TWI531622B - Pyridine ketone compound compounds - Google Patents

Description

Pyridone complex compound

This invention relates to a compound useful as a dye.

Conventionally, a dye of a metal salt-missing compound has been used for color display using reflected light or transmitted light in various fields (for example, a fiber material, a liquid crystal display device, etc.). As such a dye, for example, C.I. Solvent Yellow 21 represented by the following formula, which is a dye of a chromium complex which has an azo compound as a ligand, is known.

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

Among the above-mentioned compounds known in the prior art, the molar absorption coefficient is small, and the spectral concentration sometimes cannot sufficiently satisfy the requirements.

The present invention provides the following [1] to [8].

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

[In the formula (0), R ¹ represents a one-valent 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 An 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; and R ^4a to R ^7a 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 be bonded to each other to form a 6 to 7 membered ring containing a carbon of a benzene ring; and R ⁸ and R ⁹ each independently represent a hydrogen atom and a carbon number; a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, which is contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group The hydrogen atom may also 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; ¹¹ and R ¹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a mercapto group having 2 to 8 carbon atoms or a tetrahydroindenyl group; and R ¹¹ and R ¹² may be bonded to each other to form a hydrogen group. a ring of nitrogen atoms; R ²¹ to R ²⁵ independently of each other represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; and R ²⁶ and R ²⁷ are independently represented by each other; Hydrogen atom or methyl].

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

[In the formula (I), R ¹ represents a one-valent 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 An 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; and R ⁴ to R ⁷ independently of each other represent -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 ; R ⁸ and R ⁹ independently represent a hydrogen atom, a carbon number of 1~ 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 aliphatic hydrocarbon group, the aralkyl group and a hydrogen atom contained in the aromatic hydrocarbon group It may also 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; and R ²¹ to R ²⁵ independently represent a hydrogen atom and carbon. one number 1 to 8 or a monovalent aliphatic hydrocarbon group having 6 to 10 carbon atoms, one of the divalent aromatic hydrocarbon group; R ²⁶ and R ²⁷ independently of one another Represents a hydrogen atom or a methyl group].

[3] The compound according to [1] or [2], wherein R ¹ is a one-valent 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 [1] to [3] wherein at least 3 of R ^4a to R ^7a is a hydrogen atom, or at least 3 of R ⁴ to R ⁷ are a hydrogen atom.

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

[6] of [1] to a compound of [5], wherein R ²⁵ is one having 1 to 8 carbon atoms, divalent aliphatic hydrocarbon group.

[7] A dye comprising the compound according to any one of [1] to [6] as an active ingredient.

[8] A colored resin composition containing the dye of [7], a resin, and a solvent.

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

[In the formula (0), R ¹ represents a one-valent 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 An 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; and R ^4a to R ^7a 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 be bonded to each other to form a 6 to 7 membered ring containing a carbon of a benzene ring; and R ⁸ and R ⁹ each independently represent a hydrogen atom and a carbon number; a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, which is contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group The hydrogen atom may also 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; ¹¹ and R ¹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a mercapto group having 2 to 8 carbon atoms or a tetrahydroindenyl group; and R ¹¹ and R ¹² may be bonded to each other to form a hydrogen group. a ring of nitrogen atoms; R ²¹ to R ²⁵ independently of each other represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; and R ²⁶ and R ²⁷ are independently represented by each other; Hydrogen atom or methyl].

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

The compound (0) and the compound (I) are salts of a cation of a rhodamine compound containing a chromium partial ion of an anion moiety and a cationic moiety.

[In the formula (I), R ¹ represents a one-valent 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 An 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; and R ⁴ to R ⁷ independently of each other represent -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 ; R ⁸ and R ⁹ independently represent a hydrogen atom, a carbon number of 1~ 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 aliphatic hydrocarbon group, the aralkyl group and a hydrogen atom contained in the aromatic hydrocarbon group It may also 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; and R ²¹ to R ²⁵ independently represent a hydrogen atom and carbon. one number 1 to 8 or a monovalent aliphatic hydrocarbon group having 6 to 10 carbon atoms, one of the divalent aromatic hydrocarbon group; R ²⁶ and R ²⁷ independently of one another Represents a hydrogen atom or a methyl group].

Examples of the one-valent saturated hydrocarbon group having 1 to 8 carbon atoms in R ¹ and R ¹⁰ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group. A straight-chain saturated hydrocarbon group; isopropyl, isobutyl, t-butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl Pentyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-B 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 Base, 1,4-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl Base, 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 a cyclic saturated hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group.

Examples of the one-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ⁸ and R ⁹ include a vinyl group, a propylene group, and a different group in addition to the groups listed in the linear saturated hydrocarbon group and the branched saturated hydrocarbon group. A propylene group, a butenyl group, a 2-methylpropenyl group or the like.

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

Examples of the one-valent 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, a biphenyl group, a fluorenyl group and a fluorenyl group. Wait.

Examples of the saturated hydrocarbon group in which -CH ₂ - is substituted with -CO- include, for example, etidinyl, 3-oxobutyl, 2-oxobutyl, 3-oxopentyl, 2-oxopentyl. a saturated hydrocarbon group containing an oxo group such as 3-oxohexyl; benzamidine methyl, 2-oxo-2-naphthylethyl, 2-oxo-2-hydroxyphenylethyl, 2-oxo 2-hydroxynaphthylethyl, 2-oxo-2-methoxyphenylethyl, 2-oxo-2-methoxynaphthylethyl, 2-oxo-3-phenylpropyl And a saturated hydrocarbon group containing an aromatic hydrocarbon group or an oxo group such as 2-oxo-3-naphthylpropyl group.

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

Examples of -OR ⁸ include a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and a 2-ethylhexyloxy group. , phenoxy, benzyloxy, benzhydryloxy and the like.

As the substituted by -OR ¹⁰ -OR ^8, for example, include: methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, 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 the hydrogen atom is substituted by -OR ⁸ include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxymethoxymethyl group, a 2-hydroxyethoxymethyl group, and a 2- Hydroxy-containing saturated hydrocarbon group such as hydroxymethoxyethyl, 2-(2-hydroxyethoxy)ethyl, 2-oxo-4-hydroxybutyl; methoxymethyl, ethoxymethyl, propyl Oxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, 2-oxo-4-methoxy Alkoxy-containing saturated hydrocarbon group; methoxymethoxymethyl, 2-methoxyethoxymethyl, ethoxymethoxymethyl, 2-ethoxyethoxymethyl Base, 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 group; phenoxymethyl, 1-naphthyloxymethyl, 2-naphthyloxymethyl, hydroxyphenoxymethyl, hydroxynaphthyloxymethyl a aryloxy-containing saturated hydrocarbon group such as methoxyphenoxymethyl, methoxynaphthyloxymethyl or 3-phenoxy-2-oxopropyl; benzyloxymethyl, naphthylmethoxy Methyl, hydroxybenzyloxymethyl, hydroxynaphthylmethoxymethyl, methoxybenzyloxymethyl, methoxynaphthylmethoxymethyl, phenoxyethoxymethyl, naphthalene A saturated hydrocarbon group containing an aralkyloxy group, such as an oxyethoxymethyl group.

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

Examples of the saturated hydrocarbon group in which the hydrogen atom is substituted by -COOR ⁸ include a carboxyl group-containing saturated hydrocarbon group such as a carboxymethyl group, a carboxyethyl group, a carboxypropyl group or a carboxybutyl group; methoxycarbonylmethyl group and methoxycarbonyl group B; , ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, propoxycarbonylethyl, butoxycarbonylmethyl, butoxycarbonylethyl, phenoxymethoxy a saturated hydrocarbon group containing an alkoxycarbonyl group such as a carbonylmethyl group, a 2-hydroxyethoxycarbonylmethyl group or a 2-methoxyethoxycarbonylmethyl group; a phenoxycarbonylmethyl group, a naphthyloxycarbonylmethyl group or the like a saturated hydrocarbon group of an aryloxycarbonyl group; a saturated hydrocarbon group containing an aralkoxycarbonyl group such as a benzyloxycarbonylmethyl group or a naphthylmethoxycarbonylmethyl group; 2-oxopropoxycarbonylmethyl group, 2-(2- Oxopropoxycarbonyl)ethyl, 3-(2-oxopropoxycarbonyl)propyl, 2-oxobutoxycarbonylmethyl, 2-(2-oxobutoxycarbonyl)ethyl , 3-(2-oxobutoxycarbonyl)propyl, 2-oxopentoxycarbonylmethyl, 2-(2-oxopentyloxycarbonyl)ethyl, 3-(2-oxopentyl) Oxycarbonyl)propyl, 3-oxobutoxycarbonylmethyl, 2-(3-oxo Butoxycarbonyl)ethyl, 3-(3-oxobutoxycarbonyl)propyl, 3-oxopentoxycarbonylmethyl, 2-(3-oxopentoxycarbonyl)ethyl, 3 -(3-oxopentyloxycarbonyl)propyl, 2-oxohexyloxycarbonylmethyl, 2-(2-oxohexyloxycarbonyl)ethyl, 3-(2-oxohexyloxy) A saturated hydrocarbon group containing a -CH ₂ -CO-substituted alkoxycarbonyl group such as a carbonyl)propyl group; 3-methoxycarbonyl-2-oxopropyl group, 4-methoxycarbonyl-3-oxobutyl group , 5-methoxycarbonyl-4-oxopentyl, 3-ethoxycarbonyl-2-oxopropyl, 4-ethoxycarbonyl-3-oxobutyl, 5-ethoxycarbonyl 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-propoxy carbonyl-3-oxo-pentyl, 5-propoxycarbonyl-4-oxo-hexyl group and an alkoxycarbonyl group containing -CH ₂ - taken by -CO- The saturated hydrocarbon groups.

As the saturated hydrocarbon group in which the hydrogen atom is substituted with -CONR ⁸ R ⁹ , for example, N-methylaminocarbonylmethyl, N-methylaminocarbonylethyl, N,N-dimethylaminocarbonylmethyl , N,N-dimethylaminocarbonylethyl, N,N-ethylmethylaminocarbonylmethyl, N,N-ethylmethylcarbonylethyl, etc. a saturated hydrocarbon group; N-phenylaminocarbonylmethyl, N,N-phenylmethylcarbonylmethyl, N,N-diphenylcarbonylmethyl, N,N-phenylbenzylcarbonylmethyl, etc. a saturated hydrocarbyl group substituted with an aryl group; N-benzylaminocarbonylmethyl, N,N-dibenzylcarbonylmethyl, N,N-bis(2-phenylethyl)carbonylmethyl A saturated hydrocarbon group or the like containing an arylalkyl group substituted with an aralkyl group.

Examples of -OCOR ⁸ include an ethoxycarbonyl group, a p-pentyloxy group, a benzamidineoxy group, and the like.

Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted by -OCOR ⁸ include an ethoxymethyloxy group, an ethyl ethoxyethyl group, an ethyl carbonyloxymethyl group, an ethylcarbonyloxyethyl group, and a propylcarbonyloxy group. Methyl, propylcarbonyloxyethyl, butylcarbonyloxymethyl, butylcarbonyloxyethyl, hexyloxyethyl, 2-ethylbutyloxyethyl, 2-ethyl a saturated hydrocarbyl group containing an alkylcarbonyloxy group such as hexyloxyethyl, 2-propylhexyloxyethyl, p-pentyloxyethyl or 2-methylpropoxyethyl; Methyl, benzyl methoxyethyl, naphthyloxycarbonylmethyl, benzylcarbonyloxymethyl, naphthylmethylcarbonyloxymethyl, methylbenzhydryloxymethyl, 2-methyl Benzobenzyloxyethyl, 4-methylbenzyloxyethyl, 3,4-dimethylbenzyloxyethyl, hydroxybenzyloxymethyl, methoxybenzate An aromatic hydrocarbon group or a saturated hydrocarbon group containing a carbonyloxy group such as a methoxymethyl group, a 4-methoxybenzyloxyethyl group or a 3,4-dimethoxybenzylideneoxyethyl group.

Examples of -COR ⁸ include an ethyl fluorenyl group, a propyl fluorenyl group, an isobutyl fluorenyl group, a pentamidine group, and an isovaleryl group.

Examples of -OCOOR ⁸ include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, a n-butoxycarbonyloxy group, and an isobutoxy group. A carbonyloxy group, a second butoxycarbonyloxy group, a n-pentyloxycarbonyloxy group, a phenoxycarbonyloxy group or the like.

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

R ^{1 is} preferably a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms which is substituted by -OH or -OCOR ⁸ . When R ^{1 is} such a group, solubility in an organic solvent becomes high, and it is preferable.

R ² is a hydrogen atom, -CN or -CONH ₂ . Among them, in terms of easy access to raw materials, -CN is preferred.

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

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

Examples of the alkyl group having 1 to 4 carbon atoms which are substituted by 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 , a halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, - SO ₂ NR ⁸ R ⁹ or -NR ¹¹ R ¹² .

R ⁴ to 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 in R ^4a to R ^7a include N-methylamino group, N,N-dimethylamino group, N-ethylamino group, and N,N-diethylamine. , N-propylamino, N,N-dipropylamino, N-butylamino, N,N-dibutylamino, N-pentylamino, N-ethenylamino Wait.

-NR ¹¹ R ^{12 in} which R ¹¹ and R ¹² are bonded to each other to form a ring containing a nitrogen atom, and examples thereof include a 1-pyrazolyl group, a pyrrolidinyl group, and a piperidinyl group. Orolinic group and the like.

Among them, in terms of solubility in an organic solvent, an N-ethenylamino group is preferred.

When at least three of R ⁴ to R ⁷ are a hydrogen atom, the color density becomes high, which is preferable.

Examples of -SO ₂ NR ⁸ R ^{9 in} R ^4a to R ^7a and R ⁴ to R ⁷ include an unsubstituted sulfonamide group, an N-monosubstituted amine sulfonyl group, and an N,N-disubstituted amine sulfonate.醯基.

Examples of the N-monosubstituted amine sulfonyl group include N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, and N-isopropylamine sulfonate group. , N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonyl , N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl)aminesulfonate , N-(2,2-dimethylpropyl)amine sulfonyl, N-(1-methylbutyl)amine sulfonyl, N-(2-methylbutyl)amine sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonyl , N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1,4-di Methyl amyl sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl)hexylamine sulfonyl, N-monosubstituted amine sulfonyl group substituted with an aliphatic hydrocarbon group such as N-(1,1,2,2-tetramethylbutyl)amine sulfonyl, N-allylamine sulfonyl; N-( 2-hydroxyethyl)amine sulfonyl, N-(3-hydroxyl Aminesulfonyl, N-(2-hydroxypropyl)aminesulfonyl, N-(2,3-dihydroxypropyl)aminesulfonyl, N-(2-hydroxybutyl)aminesulfonate N-monosubstituted amine sulfonyl group substituted with a hydroxyl group-containing aliphatic hydrocarbon group such as N-(4-hydroxybutyl)amine sulfonyl group or N-(1-hydroxymethylethyl)amine sulfonyl group; N-(2-methoxyethyl)amine sulfonyl, N-(2-ethoxyethyl)amine sulfonyl, N-(1-methoxypropyl)amine sulfonyl, N- Methoxypropylamine sulfonyl, N-ethoxypropylamine sulfonyl, N-propoxypropylamine sulfonyl, N-isopropoxypropylamine sulfonyl, N-hexyl Oxypropyl propyl sulfonyl, N-(2-ethylhexyloxypropyl)amine sulfonyl, N-(3-tert-butoxypropyl)amine sulfonyl, N-(4, N-monosubstituted amine sulfonyl group substituted with alkoxy-containing alkyl group or cycloalkyl group, such as 4-dimethoxybutyl)amine sulfonyl group, N-methoxyhexylamine sulfonyl group; N- N-monosubstituted amine sulfonyl group substituted by an alkoxyalkyl group-containing aliphatic hydrocarbon group such as [1-(2-ethoxyethoxy)propyl]aminosulfonyl group; N-phenylamine sulfonium sulfonate N-monosubstituted amine sulfonyl group substituted by aryl group such as N-(1-naphthyl)amine sulfonyl group; N-benzylamine sulfonyl group N-(1-phenylethyl)amine sulfonyl, N-(2-phenylethyl)amine sulfonyl, N-(3-phenylpropyl)amine sulfonyl, N-(4- Phenylbutyl)aminesulfonyl, N-[2-(2-naphthyl)ethyl]aminesulfonyl, N-[2-(4-methylphenyl)ethyl]aminesulfonyl, An N-monosubstituted amine sulfonate substituted with an aralkyl group such as N-(3-phenyl-1-propyl)amine sulfonyl, N-(3-phenyl-1-methylpropyl)amine sulfonyl Sulfhydryl; N-(3,4,5-trimethoxybenzyl)amine sulfonyl, N-[2-(3,4-dimethoxyphenyl)ethyl]aminesulfonyl, N- An N-monosubstituted amine sulfonyl group substituted with a substituted aralkyl group such as a 2-(2-ethoxyphenyl)ethyl]amine sulfonyl group; as an N,N-disubstituted amine sulfonyl group For example, N,N-dimethylaminesulfonyl, N,N-ethylmethylaminesulfonyl, N,N-diethylaminesulfonyl, N,N-propylmethyl Aminesulfonyl, N,N-isopropylmethylaminesulfonyl, N,N-t-butylmethylaminesulfonyl, N,N-butylethylaminesulfonyl, N,N-double N,N-substituted amine sulfonyl group substituted by two aliphatic hydrocarbon groups, such as (1-methylpropyl)aminesulfonyl, N,N-heptylmethylaminesulfonyl; N,N-double ( 2-hydroxyethyl)amine sulfonyl, N,N-bis(2-methoxyethyl An N,N-disubstituted amine sulfonyl group substituted with a substituent-containing aliphatic hydrocarbon group such as an aminesulfonyl group or an N,N-bis(2-ethoxyethyl)amine sulfonyl group.

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 2 to 8 of a hydroxyl group-containing alkyl group or aryl group, or a carbon number 2 to 8 alkoxy group-containing alkyl group or aryl group, particularly preferably 2-ethylhexyl group.

The one-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ²¹ to R ²⁵ may be the same as the one-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ⁸ and R ⁹ .

The aromatic hydrocarbon group having 6 to 10 carbon atoms of one of R ²¹ to R ²⁵ may be the same as the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ⁸ , R ⁹ and R ¹⁰ .

R ²¹ to R ^{24 are} preferably each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an ethyl group. The total carbon number of R ²¹ to R ²⁴ is preferably 10 or less, more preferably 8 or less. When the carbon number is 10 or less, the spectroscopic concentration becomes high, which is preferable.

R ²⁵ tends to have a solubility in an organic solvent, and is preferably a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group.

R ²⁶ and R ²⁷ are each independently a hydrogen atom or a methyl group.

In the compound (0) and the compound (I), the cation derived from the rhodamine compound (that is, the cation represented by the following formula (II)) which is a cationic moiety is preferably a formula (II-1) to (II-). 146) The cation represented.

In the formula (II), R ²¹ to R ^{27 have} the same meanings as described above. ]

Examples of the compound (0) include the compound (I-1) to the compound (I-320). A ⁺ represents a cation derived from a rhodamine compound. In Table 1, the A ⁺ column describes the number of the cation of the above-exemplified cation. ⁿ Bu represents n-butyl and Et represents an ethyl group. Further, in the case when the column number R according to formula ^1, the group of formula described in the above-shown numbering.

Among them, the compound (I-1) to the compound (I-4), the compound (I-286), and the compound (I-299) are preferred because of the high spectral concentration.

A method for producing the compound (I) will be described as an example of a method for producing the compound of the present invention. The compound which is not the compound (I) in the compound (0) can also be produced by the same method as the method for producing the compound (I) shown below.

The compound (I) can form a chromium salt by using a compound represented by the formula (d) (hereinafter sometimes referred to as "compound (d)") and a chromium compound, and thereafter the chromium salt and the formula (II) The salt of the cation represented by the salt is produced by a salt exchange reaction.

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

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

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

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

Examples of the inorganic anion include a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, and a hypochlorite ion. Examples of the organic anion include CH ₃ -COO ^- , C ₆ H ₅ -COO ^- and the like. Preferred are chloride ions, bromide ions, 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, more preferably 0 ° C to 30 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

The method of obtaining the compound (d) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to mix the reaction mixture with an acid (for example, acetic acid or the like) and water, and the precipitated crystals are collected by filtration. The above acid is preferably prepared by previously preparing an aqueous acid solution, and then adding the reaction mixture to the above aqueous solution. The temperature at which the reaction mixture is added is usually 10 ° C or more and 50 ° C or less, preferably 20 ° C or more and 50 ° C or less, more preferably 20 ° C or more and 30 ° C or less. Further, it is preferred to add the reaction mixture to an aqueous acid solution and then stir at the same temperature for about 0.5 to 2 hours. The crystals to be filtered are preferably washed with water or the like, followed by drying. Further, it may be further purified by a known method such as recrystallization, as needed.

The chromium salt may be obtained by using 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. The reaction is carried out for 3 to 10 hours.

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

The chromium compound is preferably used in an amount of from 0.5 to 1 mol per mol of the compound (d).

Further, in order to promote the reaction, an inorganic base may be allowed to coexist.

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

The compound represented by the formula (I) can be produced by subjecting a chromium salt obtained as an anion portion to a salt of a cation which is a cationic portion and containing a cation represented by the formula (II) in a solvent. Preferably, the chromium salt is reacted with a salt containing a cation represented by the formula (II) at a molar ratio of 1:1 to 1:4.

In the formula (II'), R ²¹ to R ^{27 have} the same meanings as described above; and A ² represents an inorganic anion or an organic anion. ]

Examples of A ² include the same anions as those of A ¹ , and among them, halide ions such as fluoride ions, chloride ions, and bromide ions are preferable.

The method of obtaining the compound (I) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to mix the reaction mixture with an inorganic salt (e.g., common salt, etc.) and water, and the precipitated crystals are collected by filtration. The above inorganic salt is preferably prepared by previously preparing an aqueous solution of an inorganic salt, and adding the reaction mixture to the above aqueous solution. The temperature at the time of adding the reaction mixture is preferably 10 ° C or more and 50 ° C or less, more preferably 10 ° C or more and 40 ° C or less, and further preferably 10 ° C or more and 25 ° C or less. Further, it is preferred to add the reaction mixture to an aqueous solution of an inorganic salt, and then stir at the same temperature for about 0.5 to 2 hours. The crystals to be filtered are preferably washed with water or the like, followed by drying. Further, it may be further purified by a known method such as recrystallization, as needed.

The compound of the present invention thus obtained can be used as a dye. In particular, since the spectral density is high, it can be used as a color filter or a fiber material used for a display device such as a liquid crystal display device that performs color display using reflected light or transmitted light.

The dye of the present invention is a dye containing 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).

The coloring agent (A) may further contain a pigment and/or a dye different from the dye of the present invention, in addition to the dye of the present invention.

As the dye different from the dye of the present invention, it can be exemplified as a solvent index (Solvent), an acidity (Acid), and an alkalinity in the Colour Index (published by The Society of Dyers and Colourists). Basic), reactive, direct, disperse or reduced (Vat) dyes. More specifically, a dye of the color index (C.I.) number as described below may be mentioned, but it is 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 purple 102; CI solvent green 1, 5; CI acid green 3, 5, 9, 25, 28; CI alkaline green 1; CI reduced green 1 and so on.

As the pigment, an organic pigment or an inorganic pigment which is usually used in a pigment dispersion resist can be mentioned. Examples of the inorganic pigment include a metal compound such as a metal oxide or a metal salt, and specific examples thereof include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Composite metal oxide.

Further, specific examples of the organic pigment and the inorganic pigment include a compound classified as a pigment in a Colour Index (published by the British Society of Dyers). More specifically, the pigment of the color index (C.I.) number as described below may be mentioned, but it is not limited to these.

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 oranges 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 and so on.

The content of the colorant (A) is preferably from 5 to 60% by mass based on the solid content of the colored resin composition. Here, the solid content component means the total of the 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 from 3 to 100% by mass.

The dyes and pigments different from the dye of the present invention may be used alone or in combination of two or more kinds together with the dye 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, 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-phenyl maleimide 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, more preferably 6,000 to 30,000.

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

The content of the resin (B) is preferably from 7 to 65% by mass, and more preferably from 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 which can be polymerized by using an active radical generated by the polymerization initiator (D), an acid or the like. For example, a compound having a polymerizable carbon-carbon unsaturated bond or the like can be mentioned.

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 pentamethyl acrylate, and dipentaerythritol hexaacrylate. Dipentaerythritol hexamethacrylate or the like. The photopolymerizable compound (C) may be used singly or in combination of two or more.

The content of the polymerizable compound (C) is preferably from 5 to 65% by mass, more preferably from 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, an acid generator, and the like. The living radical generating agent generates active radicals by the action of heat or light. Examples of the living radical generating agent include a phenylalkyl ketone compound and 9-oxosulfuric acid. Compound, three Compounds, hydrazine compounds, and the like.

As the above phenylalkyl ketone compound, for example, 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, 2- Hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

As the above 9-oxygen sulfur For the compound, for example, 2-isopropyl-9-oxysulfide 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

As the above three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

Examples of the ruthenium compound include an O-fluorenyl ruthenium compound, and specific examples thereof include N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2. -imine, N-benzylideneoxy-1-(4-phenylthiophenyl)oct-1-one-2-imine, N-acetoxy-1-[9-ethyl-6 -(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2- 4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzimidyl}-9H-indazol-3-yl]ethane-1-imine .

Further, as the living radical generating agent, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 2,2'-bis(o-chlorophenyl)-4,4' may be used. 5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzoin, 9,10-phenanthrenequinone, camphorquinone, Methyl phenylglyoxylate, a titanocene compound, and the like.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenyloxyphenyldimethylate. Base p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, An anthracene salt such as phenylhydrazine p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate, or a nitrobenzyl tosylate or a benzoin tosylate.

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

The content of the polymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator is within the above range, high sensitivity is obtained, exposure time is shortened, and productivity is improved, which is preferable.

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

Examples of the above ethers include tetrahydrofuran, tetrahydropyran, and 1,4-two. 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol single Ethyl 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 Acid esters, etc.

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 glycerin.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, alkyl ester, methyl lactate, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy acetic 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-methylpropanoate, 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 above guanamines include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

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

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

The colored resin composition of the present invention may contain various additives such as a surfactant, a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, and a chain transfer agent, as needed.

The compounds of the invention are useful as dyes. Further, since the compound of the present invention has a high molar absorption coefficient and a high spectral concentration, it is particularly useful as a dye used for a color filter of a display device such as a liquid crystal display device.

Further, the colored resin composition containing the compound of the present invention can be used in a known manner for a display device having a color filter as a part of a constituent member thereof (for example, a known liquid crystal display device or an organic EL (Electroluminescence) device). Various devices related to color images, such as solid-state imaging devices.

Example

The invention will now be described more specifically by way of examples.

In the examples and comparative examples, the % and the parts indicating the content or the amount used are based on mass unless otherwise specified.

In the following examples, the structure of the compound is by NMR (Nuclear Magnetic Resonance) (JMM-ECA-500, manufactured by JEOL Ltd.), mass spectrometer (LC, Model 1200 manufactured by Agilent; MASS, Agilent manufactured LC/MSD type) and elemental analysis (VARIO-EL (Elementar)) were confirmed.

[Example 1]

After adding 170 parts of water to 17.0 parts of o-amine benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.4 parts of sodium hydroxide was added and dissolved. Under ice cooling, 25.5 parts of sodium nitrite was added, followed by a small amount of 79.5 parts of 35% hydrochloric acid. Thereafter, the mixture was stirred under ice cooling for 2 hours, and 250 parts of a 9% guanamine 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.

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

Identification of compounds represented by formula (d-1)

¹ H-NMR (500 MHz, δ (ppm, TMS basis), 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).

200 parts of N-methylpyrrolidone was added to 10 parts of the compound represented by the formula (d-1), and after heating to 80 ° C to dissolve it, 3.7 parts of chromium formate n-hydrate was added, and the mixture was stirred at 135 ° C for about 2 parts. After an hour, the temperature was lowered to 80 ° C, 1.2 parts of sodium carbonate was added, and the mixture was further stirred at 135 ° C for about 2 hours to obtain a dark orange solution. The solution was poured into 1000 parts of a 1 N aqueous solution of hydrochloric acid, and the obtained orange solid was filtered, washed twice with 80 parts of water, and then dried under vacuum at 60 ° C to obtain 7.5 parts of the compound represented by the formula (f-1). .

Identification of compounds represented by formula (f-1)

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

Accurate quality: 723.1

To the 1.3 parts of the compound represented by the formula (f-1), 19.5 parts of N-methylpyrrolidone was added to prepare a solution (s1). Further, 25.0 parts of methanol was added to 1.0 part of a rhodamine compound (Rhodamine 6G, manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the formula (g-1) to prepare a solution (t1). Thereafter, the solution (s1) was mixed with the solution (t1) at room temperature, and after stirring for about 1 hour, it was poured into 500 parts of water. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 1.6 parts of the compound represented by the formula (I-1) (yield 80%).

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

(Elemental Analysis) C 63.0 H 4.7 N 11.9 Cr 4.5

[Embodiment 2]

200 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 1.5 parts, 4-(N, N-) were added to 25.0 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.). 1.6 parts of dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 12.1 parts of ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred for about 30 minutes. Thereafter, 55.3 parts of anhydrous chloroform was added to 14.5 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.). After pre-dissolving the solution, it was stirred at room temperature for about 2 hours. After two times of liquid separation operation using 150 parts of 1 N aqueous hydrochloric acid solution, the organic layer was washed twice with 150 parts of 10% saline. Then, 43 parts of anhydrous magnesium sulfate was added, and after stirring for about 30 minutes, the desiccant was filtered, and the solvent was distilled off, whereby 23.1 parts of a rhodamine compound represented by the formula (g-2) (yield 87%) was obtained.

Identification of compounds represented by formula (g-2)

(mass spectrometer) ionization mode = ESI +: m / z = 471.2 [M-Cl ^- ] ⁺

Accurate quality: 506.2

To a solution of 3.9 parts of the compound represented by the formula (f-1), 60 parts of N-methylpyrrolidone was added to prepare a solution (s2). Further, 55 parts of N-methylpyrrolidone was added to 3.1 parts of the rhodamine compound represented by the formula (g-2) to prepare a solution (t2). Thereafter, the solution (s2) was mixed with the solution (t2) at room temperature, and after stirring for about 1 hour, it was poured into 1200 parts of water. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 6.0 parts of the compound represented by the formula (I-2) (yield 95%).

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

(Elemental Analysis) C 62.3 H 5.1 N 12.3 Cr 4.4

[Example 3]

After adding 88 parts of water to 5.5 parts of o-amine benzoic 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, followed by a small amount of 33.2 parts of 35% hydrochloric acid. Thereafter, the mixture was stirred for 3 hours under ice cooling, and 100 parts of a 9% guanamine sulfuric acid aqueous solution was slowly added for quenching excess nitrous acid, and stirred 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 were stirred at 95 ° C for 24 hours. After cooling the reaction solution to room temperature, it was added to a mixed liquid of 304 parts of water and 35 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue obtained by suction filtration, and dried to obtain 20.4 parts of the compound represented by the formula (c-3).

Then, 8.5 parts of the compound represented by the formula (c-3) was suspended in 77 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. While maintaining the pH of the suspension at 8.0 to 9.5, the suspension containing the 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 11.2 parts of the compound of formula (d-3). The structure was confirmed by ¹ H-NMR.

Identification of compounds represented by formula (d-3)

¹ H-NMR (270 MHz, δ (ppm, TMS basis), 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).

100 parts of N,N-dimethylformamide, 7.7 parts of ammonium sulfate, and 2.6 parts of sodium acetate were added to 10 parts of the compound represented by the formula (d-3), and stirred at 135 ° C for about 6 hours to obtain a dark color. Orange solution. This solution was poured into 20% saline solution, and the obtained orange solid was filtered, and dried under vacuum at 60 ° C to obtain 18 parts of the compound represented by formula (f-3).

Identification of compounds represented by formula (f-3)

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

Accurate quality: 755.1

To a solution of 2.1 parts of the compound represented by the formula (f-3), 26.3 parts of N-methylpyrrolidone was added to prepare a solution (s3). Further, 18 parts of methanol was added to 1.5 parts of a rhodamine compound (Rhodamine 6G, manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the formula (g-1) to prepare a solution (t3). Thereafter, the solution (s3) was mixed with the solution (t3) at room temperature, and after stirring for about 1 hour, it was poured into 650 parts of water. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 2.8 parts (yield 86%) of the compound of formula (I-3).

Identification of compounds represented by formula (I-3)

(Elemental Analysis) C 60.0 H 4.8 N 12.3 Cr 4.6

[Example 4]

According to the method described on page 340 of Sakaguchi General Synthetic Dye (Sankyo Publishing Co., Ltd., issued in 1968), phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3-(N, Synthesis of 4-(N,N-diethylamino)-2-benzylidenebenzoic acid by condensation reaction of N-diethylamino)phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (N-ethylamino) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) is condensed, whereby a compound represented by the formula (rh-1) is synthesized.

Then, 42 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.) was added to 6.0 parts of the compound represented by the formula (rh-1) to prepare a solution, and then camphorsulfonic acid (manufactured by Aldrich Co., Ltd.) was added in an amount of 0.4 parts. -(N,N-Dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.5 parts, 3.1 parts of ethanol, and stirred for about 30 minutes. Thereafter, 25 parts of anhydrous chloroform was added to 4.3 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.). After pre-dissolving the solution, it was stirred at room temperature for about 2 hours. After two times of liquid separation operation using 50 parts of 1 N aqueous hydrochloric acid solution, the organic layer was washed with 10% saline. Then, 20 parts of anhydrous magnesium sulfate was added, and after stirring for about 30 minutes, anhydrous magnesium sulfate was removed by filtration, and the solvent was distilled off, whereby 6.2 parts of a rhodamine compound represented by the formula (g-3) (yield 94%) was obtained.

Identification of compounds represented by formula (g-3)

(mass spectrometer) ionization mode = ESI +: m / z = 443.2 [M-Cl ^- ] ⁺

Accurate quality: 478.2

To a solution of 1.7 parts of the compound represented by the formula (f-3), 22 parts of N-methylpyrrolidone was added to prepare a solution (s4). Further, 18 parts of N-methylpyrrolidone was added to 1.2 parts of the rhodamine compound represented by the formula (g-3) to prepare a solution (t4). Thereafter, the solution (s4) was mixed with the solution (t4) at room temperature, and after stirring for about 1 hour, it was poured into 500 parts of water. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 2.2 parts (yield: 83%) of the compound of formula (I-4).

Identification of compounds represented by formula (I-4)

(Elemental Analysis) C 63.1 H 4.6 N 12.0 Cr 4.6

[Example 5]

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

Then, 20.4 parts of the compound represented by the formula (c-3) was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. To this, the above suspension containing the diazonium salt was added dropwise using a pump for 15 minutes. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, whereby a yellow suspension was obtained. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 39.1 parts of the compound of formula (d-4).

Then, 32.5 parts of hydrazine chloride (manufactured by Wako Pure Chemical Industries, Ltd.) represented by the formula (e-1) is added to 39.9 parts of the compound represented by the formula (d-4) in 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 the compound represented by the formula (d-5). The obtained compound was orange, and the maximum absorption wavelength (λmax) was measured in an ethyl lactate solvent, and the result was 459 nm. Further, 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).

To 10.0 parts of the compound represented by the formula (d-5), 150 parts of N,N-dimethylformamide, 7.7 parts of ammonium sulfate, and 2.6 parts of sodium acetate were added, and the mixture was stirred at 135 ° C for about 6 hours to obtain a dark color. Orange solution. This solution was poured into 20% saline solution, and the obtained orange solid was filtered, and dried under vacuum at 60 ° C to obtain 4.9 parts of the compound represented by formula (f-4).

Identification of compounds represented by formula (f-4)

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

Accurate quality: 1121.34

To 2.0 parts of the compound represented by the formula (f-4), 22 parts of N-methylpyrrolidone was added to prepare a solution (s5). Further, 18 parts of N-methylpyrrolidone was added to 1.0 part of the rhodamine compound represented by the formula (g-1) to prepare a solution (t5). Thereafter, the solution (s5) was mixed with the solution (t5) at room temperature, and after stirring for about 1 hour, it was poured into 500 parts of water. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 1.6 parts of a compound represented by formula (I-286) (yield 60%).

Identification of compounds represented by formula (I-286)

(Elemental Analysis) C 61.0 H 5.9 N 10.8 Cr 3.5

[Embodiment 6]

Then, 32.4 parts of benzamidine chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 30.0 parts of the compound represented by the formula (d-4), and the mixture was 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 the compound represented by the formula (d-6). The obtained compound was orange, and the maximum absorption wavelength (λmax) was measured in an ethyl lactate solvent, and the result was 459 nm. Further, the structure was confirmed by 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 ammonium sulfate, and 2.6 parts of sodium acetate were added to 9.6 parts of the compound represented by the formula (d-6), and the mixture was stirred at 135 ° C for about 6 hours. A dark orange solution was obtained. This solution was poured into 20% saline solution, and the obtained orange solid was filtered, and dried under vacuum at 60 ° C to obtain 7.1 parts of the compound represented by formula (f-5).

To the 1.9 part of the compound represented by the formula (f-5), 22 parts of N-methylpyrrolidone was added to prepare a solution (s6). Further, 18 parts of N-methylpyrrolidone was added to 1.0 part of the rhodamine compound represented by the formula (g-1) to prepare a solution (t6). Thereafter, the solution (s6) was mixed with the solution (t4) at room temperature, and after stirring for about 1 hour, it was poured into 500 parts of water. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 1.7 parts of the compound of formula (I-299).

Identification of compounds represented by formula (I-299)

(Elemental Analysis) C 65.0 H 4.5 N 11.0 Cr 3.4

<Measurement of absorbance>

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

In Table 2, the compound (R-1) was C.I. Solvent Yellow 21 (Oil Sol Permanent Yellow 2G, manufactured by Tajika Chemical Industry Co., Ltd.).

[Embodiment 7] [Preparation of Colored Photosensitive Resin Composition]

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

[Production of color filter]

The colored resin composition obtained above was applied onto the glass by a spin coating method to volatilize the volatile component. After cooling, light irradiation was performed using a patterned quartz glass mask and an exposure machine. After the light irradiation, development was carried out using an aqueous potassium hydroxide solution, and the mixture was heated to 200 ° C in an oven to obtain a color filter.

[Embodiment 8]

A colored resin composition and a color filter were obtained in the same manner as in Example 7 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-2) synthesized in Example 2.

[Embodiment 9]

A colored resin composition and a color filter were obtained in the same manner as in Example 7 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-3) synthesized in Example 3.

[Embodiment 10]

A colored resin composition and a color filter were obtained in the same manner as in Example 7 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-4) synthesized in Example 4.

[Example 11]

A colored resin composition and a color filter were obtained in the same manner as in Example 7 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-286) synthesized in Example 5.

[Example 13]

A colored resin composition and a color filter were obtained in the same manner as in Example 7 except that the compound (I-1) synthesized in Example 1 was replaced with the compound (I-299) synthesized in Example 6.

As is apparent from the results of Table 2, since the compound of the present invention has a high absorbance, it exhibits a high spectral concentration. Further, 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 are useful as dyes. Since the compound of the present invention has a high molar absorption coefficient and a high spectral concentration, it is particularly useful as a dye used for a color filter of a display device such as a liquid crystal display device.

Claims (7)

A compound represented by formula (0): [In the formula (0), R ¹ represents a one-valent saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted by -OH or -COOR ⁸ ; R ² represents a -CN or -CONH ₂ group; and R ³ represents a carbon number of 1 to 4; The alkyl group; R ^4a to R ^7a each independently represent -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , a 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 independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms of each other; R ¹⁰ represents a hydrogen atom, a C 1-8 monovalent saturated one a hydrocarbon group or a carbon number 6 to 10 monovalent aromatic hydrocarbon group; R ¹¹ and R ¹² independently of each other represent a hydrogen atom, a carbon number of 1 to 8 one-valent aliphatic hydrocarbon group, a carbon number of 2 to 8 fluorenyl group or tetrahydroanthracene R ¹¹ and R ¹² may be bonded to each other to form a ring containing a nitrogen atom; R ²¹ to R ²⁵ independently of each other represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and R ²⁶ and R ²⁷ are independently represented by each other; Hydrogen atom or methyl]. a compound represented by formula (I): [In the formula (I), R ¹ represents a one-valent saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted by -OH or -COOR ⁸ ; R ² represents -CN or -CONH ₂ ; and R ³ represents a carbon number of 1 to 4; alkyl group; R ⁴ ~ R ⁷ each independently represents ^{-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 ; R ⁸ and R ⁹ independently of each other represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or a carbon number of 6 to 10; The monovalent aromatic hydrocarbon group; R ²¹ to R ²⁵ independently of each other represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and R ²⁶ and R ²⁷ each independently represent a hydrogen atom or a methyl group]. The compound of claim 1 or 2, wherein at least 3 of R ^4a to R ^7a are a hydrogen atom, or at least 3 of R ⁴ to R ⁷ are a hydrogen atom. The compound of claim 1 or 2, wherein R ² is -CN. The compound of claim 1 or 2, wherein R ²⁵ is an alkyl group having 1 to 8 carbon atoms. A dye comprising the compound of claim 1 or 2 as an active ingredient. A colored resin composition containing the dye, resin and solvent of claim 6.