JP2011148993A - Compound - Google Patents

Abstract

【選択図】なしA compound having a high molar extinction coefficient and a high spectral concentration is provided.
A compound represented by formula (0). In formula (0), X ¹ and X ² represent —CO—O— or —O—CO—. L ¹ and L ² represent an alkanediyl group having 1 to 8 carbon atoms. R ¹ represents a hydrogen atom, a methyl group or an ethyl group. R ² represents a hydrogen atom, —CN, or —CONH ₂ .

[Selection figure] None

Description

  The present invention relates to compounds useful as dyes.

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

Industrial Dies Chemistry, Properties, Applications, WILEY-VCH, 2003.

  However, the above known compounds have a low molar extinction coefficient and are not sufficiently satisfactory in terms of spectral concentration.

The present invention provides the following [1] to [6].
[1] A compound represented by the formula (0).

[In Formula (0), X ¹ and X ² each independently represent —CO—O— or —O—CO—.
L ¹ and L ² each independently represent an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a hydrogen atom, a methyl group or an ethyl group.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4a to} R ^7a are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —COR ⁸ , —OCOOR ⁸ , —OCOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, It represents a _{-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 carbon of a benzene ring.
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -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 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ¹¹ and R ¹² may be bonded to each other to form a ring containing a nitrogen atom.
A ⁺ represents a hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms. ]

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

[In Formula (I), X ¹ and X ² each independently represent —CO—O— or —O—CO—.
L ¹ and L ² each independently represent an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a hydrogen atom, a methyl group or an ethyl group.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4 to} R ⁷ are, independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K or —SO _{3. 2} represents NR ⁸ R ⁹
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -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.
A ⁺ represents a hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms. ]

[3] The compound according to [1] or [2] above, wherein X ¹ is * —O—CO— (* represents a bonding position with L ¹ ).
[4] The compound according to any one of the above [1] to [3], wherein R ² is —CN.
[5] A dye comprising the compound according to any one of [1] to [4] as an active ingredient.
[6] A colored resin composition comprising the dye, resin and solvent according to the above [5].

  The compound of the present invention has a high molar extinction 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 tautomers thereof.

[In Formula (0), X ¹ and X ² each independently represent —CO—O— or —O—CO—.
L ¹ and L ² each independently represent an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a hydrogen atom, a methyl group or an ethyl group.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4a to} R ^7a are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —COR ⁸ , —OCOOR ⁸ , —OCOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, It represents a _{-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 carbon of a benzene ring.
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -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 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ¹¹ and R ¹² may be bonded to each other to form a ring containing a nitrogen atom.
A ⁺ represents a hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms. ]

  As the compound of the present invention, a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)) is preferable.

[In Formula (I), X ¹ and X ² each independently represent —CO—O— or —O—CO—.
L ¹ and L ² each independently represent an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a hydrogen atom, a methyl group or an ethyl group.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4 to} R ⁷ are, independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K or —SO _{3. 2} represents NR ⁸ R ⁹
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -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.
A ⁺ represents a hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms. ]

X ¹ and X ² are —CO—O— or —O—CO—, and the bond orientations may be the same or different from each other.
Among these, X ¹ is preferably * —O—CO— (* represents a bond with L ¹ ). It is preferable that X ¹ is * —O—CO— because the compound of the present invention can be easily produced.

L ¹ and L ² are each independently an alkanediyl group having 1 to 8 carbon atoms, preferably an alkanediyl group having 1 to 4 carbon atoms, and an alkanediyl group having 1 to 3 carbon atoms. Are more preferable, and an alkanediyl group having 1 or 2 carbon atoms is more preferable.
Examples of the alkanediyl group having 1 to 8 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, and butane-1 , 3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like.

R ¹ is a hydrogen atom, a methyl group or an ethyl group.

-L ¹ -X ¹ -L ² -X ² -R ¹ is a group having two groups having an ester bond or one ester bond and one carboxyl group. Having such a group is preferable because the solubility in an organic solvent tends to be improved.
The ^{-L 1 -X 1 -L 2 -X 2} -R 1, for example, groups represented by the formula (f-1) ~ formula (f-18) are mentioned.

  Especially, since the group represented by Formula (f-4) and Formula (f-5) is easy to acquire a raw material, it is preferable.

R ² is a hydrogen atom, —CN or —CONH ₂ . Especially, -CN is preferable at the point which is easy to acquire a raw material.

R ³ is a hydrogen atom, 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an N-butyl group, a sec-butyl group, and a tert-butyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As a C1-C4 alkyl group substituted by the halogen atom, a trifluoromethyl group, a pentafluoroethyl group, etc. are mentioned, for example.
R ³ is preferably a methyl group or a trifluoromethyl group, and more preferably a methyl group.

R ^{4a to} R ^7a are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —COR ⁸ , —OCOOR ⁸ , —OCOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, -SO _{3 Na,} -SO _{3 K,} a -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 carbon of a benzene ring.

R ^{4a to} R ^7a are, independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K, —SO ₃ . it is preferably ₂ NR ⁸ R ⁹ or ^-NR 11 ^{R 12.} When R ^{4a to} R ^7a are these groups, it is easy to obtain raw materials.

R ^{4 to} R ⁷ are independently of each other, —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 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. It is a hydrocarbon group, and the hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group, and the aromatic hydrocarbon group may be substituted with —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 ^6a is preferably —R ⁸ or —OR ⁸ , and more preferably a hydrogen atom or a methoxy group.
When R ^6a is a hydrogen atom, R ^5a is preferably —OR ⁸ or —NR ¹¹ R ¹² , and more preferably —OH or —NHCOCH ₃ .

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ⁸ and R ⁹ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. A linear aliphatic hydrocarbon group such as n-heptyl group and n-octyl group;
Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl Group, 1- (1-methylethyl) butyl group, 1- (1-methylethyl) -2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group Group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1- (1-methylethyl) pentyl group, 1-butylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl-3 -Methylbutyl group, 1- (1,1-dimethylethyl) butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3- Dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4- Dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethyl Rupentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1, 1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3- Dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl Group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1 -Propyl-3-methylbutyl group, 1- (1-methylethyl) -1-methylbutyl group, 1- (1-methylethyl) -2-methylbutyl group, 1- (1-methylethyl) -3-methylbutyl group, And branched aliphatic hydrocarbon groups such as 1,1-diethylbutyl group and 1,2-diethylbutyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms in R ⁸ and R ⁹ include a benzyl group, a diphenylmethyl group, a phenylethyl group, and a 3-phenylpropyl group.
Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ⁸ and R ⁹ include aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, and an anthryl group.

Examples of —OR ⁸ in R ^{4a to} R ^7a and R ^{4 to} R ⁷ include a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. , 2-ethylhexyloxy group, phenoxy group, benzyloxy group, benzoyloxy group and the like.
Examples of —OR ⁸ substituted with —OR ¹⁰ include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, 1-ethoxypropyl group, 2-ethoxypropyl group, 1- Ethoxy-1-methylethyl group, 1-methyl-2-ethoxyethyl group, 1- (1-methylethoxy) propyl group, 2- (1-methylethoxy) propyl group, 1- (1-methylethoxy) -1 -Methylethyl group, 2- (1-methylethoxy) -1-methylethyl group, 3-ethoxypropyl group and the like can be mentioned.

Examples of —COOR ⁸ in R ^{4a to} R ^7a and R ^{4 to} R ⁷ include a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group.

Examples of —COR ⁸ in R ^{4a to} R ^7a include an acetyl group, a propionyl group, an isobutyryl group, a valeryl group, and an isovaleryl group.
Examples of —OCOOR ⁸ in R ^{4a to} R ^7a include, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, an n-butoxycarbonyloxy group, an isobutoxycarbonyloxy group, Examples include sec-butoxycarbonyloxy group, n-pentyloxycarbonyloxy group, phenoxycarbonyloxy group and the like.
Examples of —OCOR ⁸ in R ^{4a to} R ^7a include an acetyloxy group and a pivaloyloxy group.

Examples of —NR ¹¹ R ¹² in R ^{4a to} R ^7a include N-methylamino group, N, N-dimethylamino group, N-ethylamino group, N, N-diethylamino group, N-propylamino group, N , N-dipropylamino group, N-butylamino group, N, N-dibutylamino group, N-pentylamino group, N-acetylamino group and the like.
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 a 1-pyrazolyl group, a pyrrolidino group, a piperidino group, and a morpholino group.
Among these, an N-acetylamino group is preferable from the viewpoint of solubility in an organic solvent.

Examples of —SO ₂ NR ⁸ R ⁹ in R ^{4a to} R ^7a and R ^{4 to} R ⁷ include an unsubstituted sulfamoyl group, an N-1 substituted sulfamoyl group, and an N, N-2 substituted sulfamoyl group.
Examples of the N-1-substituted sulfamoyl group include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, and N-butylsulfamoyl group. N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- ( 2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentyl Rufamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1- Methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group An N-1 substituted sulfamoyl group substituted with an aliphatic hydrocarbon group such as a group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N-allylsulfamoyl group;
N- (2-hydroxyethyl) sulfamoyl group, N- (3-hydroxypropyl) sulfamoyl group, N- (2-hydroxypropyl) sulfamoyl group, N- (2,3-dihydroxypropyl) sulfamoyl group, N- (2 -Hydroxybutyl) sulfamoyl group, N- (4-hydroxybutyl) sulfamoyl group, N-substituted sulfamoyl group substituted with an aliphatic hydrocarbon group having a hydroxy group such as N- (1-hydroxymethylethyl) sulfamoyl group ;
N- (2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N-methoxypropylsulfamoyl group, N-ethoxypropylsulfamoyl group N-propoxypropylsulfamoyl group, N-isopropoxypropylsulfamoyl group, N-hexyloxypropylsulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (3-tert- Butoxypropyl) sulfamoyl group, N- (4,4-dimethoxybutyl) sulfamoyl group, N-substituted sulfamoyl group substituted with an alkyl group or cycloalkyl group having an alkoxy group such as N-methoxyhexylsulfamoyl group;
An N-1 substituted sulfamoyl group substituted with an aliphatic hydrocarbon group having an alkoxyalkyl group such as an N- [1- (2-ethoxyethoxy) propyl] sulfamoyl group;
An N-1-substituted sulfamoyl group substituted with an aryl group such as an N-phenylsulfamoyl group and an N- (1-naphthyl) sulfamoyl group;
N-benzylsulfamoyl group, N- (1-phenylethyl) sulfamoyl group, N- (2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl Group, N- [2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) ethyl] sulfamoyl group, N- (3-phenyl-1-propyl) sulfamoyl group, N- ( N-1-substituted sulfamoyl group substituted with an aralkyl group such as 3-phenyl-1-methylpropyl) sulfamoyl group;
N- (3,4,5-trimethoxybenzyl) sulfamoyl group, N- [2- (3,4-dimethoxyphenyl) ethyl] sulfamoyl group, N- [2- (2-ethoxyphenyl) ethyl] sulfamoyl group, etc. N-1 substituted sulfamoyl group substituted with an aralkyl group having the following substituents;

Examples of the N, N-2 substituted sulfamoyl group include N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, and N, N-propylmethyl. Sulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) ) N, N-substituted sulfamoyl group substituted by two aliphatic hydrocarbon groups such as sulfamoyl group, N, N-heptylmethylsulfamoyl group;
N, N-bis (2-hydroxyethyl) sulfamoyl group, N, N-bis (2-methoxyethyl) sulfamoyl group, aliphatic hydrocarbon having substitution such as N, N-bis (2-ethoxyethyl) sulfamoyl group And N, N-2 substituted sulfamoyl group substituted with a group.

R ⁸ and R ⁹ contained in —SO ₂ NR ⁸ R ⁹ include a branched alkyl group having 6 to 8 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, and 2 to 2 carbon atoms. An hydroxy group-containing alkyl group or aryl group having 8 hydroxy groups or an alkoxy group-containing alkyl group or aryl group having 2 to 8 carbon atoms is preferable, and a 2-ethylhexyl group is particularly preferable.

A ⁺ is hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms.
The tetraalkylammonium cation is a quaternary ammonium cation having four alkyl groups, and one alkyl group has 1 to 4 carbon atoms.
Examples of the tetraalkylammonium cation include a tetramethylammonium cation, a tetraethylammonium cation, a tetrabutylammonium cation, and a dimethyldibutylammonium cation, and a tetrabutylammonium cation is preferable.

Examples of compound (0) include compound (I-1) to compound (I-98). Y ^{1 represents} a ^{-L 1 -X 1 -L 2 -X 2} -R 1. In Table 1, the Y ¹ column indicates the number of the group formula exemplified above. n-Bu represents an n-butyl group.

  Especially, since spectral density is high, a compound (I-1)-a compound (I-4) and a compound (I-97) are preferable.

As an example of a method for producing the compound of the present invention, a method for producing compound (I) will be described. Among compounds (0), a compound that is not compound (I) can also be produced by a method similar to the method for producing compound (I) shown below.
Compound (I) can be produced by forming a complex from a compound represented by formula (d) (hereinafter sometimes referred to as “compound (d)”) and a chromium compound.

[In formula (d), R ^{1 to} R ⁷ , L ¹ , L ² , X ¹ and X ² represent the same meaning as in formula (I). ]

First, a method for producing the compound (d) will be described.
The azo compound can be produced by the method described in JP-B-7-88633, diazo coupling of a diazonium salt and a pyridone compound.
The diazonium salt represented by the formula (a2) can be obtained, for example, by diazotizing the amine represented by the formula (a1) with nitrous acid, nitrite or nitrite.

[In formula (a1) and formula (a2), R ^{4 to} R ⁷ represent the same meaning as in formula (I). A ¹ represents an inorganic or 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.
Preferably, chloride ion, bromide _ion, CH 3 COO ^-, and the like.

Compound (d) wherein X ¹ is * —O—CO— (* represents a bond to L ¹ ), that is, a compound represented by formula (d1) (hereinafter referred to as “compound (d1)”) Will be described.

[In formula (d1), R ^{1 to} R ⁷ , L ¹ , L ² and X ² represent the same meaning as in formula (I). ]

  The diazonium salt represented by the formula (a2) and the compound represented by the formula (b1) are subjected to diazo coupling in an aqueous solvent, whereby the compound represented by the formula (c1) (hereinafter referred to as “compound (c1) ) ”May be manufactured. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

[In formula (b1) and formula (c1), R ^{2 to} R ⁷ and L ¹ represent the same meaning as in formula (I). ]

  Next, compound (d1) is obtained by reacting compound (c1) with a compound represented by formula (e1) (hereinafter sometimes referred to as “compound (e1)”) in the presence of an organic solvent. Can do. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

[In formula (e1), R ¹ , L ² and X ² represent the same meaning as in formula (I). Z ¹ represents a chlorine atom or a bromine atom. ]

  Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform, alcohol solvents such as methanol, ethanol and butanol, and nitro hydrocarbon solvents such as nitrobenzene. And ketone solvents such as methyl isobutyl ketone, and amide solvents such as 1-methyl-2-pyrrolidone.

  The amount of compound (b2) to be used is preferably 1 mol or more and 8 mol or less, more preferably 1 mol or more and 4 mol or less, per 1 mol of compound (c1).

Next, compound (d) in which X ¹ is * —CO—O— (* represents a bond to L ¹ ), that is, a compound represented by formula (d2) (hereinafter “compound (d2)”) Will be described.

[In formula (d2), R ^{1 to} R ⁷ , L ¹ , L ² and X ² represent the same meaning as in formula (I). ]

  In the same manner as described above, the diazonium salt represented by the formula (a2) and the compound represented by the formula (b2) are subjected to diazo coupling in an aqueous solvent, whereby the compound represented by the formula (c2) ( Hereinafter, it may be referred to as “compound (c2)”. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include the same solvents as mentioned above.

[In formula (b2) and formula (c2), R ^{2 to} R ⁷ and L ¹ represent the same meaning as in formula (I). ]

Next, the compound (d2) is obtained by reacting the compound (c2) with the compound represented by the formula (e2) (hereinafter sometimes referred to as “compound (b4)”) in the presence of an organic solvent. Can do. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.
R ¹ —X ² —L ² —OH (e2)
[In formula (b4), R ¹ , X ² and L ² represent the same meaning as in formula (I). ]
Examples of the organic solvent used here include the same solvents as those used in the reaction between the compound (c1) and the compound (e1).

  The amount of compound (e2) to be used is preferably 1 to 8 mol, more preferably 1 to 4 mol, per 1 mol of compound (c2).

In the reaction, it is more preferable to add an acidic catalyst so that the reaction proceeds smoothly.
Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.
Although the usage-amount of these catalysts is arbitrary, Preferably it is 0.01 mol or more and 4 mol or less with respect to 1 mol of compounds (e2), More preferably, it is 0.8-2 mol.

  The method for obtaining the target compound (d) (that is, the compound (d1) or the compound (d2)) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, the reaction mixture is preferably mixed with an acid (for example, acetic acid and the like) and water, and the precipitated crystals are collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 50 ° C. or lower, and further preferably 20 ° C. or higher and 30 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  Compound (I) is preferably a compound (d) and a chromium compound in an aqueous solvent (eg, N, N-dimethylformamide, N-methylpyrrolidone, etc.), preferably 70 to 150 ° C. (more preferably 70 to 130 ° C.). ) And reacting for 3 to 10 hours.

Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, chromium fluoride, ammonium sulfate chromium, and preferably chromium formate, ammonium sulfate, and the like.
It is preferable that the usage-amount of a chromium compound is 0.5-1 mol with respect to 1 mol of compounds (d).

  In order to promote the reaction, an inorganic base can be present together.

  Examples of the inorganic base include sodium hydroxide, calcium hydroxide, sodium carbonate, calcium carbonate, sodium acetate, calcium acetate and the like, preferably sodium carbonate and sodium acetate.

  The method for obtaining the target compound (I) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, it is preferable that the reaction mixture is mixed with an inorganic salt (for example, sodium chloride) and water, and the precipitated crystals are collected by filtration. The inorganic salt is preferably prepared by preparing an aqueous solution of an inorganic salt in advance and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is 10 ° C. or higher and 50 ° C. or lower, preferably 10 ° C. or higher and 40 ° C. or lower, preferably 10 ° C. or higher and 25 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an inorganic salt, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The compound of the present invention thus obtained is useful as a dye. In particular, since the compound of the present invention has a high spectral density, it is useful as a dye used for color filters, fiber materials, etc. of display devices such as liquid crystal display devices that display colors 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).

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.
As dyes different from the dyes of the present invention, the Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, reactive, direct And dyes classified as (Direct), Disperse, or Vat. More specifically, dyes having the following color index (CI) numbers can be mentioned, but the dye is not limited thereto.
C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54,76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Green 1,5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

  Examples of the pigment include organic pigments and inorganic pigments usually used for pigment dispersion resists. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and other metal compounds. Oxides or mixed metal oxides may be mentioned. Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment under the Color Index (published by The Society of Dyers and Colorists). More specifically, pigments having the following color index (CI) numbers can be mentioned, but the invention is not limited to these.

C. I. 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;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment Green 7, 10, 15, 25, 36, 47 and 58 etc.

The content of the colorant (A) is preferably 5 to 60% by mass with respect to the solid content in the colored resin composition. Here, solid content means the sum total of the component except a solvent in a colored resin composition.
The content of the dye of the present invention contained in the colorant (A) is preferably 3 to 100% by mass.
Dyes and pigments different from the dye of the present invention may be used alone or in combination of two or more with the dye of the present invention.

  The resin (B) is not particularly limited, and any resin may 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 represents 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 / isobornyl methacrylate copolymer, methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, and the like.

The weight average molecular weight in terms of polystyrene 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.
Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a colored resin composition, More preferably, it is 13-60 mass%.

  The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical, an acid, or the like generated from the polymerization initiator (D). For example, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned.

The polymerizable compound (C) is preferably a photopolymerizable compound having 3 or more polymerizable groups. Examples of the photopolymerizable compound having 3 or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Is mentioned. The photopolymerizable compounds (C) may be used alone or in combination of two or more.
It is preferable that content of a polymeric compound (C) is 5-65 mass% with respect to solid content of a colored resin composition, More preferably, it is 10-60 mass%.

As said polymerization initiator (D), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by the action of heat or light. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.
Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Examples include benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine and the like.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.
The polymerization initiators (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, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator 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, amides, and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 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 ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and cyclopentanone. And cyclohexanone.
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, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Chill, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ -Butyrolactone etc. are mentioned.

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Content of the solvent (E) in a colored resin composition becomes like this. Preferably it is 70-95 mass% with respect to a colored resin composition, More preferably, it is 75-90 mass%.

  The colored resin composition of the present invention can be used in various ways such as surfactants, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc. An additive may be included.

The compounds of the present invention are useful as dyes. In addition, since the compound of the present invention has a high molar extinction coefficient and a high spectral density, it is particularly useful as a dye for use in a color filter of a display device such as a liquid crystal display device.
In addition, the colored resin composition containing the compound of the present invention has various colors such as a display device (for example, a known liquid crystal display device or an organic EL device) having a color filter as a part of its constituent parts, a solid-state imaging device, or the like. It can be used in a known manner for devices related to images.

Next, the present invention will be described more specifically with reference to examples.
In Examples and Comparative Examples,% and part representing content or amount used are based on mass unless otherwise specified.

  In the following examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) and mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[Example 1]
After adding 80 parts of water to 13.7 parts of anthranilic 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 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  On the other hand, 26.0 parts of acetoacetic acid ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 24.4 parts of 2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) The parts were mixed and stirred at 95 ° C. for 24 hours. The reaction solution was cooled to room temperature, 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 crystals were obtained as a residue of a suction filter and dried to obtain 20.4 parts of a compound represented by the formula (b1a).

  Subsequently, 20.4 parts of the compound represented by the formula (b1a) were suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 33.5 parts of a compound represented by the formula (c1a).

Next, 27.28 parts of the acid chloride represented by the formula (e1a) was added to 34.2 parts of the compound represented by (c1a), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 42.35 parts of a compound represented by the formula (d1a). ^The structure was confirmed by ¹ H-NMR.

Identification of compound represented by formula (d1a)
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.05 (3H, s), 2.57 (3H, s), 4.13 (2H, t), 4 .31 (2H, t), 4.57 (2H, s), 7.38 (1H, t), 7.76 (1H, t), 8.02 (1H, d), 8.04 (1H, d), 15.7 (1H, s).

  Next, after adding 50 parts of N-methylpyrrolidone to 2.0 parts of the compound represented by the formula (d1a) and heating to 80 ° C. to dissolve, chromium formate n hydrate (manufactured by Nacalai Tesque) 1.2 parts were added and stirred at 120 ° C. for about 7 hours to obtain a dark orange solution. This solution was poured into 300 parts of a 20% saline solution, and the resulting orange solid was filtered and dried at 60 ° C. under vacuum to obtain 1.6 parts of a compound represented by the formula (I-1) 76%).

Identification of compound represented by formula (I-1) (mass spectrometry) ionization mode = ESI−: m / z = 932.2 [M−H] ⁻
Exact Mass: 933.1

[Example 2]
A compound represented by the formula (d1b) was obtained in the same manner as in Example 1 except that the acid chloride represented by the formula (e1a) was replaced with the acid chloride represented by the formula (e1b). ^The structure was confirmed by ¹ H-NMR. ^The structure was confirmed by ¹ H-NMR.

Identification of compound represented by formula (d1b)
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.50 (2H, 2H, overlapped) 2.55 (3H, s), 3.51 (3H, s), 4.11 (2H, t), 4.23 (2H, t), 7.37 (1H, t), 7.74 (1H, t), 8.02 (1H, d), 8.03 (1H , D), 15.6 (1H, s).

  Next, 93 parts of N-methylpyrrolidone is added to 3.7 parts of the compound represented by the formula (d1b), heated to 80 ° C. and dissolved, and then 1.8 parts of chromium formate n hydrate is added to 120 parts. Stir at about 7 hours for a dark orange solution. This solution was poured into 210 parts of a 20% saline solution, and the resulting orange solid was filtered and dried under vacuum at 60 ° C., whereby 3.2 parts of the compound represented by the formula (I-2) ( Yield 82%).

Identification of compound represented by formula (f-2) (mass spectrometry) ionization mode = ESI−: m / z = 960.0 [M−H] ⁻
Exact Mass: 961.2

Example 3
After adding 100 parts of water to 5.5 parts of 2-amino-4,5-dimethoxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.2 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 6.1 parts of sodium nitrite was added, and then 23.1 parts of 35% hydrochloric acid was added little by little. Thereafter, the mixture was stirred for 2.5 hours under ice cooling, and 70 parts of a 9% amidosulfuric acid aqueous solution was slowly added to quench excess nitrous acid, followed by stirring for about 10 minutes to obtain a suspension containing a diazonium salt.

  Next, 5.9 parts of the compound represented by the formula (b1a) was suspended in 53 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. Here, the suspension containing the diazonium salt was dropped with a pump over about 1 hour while maintaining the pH of the suspension at 7.5 to 9.0. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours to obtain a red-orange suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 9.3 parts of the compound represented by the formula (c1c).

Next, 3.1 parts of acid chloride (e1b) was added to 4.2 parts of the compound represented by the formula (c1c), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 4.9 parts of a pyridone azo compound (d1c) represented by the following structure. ^The structure was confirmed by ¹ H-NMR. ^The structure was confirmed by ¹ H-NMR.

Identification of compound represented by formula (d1c)
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.50-2.52 (2H, 2H, overlapped), 2.56 (3H, t), 3.52 ( 3H, s), 3.83 (3H, s), 3.93 (3H, s), 4.11 (2H, t), 4.23 (2H, t), 7.43 (1H, s), 7.48 (1H, s), 15.7 (1H, s).

Next, 120 parts of N-methylpyrrolidone is added to 11.0 parts of the compound represented by the formula (d1c) and heated to 80 ° C. to dissolve, and then 1.0 part of chromium formate n hydrate is added to 110 parts. Stir at about 0 ° C. for about 1 hour. The temperature was then lowered to 80 ° C., 2.3 parts of sodium carbonate was added, and the mixture was again stirred at 110 ° C. for about 3.5 hours to obtain a dark orange solution. This solution was poured into 530 parts of a 10% saline solution, and the resulting orange solid was filtered and dried under vacuum at 60 ° C. to obtain a compound represented by the formula (I-3) (yield 65%). Of 7.6 parts.

Identification of compound represented by formula (I-3) (mass spectrometry) ionization mode = ESI−: m / z = 1080.2 [M−Na] ⁻
Exact Mass: 1103.2

Example 4
After 90 parts of water was added to 5.5 parts of 2-amino-5-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.9 parts of sodium hydroxide was added and dissolved. Under ice cooling, 8.0 parts of sodium nitrite was added, and then 29.7 parts of 35% hydrochloric acid was added little by little. Thereafter, the mixture was stirred for 2 hours under ice-cooling, and 87 parts of 9% amidosulfuric acid aqueous solution was slowly added to quench excess nitrous acid, followed by stirring for about 10 minutes to obtain a suspension containing a diazonium salt.

Next, 7.6 parts of the compound represented by the formula (b1a) was suspended in 68.6 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. Here, the suspension containing the diazonium salt was dropped by a pump over about 1 hour while maintaining the pH of the suspension at 1.0 or lower. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours to obtain an orange suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 9.3 parts of a compound represented by the formula (c1d). ^The structure was confirmed by ¹ H-NMR.

Identification of compound represented by formula (c1d)
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.44 (3H, s), 3.52 (2H, d), 3.90 (2H, t), 4 .92 (1H, brs), 7.09 (1H, dd), 7.34 (1H, d), 7.76 (1H, d), 10.1 (1H, s), 15.5 (1H, s).

Next, 4.4 parts of acid chloride (e1b) was added to 4.2 parts of the compound represented by (c1d), and the mixture was stirred at 70 ° C. for 3 hours in a solvent of N-methylpyrrolidone. After completion of the reaction, the reaction mixture was charged in water to obtain 4.6 parts of a compound represented by the formula (d1d). ^The structure was confirmed by ¹ H-NMR.

Identification of compound represented by formula (d1d)
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.48-2.51 (2H, 2H, 3H, overlapped), 3.52 (3H, s) 10 (2H, t), 4.22 (2H, t), 7.12 (1H, dd), 7.37 (1H, d), 7.82 (1H, d), 10.2 (1H, s) ), 15.6 (1H, s).

Next, 98 parts of N-methylpyrrolidone is added to 6.5 parts of the compound represented by the formula (d1d), heated to 80 ° C. and dissolved, and then 1.6 parts of chromium formate n hydrate is added to add 110 parts. Stir at about 0 ° C. for about 1 hour. The temperature was then lowered to 80 ° C., 2 parts of sodium carbonate was added, and the mixture was stirred again at 110 ° C. for about 5 hours to obtain a dark orange solution. This solution was poured into 330 parts of a 20% saline solution, and the resulting orange solid was filtered and dried under vacuum at 60 ° C., whereby 4.1 parts of the compound represented by the formula (I-4) ( Yield 59%).

Identification of compound represented by formula (I-4) (mass spectrometry) ionization mode = ESI−: m / z = 992.2 [M−Na] ⁻
Exact Mass: 1015.2

Example 5
After adding 80 parts of water to 19.4 parts of 5- (N-acetylamino) anthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.
Subsequently, 20.4 parts of the compound represented by the formula (b1a) were suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 39.1 parts of a compound represented by the formula (c1e).

Next, 30.1 parts of acid chloride (Wako Pure Chemical Industries, Ltd.) represented by the formula (e1b) is added to 39.9 parts of the compound represented by the formula (c1e), and in N-methylpyrrolidone, Stir at 70 ° C. for 3 hours. After completion of the reaction, the reaction mixture was charged in water to obtain 50.1 parts of a compound represented by the formula (d1e). The obtained compound was orange and the maximum absorption wavelength (λmax) was measured in an ethyl lactate solvent to show 459 nm. The structure was confirmed by ¹ H-NMR.
¹ H-NMR: 1.05 (3H, m), 2.06 (3H, s), 2.37 (2H, t), 2.40 (2H, t), 2.48 (3H, m), 3.83 (2H, m), 3.91 (2H , m), 5.08 (2H, m), 7.88 (1H, s), 7.89 (1H, s), 8.29 (1H, m), 10.2 (1H, d)

  Next, 98 parts of N-methylpyrrolidone is added to 7.0 parts of the compound represented by the formula (d1e) and heated to 80 ° C. to dissolve, and then 1.6 parts of chromium formate n hydrate is added to add 110 parts. Stir at about 0 ° C. for about 1 hour. The temperature was then lowered to 80 ° C., 2 parts of sodium carbonate was added, and the mixture was stirred again at 110 ° C. for about 5 hours to obtain a dark orange solution. This solution was poured into 330 parts of a 20% saline solution, and the resulting orange solid was filtered and dried under vacuum at 60 ° C. to obtain 2.7 parts of the compound represented by the formula (I-97) ( Yield 40%).

Identification of compound represented by formula (I-97) (mass spectrometry) ionization mode = ESI−: m / z = 1074.2 [M-Na] ⁻
Exact Mass: 1097.2

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

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

Example 6
<Preparation of colored resin composition>
(A) Colorant: Compound (I-1): Compound synthesized in Example 1 20 parts (B-1) Resin: Methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, Acid value 70 mg KOH / g) 70 parts (C-1) polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 30 parts (D-1) photopolymerization initiator: benzyl dimethyl ketal (Irgacure 651; BASF Japan) 15 parts (E-1) solvent: 680 parts of ethyl lactate are mixed to obtain a colored resin composition.

<Preparation of color filter>
On the glass, the colored resin composition obtained above is applied by a spin coating method to volatilize volatile components. After cooling, light irradiation is performed using a quartz glass photomask having a pattern and an exposure machine. After light irradiation, development is performed with an aqueous potassium hydroxide solution, and the color filter is obtained by heating to 200 ° C. in an oven.

Example 7
A colored resin composition and a color filter are obtained in the same manner as in Example 6 except that the compound (I-1) synthesized in Example 1 is replaced with the compound (I-2) synthesized in Example 2.

Example 8
A colored resin composition and a color filter are obtained in the same manner as in Example 6 except that the compound (I-1) synthesized in Example 1 is replaced with the compound (I-3) synthesized in Example 3.

Example 9
A colored resin composition and a color filter are obtained in the same manner as in Example 6 except that the compound (I-1) synthesized in Example 1 is replaced with the compound (I-4) synthesized in Example 4.

Example 10
A colored resin composition and a color filter are obtained in the same manner as in Example 6 except that the compound (I-1) synthesized in Example 1 is replaced with the compound (I-97) synthesized in Example 5.

  From the results in Table 2, it can be seen that the compound of the present invention has a high absorbance because of its high absorbance. In addition, the colored resin composition containing the compound has excellent color performance and can produce a high-quality color filter.

  The compounds of the present invention are useful as dyes. Since the compound of the present invention has a high molar extinction coefficient and a high spectral density, it is particularly useful as a dye for use in a color filter of a display device such as a liquid crystal display device.

Claims (6)

Compound represented by formula (0).

[In Formula (0), X ¹ and X ² each independently represent —CO—O— or —O—CO—.
L ¹ and L ² each independently represent an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a hydrogen atom, a methyl group or an ethyl group.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4a to} R ^7a are independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —COR ⁸ , —OCOOR ⁸ , —OCOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, It represents a _{-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 carbon of a benzene ring.
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -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 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ¹¹ and R ¹² may be bonded to each other to form a ring containing a nitrogen atom.
A ⁺ represents a hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms. ] A compound represented by formula (I).

[In Formula (I), X ¹ and X ² each independently represent —CO—O— or —O—CO—.
L ¹ and L ² each independently represent an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a hydrogen atom, a methyl group or an ethyl group.
R ² represents a hydrogen atom, —CN, or —CONH ₂ .
R ³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ^{4 to} R ⁷ are, independently of each other, —R ⁸ , —OR ⁸ , —COOR ⁸ , —CN, —NO ₂ , a halogen atom, —SO ₃ H, —SO ₃ Na, —SO ₃ K or —SO _{3. 2} represents NR ⁸ R ⁹
R ⁸ and R ⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with -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.
A ⁺ represents a hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms. ] The compound according to claim ¹ , wherein X ¹ is * —O—CO— (* represents a bonding position with L ¹ ). R ² is A compound according to claim 1 is -CN.   The dye which uses the compound in any one of Claims 1-4 as an active ingredient.   A colored resin composition comprising the dye, resin and solvent according to claim 5.