutyl) aminosulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N- (1,3-dimethylbutyl) sulfanyl , N- (3,3-dimethylbutyl) aminosulfonyl, N-heptylaminesulfonyl, N- (1-methylhexyl) sulfanilino, N- (1,4-di Methylpentyl) sulfamoyl, N-octylaminosulfonyl, N- (2-ethylhexyl) aminesulfonyl, N- (1,5-dimethyl) hexylaminesulfonyl, N- (1,1,2,2-tetramethylbutyl) aminosulfonyl, N-allylaminesulfonyl and other substituted N-monosubstituted aminesulfonyl groups with aliphatic hydrocarbon groups; N- ( 2-hydroxyethyl) sulfamoyl, N- (3-hydroxy Sulfamoyl, N- (2-hydroxypropyl) sulfamoyl, N- (2,3-dihydroxypropyl) sulfamoyl, N- (2-hydroxybutyl) sulfamo N- (4-hydroxybutyl) sulfamoryl, N- (1-hydroxymethylethyl) sulfamolyl, and other N-monosubstituted sulfamolyl substituted with an aliphatic hydrocarbon group having a hydroxyl group; N- (2-methoxyethyl) aminosulfonyl, N- (2-ethoxyethyl) aminosulfonyl, N- (1-methoxypropyl) aminosulfonyl, N- Methoxypropylaminesulfonyl, N-ethoxypropylaminesulfonyl, N-propoxypropylaminesulfonyl, N-isopropoxypropylaminesulfonyl, N-hexane Oxypropylaminesulfonyl, N- (2-ethylhexyloxypropyl) aminesulfonyl, N- (3-thirdbutoxypropyl) aminesulfonyl, N- (4, 4-dimethoxybutyl) aminosulfonyl, N-methoxyhexylaminesulfonyl, and the like, N-monosubstituted aminesulfonyl substituted with alkyl or cycloalkyl having alkoxy; N- [1- (2-ethoxyethoxy) propyl] aminosulfonyl groups such as N-monosubstituted aminesulfonyl groups substituted with an aliphatic hydrocarbon group having an alkoxyalkyl group; N-phenylaminesulfonyl Aryl-substituted N-monosubstituted aminesulfonyl groups such as N- (1-naphthyl) aminosulfonyl; N-benzylamine Fluorenyl, N- (1-phenylethyl) sulfamomidino, N- (2-phenylethyl) sulfamomidino, N- (3-phenylpropyl) sulfamomidino, N- (4-phenylbutyl) aminosulfonyl, N- [2- (2-naphthyl) ethyl] aminesulfonyl, N- [2- (4-methylphenyl) ethyl] aminesulfonyl Aryl-substituted N-mono groups such as fluorenyl, N- (3-phenyl-1-propyl) sulfamomidino, N- (3-phenyl-1-methylpropyl) sulfamomidino Substituted Aminosulfonyl; N- (3,4,5-trimethoxybenzyl) aminesulfonyl, N- [2- (3,4-dimethoxyphenyl) ethyl] aminesulfonyl , N- [2- (2-ethoxyphenyl) ethyl] aminosulfonyl and other N-monosubstituted aminesulfonyl substituted with an aralkyl group having a substituent; as N, N-disubstituted amine Examples of the sulfonyl group include N, N-dimethylaminesulfonyl, N, N-ethylmethylaminesulfonyl, N, N-diethylaminesulfonyl, N, N-propyl Methylmethylaminesulfonyl, N, N-isopropylmethylaminesulfonyl, N, N-third butylmethylaminesulfonyl, N, N-butylethylaminesulfonyl, N, N, N-substituted aminesulfonyl groups substituted with 2 aliphatic hydrocarbon groups, such as N-bis (1-methylpropyl) sulfamoyl, N, N-heptylmethylaminesulfonyl; N, N -Bis (2-hydroxyethyl) aminesulfonyl, N, N-bis (2-methyl (Oxyethyl) sulfamoyl, N, N-bis (2-ethoxyethyl) sulfamoyl, etc. N, N-disubstituted aminesulfonyl substituted with aliphatic hydrocarbon group having a substituent .

A -SO ₂ NR ⁸ R ⁹ in the R ⁸ and R ^9, preferably branched chain alkyl group having a carbon number of 6-8, allyl, phenyl, 8 to 10 carbon atoms, aralkyl group of carbon number The hydroxy-containing alkyl group or aryl group having 2 to 8 or the alkoxy group-containing alkyl group or aryl group having 2 to 8 carbon atoms is particularly preferably 2-ethylhexyl.

A ⁺ is a hydrogen cation, a sodium cation, a potassium cation, or a tetraalkylammonium cation having a carbon number of 1 to 4.

A tetraalkylammonium cation is a quaternary ammonium cation having four alkyl groups, and the carbon number of one alkyl group is 1 to 4.

Examples of the tetraalkylammonium cation include a tetramethylammonium cation, a tetraethylammonium cation, a tetrabutylammonium cation, and a dimethyldibutylammonium cation. A tetrabutylammonium cation is preferable.

Examples of the compound (0) include compounds (I-1) to (I-177). In Table 1, ⁿ Bu represents n-butyl. In Table 1, when formula numbers are described in the column R ^{1, the} formula numbers of the bases shown above and below are described. In the formulae (f-15) to (f-18), * represents a bonding position with a nitrogen atom on a pyridone ring.

Among them, the compound (I-1) to the compound (I-5), the compound (I-143), and the compound (I-156) are preferable because the spectral concentration is high.

As an example of a method for producing the compound of the present invention, a method for producing the compound (I) will be described. A compound other than the compound (I) among the compounds (0) can also be produced by the same method as the method for producing the compound (I) shown below.

The compound (I) can be produced by using a compound represented by formula (d) (hereinafter sometimes referred to as "compound (d)") and a chromium compound to form a complex.

[In formula (d), R ¹ to R ⁷ have the same meanings as those in formula (I). ]

As a method for producing the compound (d), a diazonium salt and a pyridone compound can be produced by diazo coupling using a method described in Japanese Patent Publication No. 7-88633.

Specifically, the compound (d) can be produced by diazo coupling of a diazonium salt represented by the formula (b) and a pyridone compound represented by the formula (c). The diazonium salt represented by the formula (b) can be obtained, for example, by diazotizing the amine represented by the formula (a) by using nitrous acid, a nitrite, or a nitrite.

[In formulas (a), (b), and (c), R ¹ to R ⁷ have the same meanings as those in formula (I); A ¹ represents an inorganic anion or an organic anion. ]

Examples of the inorganic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, and the like. Examples of the organic anion, for example, ^{_{CH 3 -COO -, C 6 H}} 5 -COO - and the like. It is preferably a chloride ion, a bromide ion, CH ₃ -COO ^-.

The compound (d) can be produced by reacting a diazonium salt represented by the formula (b) with a pyridone compound represented by the formula (c) in an aqueous solvent. The reaction temperature is preferably -5 ° C to 60 ° C, and more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

The method for obtaining the compound (d) as a target compound from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, the reaction mixture is preferably mixed with an acid (for example, acetic acid, etc.) and water, and the precipitated crystals are collected by filtration. The acid is preferably an aqueous solution of the acid, and the reaction mixture is added to the aqueous solution. The temperature at which the reaction mixture is added is usually 10 ° C to 50 ° C, preferably 20 ° C to 50 ° C, and more preferably 20 ° C to 30 ° C. The reaction mixture is preferably added to an acid aqueous solution, and then stirred at the same temperature for about 0.5 to 2 hours. The filtered crystal is preferably washed with water or the like and then dried. If necessary, further purification can be performed by a known method such as recrystallization.

The compound (I) can be prepared by dissolving the compound (d) and the chromium compound in an aqueous solvent (for example, N, N-dimethylformamide, N-methylpyrrolidone, etc.), preferably at 70 to 150 ° C. It is produced by reacting for 3 to 10 hours.

Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, chromium fluoride, and chromium ammonium sulfate. Preferred examples include chromium formate, chromium ammonium sulfate, and the like.

The amount of the chromium compound used is preferably 0.5 to 1 mole relative to 1 mole of the compound (d).

In order to promote the reaction, an inorganic base may be coexisted.

Examples of the inorganic base include sodium hydroxide, calcium hydroxide, sodium carbonate, calcium carbonate, sodium acetate, and calcium acetate. Preferred examples include sodium carbonate and sodium acetate.

The method for obtaining the compound (I) as a target compound from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, it is preferable to mix the reaction mixture with an inorganic salt (for example, common salt, etc.) and water, and to filter out the precipitated crystals. The inorganic salt is preferably prepared by preparing an aqueous solution of the inorganic salt in advance, and then adding the reaction mixture to the aqueous solution. The temperature when the reaction mixture is added is preferably 10 ° C or higher and 50 ° C or lower, more preferably 10 ° C or higher and 40 ° C or lower, and even more preferably 10 ° C or higher and 25 ° C or lower. The reaction mixture is preferably added to an aqueous solution of an inorganic salt, and then stirred at the same temperature for about 0.5 to 2 hours. The filtered crystal is preferably washed with water or the like and then dried. If necessary, further purification can be performed by a known method such as recrystallization.

The compound of the present invention thus obtained can be used as a dye. Since the compound of the present invention has a high spectral density, it can be used as a dye for color filters or fiber materials of display devices such as liquid crystal display devices that perform color display using reflected light or transmitted light.

The dye of the present invention is a dye having the compound of the present invention as an active ingredient.

The colored resin composition of the present invention contains the dye of the present invention as a colorant (hereinafter sometimes referred to as "colorant (A)"), and further contains a resin (B) and a solvent (E). The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).

In addition to the dye of the present invention, the colorant (A) may further contain a pigment and / or a dye different from the dye of the present invention.

Examples of dyes different from the dyes of the present invention include Color Index (published by The Society of Dyers and Colourists), which is classified as Solvent, Acid, and Basic ( Basic), reactive, direct, disperse or Vat dyes. More specifically, dyes with a color index (C.I.) number as described below may be listed, but are not limited to these.

CI Solvent Yellow 25, 79, 81, 82, 83, 89; CI Acid Yellow 7, 23, 25, 42, 65, 76; CI Reaction Yellow 2, 76, 116; CI Direct Yellow 4, 28, 44, 86, 132; CI Disperse Yellow 54, 76; CI Solvent Orange 41, 54, 56, 99; CI Acid Orange 56, 74, 95, 108, 149, 162; CI Reaction Orange 16, CI Direct Orange 26; CI Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; CI Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 102; CI solvent green 1, 5; CI acid green 3, 5, 9, 25, 28; CI basic green 1; CI reduced green 1 and the like.

Examples of the pigment include organic pigments and inorganic pigments generally used in pigment-dispersed resists. Examples of the inorganic pigment include metal compounds such as metal oxides and metal salts, and specific examples include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, or Composite metal oxide.

Further, as the organic pigment and the inorganic pigment, specifically, compounds classified as pigments in the Colour Index (published by the British Society of Dyes) can be cited. More specifically, pigments having a colorant index (C.I.) number as described below may be mentioned, but are not limited thereto.

CI Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, and 180; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168 , 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38; CI Pigment Green 7, 10 , 15, 25, 36, 47, and 58.

The content of the colorant (A) is preferably 5 to 60% by mass based on the solid content of the colored resin composition. Here, the solid content means a total of components other than the solvent in the colored resin composition.

The content of the dye of the present invention contained in the colorant (A) is preferably 3 to 100% by mass.

The dyes and pigments different from the dyes of the present invention may be used alone or in combination with two or more dyes of the present invention.

The resin (B) is not particularly limited, and any resin can be used. The resin (B) is preferably an alkali-soluble resin, and more preferably a resin containing a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

Specific examples of the resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / methacrylic acid different Ester copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylcis butylene diimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, and the like.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 5,000 to 35,000, and more preferably 6,000 to 30,000.

The acid value of the resin (B) is preferably 50 to 150, and more preferably 60 to 135.

The content of the resin (B) is preferably 7 to 65% by mass, and more preferably 13 to 60% by mass based on the solid content of the colored resin composition.

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized using living radicals, acids, and the like generated from the polymerization initiator (D). Examples thereof include compounds having a polymerizable carbon-carbon unsaturated bond.

The polymerizable compound (C) is preferably a photopolymerizable compound having three or more polymerizable groups. Examples of the photopolymerizable compound having three or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and dipentaerythritol hexaacrylate. , Dipentaerythritol hexamethacrylate and the like. The photopolymerizable compound (C) may be used alone or in combination of two or more.

The content of the polymerizable compound (C) is preferably 5 to 65% by mass, and more preferably 10 to 60% by mass based on the solid content of the colored resin composition.

Examples of the polymerization initiator (D) include a living radical generator and an acid generator. An active radical generator generates an active radical by the action of heat or light. Examples of the above-mentioned active radical generator include an benzoyl ketone compound and 9-oxysulfur Compound, three Compounds, oxime compounds, etc.

Examples of the benzoalkyl ketone compound include 2-methyl-2- Phenyl-1- (4-methylthiophenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone dimethyl ketal, 2- Hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, and the like.

As the above 9-oxysulfur Examples of the compound include 2-isopropyl-9-oxosulfide 4-isopropyl-9-oxysulfur , 2,4-diethyl-9-oxysulfur , 2,4-dichloro-9-oxysulfur , 1-chloro-4-propoxy-9-oxysulfur Wait.

As above three Examples of the compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

Examples of the oxime compound include O-fluorenyl oxime-based compounds, and specific examples thereof include N-benzyloxy-1- (4-phenylthiophenyl) butan-1-one-2 -Imine, N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6 -(2-methylbenzyl) -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl 4- (3,3-dimethyl-2,4-dioxolylmethoxy) benzyl) -9H-carbazol-3-yl] ethane-1-imine, etc. .

Further, as the active radical generator, for example, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzodiazone, 9,10-phenanthrenequinone, camphorquinone, Methyl phenylglyoxylate, titanocene compounds, etc.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethoxyloxyphenyldimethylformate. Hydrazone p-toluenesulfonate, 4-ethoxyfluorenyl-methyl-benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, Onium salts such as phenylsulfonium p-toluenesulfonate and diphenylsulfonium hexafluoroantimonate, or nitrobenzyltoluenesulfonate, benzoin tosylate and the like.

The polymerization initiator (D) may be used alone or in combination of two or more.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator is within the above range, it is preferable because the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, and amidines.

Examples of the ethers include tetrahydrofuran, tetrahydropyran, and 1,4-dihydrofuran. Alkane, 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 Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Diethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether ethyl Esters and so on.

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

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

Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid Methyl ester, 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, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate , Ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, and the like.

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

These solvents may be used alone or in combination of two or more.

The content of the solvent (E) in the colored resin composition is preferably 70 to 95% by mass, and more preferably 75 to 90% by mass relative to the colored resin composition.

The colored resin composition of the present invention may contain various additives such as surfactants, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents, as needed.

The compounds of the invention can be used as dyes. In addition, the compound of the present invention is particularly useful as a dye for a color filter of a display device such as a liquid crystal display device because of its high Mohr absorption coefficient and high spectral density.

In addition, the colored resin composition containing the compound of the present invention can be used in a publicly known form for a display device (for example, a known liquid crystal display device, organic EL (Electroluminescence) device) having a color filter as a constituent part thereof. Etc.), solid-state image sensors, and other devices related to color images.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples.

In the examples and comparative examples, the percentages and parts indicating the content or usage amount are based on quality unless otherwise specified.

In the following examples, the structure of the compound is determined by NMR (Nuclear Magnetic Resonance, Nuclear Magnetic Resonance) (JMM-ECA-500, manufactured by Japan Electronics Co., Ltd.), mass spectrometer (LC, Model 1200 manufactured by Agilent; MASS, LC / MSD type manufactured by Agilent).

[Example 1]

After adding 90 parts of water to 13.0 parts of anthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.1 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.5 parts of sodium nitrite was added, followed by 58.53 parts of 35% hydrochloric acid in small amounts. Then, it was stirred for 2 hours under cooling in an ice bath, and 200 parts of a 9% ammonium sulphuric acid aqueous solution was slowly added to quench the excess nitrous acid and stirred for about 5 minutes to obtain a suspension containing a diazonium salt.

Next, 21.4 parts of the compound represented by formula (c-1) was suspended in 150 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. To this, while maintaining the pH of the suspension at 8.0 to 9.5, the above-mentioned suspension containing a diazonium salt was added dropwise using a pump over about 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours to obtain a yellow suspension. The yellow solid obtained after filtration was dried at 60 ° C. under reduced pressure to obtain 30.5 parts of a compound represented by formula (d-1). The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by formula (d-1)

¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ): 0.90 (3H, t), 1.29 (2H, sextet), 1.48 (2H, quintet), 2.58 (3H, s) , 3.84 (2H, t), 7.31 (1H, t), 7.57 (1H, td), 7.84 (1H, d), 8.05 (1H, dd), 16.4 (1H, s).

225 parts of N-methylpyrrolidone was added to 4.5 parts of the compound represented by formula (d-1), and heated to 80 ° C to dissolve, and then 1.8 parts of chromium formate n hydrate (manufactured by Nacalai Tesque (stock)) was added. , And stirred at 130 ° C. for about 7 hours to obtain a dark orange solution. This solution was poured into 500 parts of a 1 N aqueous hydrochloric acid solution, and the obtained orange solid was filtered, washed with 50 parts of water twice, and then vacuum-dried at 60 ° C to obtain 3.9 parts of a compound represented by formula (I-1). (78% yield).

Identification of the compound represented by formula (I-1)

(Mass spectrometer) Ionization mode = ESI-: m / z = 756.2 [MH] ^-

Accurate mass: 757.2

[Example 2]

After 170 parts of water was added to 17.0 parts of anthranilic acid, 5.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 25.5 parts of sodium nitrite was added, and then 79.5 parts of 35% hydrochloric acid was added in small amounts. Then, it was stirred for 2 hours under cooling in an ice bath, and 250 parts of a 9% ammonium sulfuric acid aqueous solution was slowly added to quench the excess nitrous acid, and stirred for about 10 minutes to obtain a suspension containing a diazonium salt.

Next, 24.1 parts of the compound represented by formula (c-2) was suspended in 170 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. To this, while maintaining the pH of the suspension at 8.0 to 9.5, the above-mentioned suspension containing a diazonium salt was added dropwise using a pump over about 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 39.9 parts of a compound represented by formula (d-2). The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by formula (d-2)

¹ H-NMR (500 MHz, δ value (ppm, TMS reference), DMSO-d ₆ ): 1.08 (3H, t), 2.58 (3H, s), 3.88 (2H, q), 7.32 (1H, t) , 7.58 (1H, td), 7.85 (1H, d), 8.05 (1H, dd), 16.4 (1H, s).

Add 200 parts of N-methylpyrrolidone to 10 parts of the compound represented by formula (d-2), heat to 80 ° C to dissolve, add 3.7 parts of chromium formate n hydrate, and stir at 135 ° C for about 2 Then, the temperature was lowered to 80 ° C., 1.2 parts of sodium carbonate was added, and the mixture was stirred at 135 ° C. for about 2 hours to obtain a dark orange solution. This solution was poured into 1000 parts of a 1 N aqueous hydrochloric acid solution, and the obtained orange solid was filtered, washed with 80 parts of water twice, and then dried under vacuum at 60 ° C., thereby obtaining 7.5 parts of a compound represented by formula (I-2) (68% yield).

Identification of the compound represented by formula (I-2)

(Mass spectrometer) Ionization mode = ESI-: m / z = 700.1 [M-Na] ^-

Accurate mass: 723.1

[Example 3]

After 150 parts of water was added to 13.0 parts of 2-amino-1,4-phthalic acid, 5.1 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 14.8 parts of sodium nitrite was added, and then 59.4 parts of 35% hydrochloric acid was added in small amounts. Thereafter, the mixture was stirred for 3 hours under cooling in an ice bath, and 150 parts of a 9% ammonium sulphuric acid aqueous solution was slowly added to quench the excess nitrous acid and stirred for about 10 minutes to obtain a suspension containing a diazonium salt.

Next, 16.2 parts of the compound represented by formula (c-1) was suspended in 120 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. To this, while maintaining the pH of the suspension at 8.5 to 10.5, the above-mentioned suspension containing a diazonium salt was added dropwise using a pump over about 1 hour. After the dropwise addition was completed, the mixture was further stirred at room temperature for 2 hours to obtain a dark orange solution. When a 1 N aqueous hydrochloric acid solution was added to a pH of 3, a yellow suspension was obtained. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 24.9 parts of a compound represented by formula (d-3). The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by formula (d-3)

¹ H-NMR (500 MHz, δ value (ppm, TMS reference), DMSO-d ₆ ): 0.91 (3H, t), 1.31 (2H, sextet), 1.50 (2H, quintet), 2.47 (3H, s) , 3.78 (2H, t), 7.74 (1H, d), 8.02 (1H, d), 8.30 (1H, s), 15.5 (1H, s).

Add 125 parts of water to 2.5 parts of the compound represented by formula (d-3), heat to 75 ° C to dissolve, add 1.2 parts of chromium formate n hydrate, and stir at 100 ° C for about 8 hours to obtain a dark orange solution. . This solution was poured into 300 parts of a 1 N aqueous hydrochloric acid solution, and the obtained orange solid was filtered and then dried under vacuum at 60 ° C., thereby obtaining 1.7 parts (yield 65%) of a compound represented by formula (I-3).

Identification of the compound represented by formula (I-3)

(Mass spectrometer) Ionization mode = ESI-: m / z = 844.2 [MH] ^-

Accurate mass: 845.2

[Example 4]

After adding 70 parts of water to 10.0 parts of 2-amino-5-nitrobenzoic acid, 2.4 parts of sodium hydroxide was added to prepare a yellow suspension. Under ice-cooling, 11.3 parts of sodium nitrite was added, and then 35.2 parts of 35% hydrochloric acid was added in small amounts. Thereafter, the mixture was stirred under ice-cooling for 3.5 hours, and 120 parts of a 9% ammonium sulphuric acid aqueous solution was slowly added to quench the excess nitrous acid and stirred for about 10 minutes to obtain a suspension containing a diazonium salt.

Next, 11.8 parts of the compound represented by formula (c-3) was suspended in 85 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. To this, while maintaining the pH of the suspension at 7.5 to 9.5, the above-mentioned suspension containing a diazonium salt was added dropwise over about 1 hour using a pump. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 15.9 parts of a compound represented by formula (d-4). The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by formula (d-4)

¹ H-NMR (500 MHz, δ value (ppm, TMS reference), DMSO-d ₆ ): 1.14 (3H, t), 2.24 (3H, s), 3.86 (2H, dd), 7.69 (2H, dd) , 8.06 (1H, d), 8.40 (1H, dd), 8.67 (1H, d), 15.3 (1H, s).

Add 150 parts of N-methylpyrrolidone to 5.0 parts of the compound represented by formula (d-4), heat to 50 ° C to dissolve, add 1.8 parts of chromium formate n hydrate, and stir at 120 ° C for about 2 After 6 hours, 0.6 parts of sodium carbonate was added, and the mixture was stirred for 3 hours to obtain a dark orange solution. This solution was poured into 20% saline, and the obtained orange solid was filtered, and then vacuum-dried at 60 ° C, thereby obtaining 2.9 parts (yield 53%) of the compound represented by the formula (I-4).

Identification of the compound represented by formula (I-4)

(Mass spectrometer) Ionization mode = ESI-: m / z = 826.1 [M-Na] ^-

Accurate quality: 849.1

[Example 5]

After adding 88 parts of water to 5.5 parts of anthranilic acid, 3.2 parts of sodium hydroxide was added to prepare a yellow suspension. Under ice-cooling, 8.9 parts of sodium nitrite was added, and then 33.2 parts of 35% hydrochloric acid was added in small amounts. Thereafter, the mixture was stirred for 3 hours under cooling in an ice bath, and 100 parts of a 9% ammonium sulphuric acid aqueous solution was slowly added to quench the excess nitrous acid, followed by stirring for about 10 minutes to obtain a suspension containing a diazonium salt.

On the other hand, 26.0 parts of ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) 24.4 parts, and stirred at 95 ° C for 24 hours. The reaction solution was cooled to room temperature, and then added to a mixed solution of 304 parts of water and 35 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystal was obtained as a residue by suction filtration and then dried to obtain 20.4 parts of a compound represented by formula (c-4).

Then, 8.5 parts of the compound represented by formula (c-4) was suspended in 77 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. To this, while maintaining the pH of the suspension at 8.0 to 9.5, the above-mentioned suspension containing a diazonium salt was added dropwise for about 1 hour using a pump. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 11.2 parts of a compound represented by formula (d-5). The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by formula (d-5)

¹ H-NMR (270 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ): 2.56 (3H, s), 3.52 (2H, t), 3.93 (2H, t), 4.82 (1H, brs) , 7.36 (1H, t), 7.74 (1H, t), 8.02-8.06 (1H, 1H, overlapped), 15.7 (1H, s).

150 parts of N, N-dimethylformamide, 7.7 parts of chromium ammonium sulfate, and 2.6 parts of sodium acetate were added to 10 parts of the compound represented by formula (d-5), and the mixture was stirred at 135 ° C for about 6 hours to obtain a dark Orange solution. This solution was poured into 20% saline, and the obtained orange solid was filtered, and then vacuum-dried at 60 ° C., thereby obtaining 8.0 parts (yield 73%) of a compound represented by the formula (I-5).

Identification of the compound represented by formula (I-5)

(Mass spectrometer) Ionization mode = ESI-: m / z = 732.1 [M-Na] ^-

Accurate quality: 755.1

[Example 6]

After adding 80 parts of water to 19.4 parts of 5- (N-acetamido) anthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 part of sodium hydroxide was added to dissolve. Under ice-cooling, 19.7 parts of a 35% sodium nitrite aqueous solution was added, and then 26.2 parts of 35% hydrochloric acid was added in small amounts one by one to dissolve, and stirred for 2 hours to obtain a suspension containing a diazonium salt.

Next, 20.4 parts of the compound represented by formula (c-4) was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. To this, the above-mentioned suspension containing a diazonium salt was added dropwise using a pump over 15 minutes. After completion of the dropwise addition, the mixture was stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 39.1 parts of a compound represented by formula (d-6).

Next, to 39.9 parts of the compound represented by formula (d-6), 32.5 parts of osmium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) represented by formula (e-1) was added to N-methylpyrrolidone. Stir at 70 ° C for 3 hours. After completion of the reaction, it was added to water to obtain 50.1 parts of a compound represented by formula (d-7). The obtained compound was orange, and the maximum absorption wavelength (λmax) was measured in an ethyl lactate solvent, and the result showed 459 nm. The structure was confirmed by ¹ H-NMR.

¹ H-NMR: 0.72 (3H, m), 0.75 (3H, m), 1.02 (2H, m), 1.07 (2H, m), 1.23 (2H, m), 1.31 (2H, m), 2.06 (3H , s), 2.11 (1H, m), 4.10 (2H, m), 4.24 (2H, m), 7.88 (1H, m), 7.92 (1H, m), 8.32 (1H, d), 10.26 (1H, s), 15.63 (1H, s).

150 parts of N, N-dimethylformamidine, 7.7 parts of chromium ammonium sulfate, and 2.6 parts of sodium acetate were added to 10.0 parts of the compound represented by formula (d-7), and stirred at 135 ° C for about 6 hours to obtain a dark Orange solution. This solution was poured into 20% saline, and the obtained orange solid was filtered, and then vacuum-dried at 60 ° C to obtain 4.9 parts of a compound represented by formula (I-143).

Identification of the compound represented by formula (I-143)

(Mass spectrometer) Ionization mode = ESI-: m / z = 1098.3 [M-Na] ^-

Accurate quality: 1121.34

[Example 7]

Next, 32.4 parts of benzamidine chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 30.0 parts of the compound represented by formula (d-6), and stirred at 70 ° C for 3 hours in N-methylpyrrolidone. . After completion of the reaction, it was added to water to obtain 35.8 parts of a compound represented by formula (d-8). The obtained compound was orange, and the maximum absorption wavelength (λmax) was measured in an ethyl lactate solvent, and the result showed 459 nm. The structure was confirmed by ¹ H-NMR.

¹ H-NMR: 2.70 (3H, s), 2.50 (3H, s), 4.28 (2H, t), 4.44 (2H, t), 7.43 (1H, t), 7.57 (1H, m), 7.89 (1H , m), 7.95 (1H, m), 8.35 (1H, m), 10.27 (1H, s), 15.67 (1H, s).

Then, 150 parts of N, N-dimethylformamide, 7.7 parts of chromium ammonium sulfate, and 2.6 parts of sodium acetate were added to 9.6 parts of the compound represented by formula (d-8), and stirred at 135 ° C for about 6 hours. A dark orange solution was obtained. This solution was poured into 20% sodium chloride solution, and the obtained orange solid was filtered, and then vacuum-dried at 60 ° C., thereby obtaining 7.1 parts of a compound represented by the formula (I-156).

Identification of the compound represented by formula (I-156)

(Mass spectrometer) Ionization mode = ESI-: m / z = 1054.20 [M-Na] ^-

Accurate quality: 1077.19

<Measurement of absorbance>

0.35 g of the compound was dissolved in ethyl lactate to a volume of 250 cm ³ , and 2 cm ^{3 of} the compound was diluted with ethyl lactate to make 100 cm ³ to prepare a solution having a concentration of 0.028 g / L. For this solution, the absorbance at the maximum absorption wavelength (λmax) and the maximum absorption wavelength (λmax) were measured using a UV-visible spectrophotometer (V-650DS, manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). . The results are shown in Table 2.

In the table, the compound (R-1) is C.I. Solvent Yellow 21 (Olesol Permanent Yellow 2G, manufactured by Taoka Chemical Industry Co., Ltd.).

[Example 8] [Preparation of colored photosensitive resin composition]

The following ingredients are mixed to obtain a colored resin composition:

(A) Colorant: Compound (I-1): 20 parts of compound synthesized in Example 1

(B-1) Resin: methacrylic acid / benzyl methacrylate copolymer (Molar ratio: 30/70, weight average molecular weight 10700, acid value 70 mgKOH / g) 70 parts

(C-1) Polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 30 parts

(D-1) Photopolymerization initiator: Benzophenone dimethyl ketal (Irgacure 651, manufactured by Ciba Japan) 15 parts

(E-1) Solvent: 680 parts of ethyl lactate.

[Production of color filters]

The colored resin composition obtained above was coated on glass by a spin coating method to volatilize volatile components. After cooling, light irradiation was performed using a patterned quartz glass mask and an exposure machine. After light irradiation, development was performed with an aqueous potassium hydroxide solution, and an oven was heated to 200 ° C. to obtain a color filter.

[Example 9]

A colored resin composition and a color filter were obtained in the same manner as in Example 8 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-2) synthesized in Example 2.

[Example 10]

A colored resin composition and a color filter were obtained in the same manner as in Example 8 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-3) synthesized in Example 3.

[Example 11]

A colored resin composition and a color filter were obtained in the same manner as in Example 8 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-4) synthesized in Example 4.

[Example 12]

A colored resin composition and a color filter were obtained in the same manner as in Example 8 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-5) synthesized in Example 5.

[Example 13]

A colored resin composition and a color filter were obtained in the same manner as in Example 8 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-143) synthesized in Example 6.

[Example 14]

A colored resin composition and a color filter were obtained in the same manner as in Example 8 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-156) synthesized in Example 7.

As can be seen from the results in Table 2, the compound of the present invention exhibits a high spectroscopic concentration due to its high absorbance. In addition, the colored resin composition containing the compound has excellent color properties and can produce a high-quality color filter.

Industrial availability

The compounds of the invention can be used as dyes. The compound of the present invention is particularly useful as a dye for a color filter of a display device such as a liquid crystal display device because of its high Mohr absorption coefficient and high spectral density.

Claims (5)

A compound, which is represented by formula (0):

[In formula (0), R ¹ represents a monovalent saturated hydrocarbon group of 1 to 8 carbon atoms which can be substituted with -OH or a hydrogen atom by -COOR ⁸ ; R ² represents a -CN group; R ³ represents an alkane of 1 to 4 carbon atoms Radical; R ^4a ~ R ^7a independently represent -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, -SO ₂ NR ⁸ R ⁹ or -NR ¹¹ R ¹² ; R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ¹¹ and R ¹² each independently represent a hydrogen atom and a carbon number 1 to 8 Monovalent aliphatic hydrocarbon group, acyl group having 2 to 8 carbon atoms or tetrahydrofurfuryl group; R ¹¹ and R ¹² can also be bonded to each other to form a ring containing a nitrogen atom; A ⁺ represents hydrogen cation, sodium cation, potassium cation Or tetraalkylammonium cation with carbon number 1 ~ 4]. A compound represented by formula (I):

[In formula (I), R ¹ represents a monovalent saturated hydrocarbon group of 1 to 8 carbon atoms which may be substituted with -OH or a hydrogen atom by -COOR ⁸ ; R ² represents -CN; R ³ represents an alkyl group of 1 to 4 carbon atoms ; R ⁴ ~ R ⁷ independently represent -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, or -SO ₂ NR ⁸ R ⁹ ; R ⁸ and R ⁹ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; A ⁺ represents a hydrogen cation, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms] . The compound according to claim 1 or 2, wherein at least 3 of R ⁴ to R ⁷ are hydrogen atoms. A dye comprising the compound as claimed in claim 1 or 2 as an active ingredient. A coloring resin composition containing the dye, resin, and solvent according to claim 4.