KR101967823B1 - Pyridone complex compounds - Google Patents

Abstract

A colored resin composition comprising a pyridone complex compound, a dye containing a pyridone complex compound as an active ingredient, and a dye containing a pyridone complex compound as an active ingredient, a resin and a solvent.

Description

PYRIDONE COMPLEX COMPOUNDS < RTI ID = 0.0 >

The present invention relates to compounds useful as dyes.

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

[Non-Patent Document 1]

Industriale Dyes Chemistry, Properties, Applications, WILEY-VCH, 2003.

However, conventionally known compounds as described above have a small molar absorptivity and can not sufficiently satisfy the spectral concentration.

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

[1] A compound represented by the formula (O).

[In the formula (O), X ¹ and X ² independently represent -CO-O- or -O-CO-.

L ¹ and L ² 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 group.

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 independently represent -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, -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 combine with each other to form a 6- to 7-membered ring containing a carbon of a benzene ring.

R ⁸ and R ⁹ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the aliphatic hydrocarbon group , The hydrogen atom contained in 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 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 combine with each other to form a ring containing a nitrogen atom.

A ⁺ represents a hydronone, sodium cation, potassium cation or tetraalkylammonium cation of 1 to 4 carbon atoms.

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

[In the formula (I), X ¹ and X ² independently represent -CO-O- or -O-CO-.

L ¹ and L ² 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 group.

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 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 .

R ⁸ and R ⁹ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the aliphatic hydrocarbon group , The hydrogen atom contained in 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 hydronone, sodium cation, potassium cation or tetraalkylammonium cation of 1 to 4 carbon atoms.

[3] The compound according to [1] or [2], wherein X ¹ represents * -O-CO- (* represents a bonding position to L ¹ ).

[4] The compound according to any one of [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, the resin and the solvent according to [5].

The compound of the present invention is a compound represented by formula (O) [hereinafter sometimes referred to as compound (O)). The compound of the present invention also includes tautomers thereof.

[In the formula (O), X ¹ and X ² independently represent -CO-O- or -O-CO-.

L ¹ and L ² 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 group.

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 independently represent -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, -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 combine with each other to form a 6- to 7-membered ring containing a carbon of a benzene ring.

R ⁸ and R ⁹ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the aliphatic hydrocarbon group , The hydrogen atom contained in 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 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 combine with each other to form a ring containing a nitrogen atom.

A ⁺ represents a hydronone, sodium cation, potassium cation or tetraalkylammonium cation of 1 to 4 carbon atoms.

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

[In the formula (I), X ¹ and X ² independently represent -CO-O- or -O-CO-.

L ¹ and L ² 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 group.

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 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 .

R ⁸ and R ⁹ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the aliphatic hydrocarbon group , The hydrogen atom contained in 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 hydronone, sodium cation, potassium cation or tetraalkylammonium cation of 1 to 4 carbon atoms.

X ¹ and X ² are -CO-O- or -O-CO-, and the bonding direction may be the same or different.

Among them, X ¹ is preferably * -O-CO- (* represents a bond with L ¹ ). When X < ^{1 >} is * -O-CO-, it is preferable because the preparation of the compound of the present invention is easy.

Each of L ¹ and L ² independently of each other is an alkanediyl group having 1 to 8 carbon atoms, preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms, Or 2 is an alkanediyl group.

Examples of the alkanediyl group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane- , A 3-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group and an octane-1,8-diyl group.

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

-L ¹ -X ¹ -L ² -X ² -R ¹ is a group having two ester bonds or a group having one ester bond and one carboxyl group. Having such a group tends to improve solubility in an organic solvent, which is preferable.

Examples of -L ¹ -X ¹ -L ² -X ² -R ¹ include groups represented by formulas (f-1) to (f-18).

Among them, groups represented by the formulas (f-4) and (f-5) are preferable because the raw materials are easily obtained.

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

R ³ is a hydrogen atom or 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.

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

As R ³ , a methyl group and a trifluoromethyl group are preferable, and a methyl group is particularly preferable.

R ^4a to R ^7a independently represent -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,} -SO 2 NR 8 R 9 Or a -NR ¹² R ^ll. R ^4a and R ^5a , R ^5a and R ^6a and R ^6a and R ^7a may combine with each other to form a 6- to 7-membered ring containing a carbon of a benzene ring.

R ^4a to R ^7a 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 preferably an -NR ¹² R ^ll.

R ⁴ to R ⁷ independently represent -R ⁸ , -OR ⁸ , -COOR ⁸ , -CN, -NO ₂ , a halogen atom, -SO ₃ H, -SO ₃ Na, -SO ₃ K, or it is -SO ₂ NR ⁸ R ^9.

R ⁸ and R ⁹ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the aliphatic hydrocarbon group , The hydrogen atom contained in 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 -R ⁸ Or -OR ⁸ , more preferably a hydrogen atom or a methoxy group.

When R ^6a is a hydrogen atom, R ^5a is -OR ⁸ Or -NR ¹¹ R ¹² , 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, A straight chain aliphatic hydrocarbon group such as a heptyl group and an n-octyl group;

A methylpentyl group, a 4-methylpentyl group, a 1-ethylbutyl group, a 2-ethylpentyl group, an isobutyl group, an isobutyl group, an isopentyl group, Propylphenyl group, 3-ethylpentyl group, 3-methylpentyl group, 3-methylpentyl group, 3-methylpentyl group, 3-methylpentyl group, Methylpropyl group, a 1-methylbutyl group, a 2-methylheptyl group, a 3-methylheptyl group, a 1- , 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, Methylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl-3-methylbutyl group, 1- (1,1- Dimethylbutyl, tert-butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethyl Butyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, Ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl- 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, Ethylhexylmethylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-2-methylpentyl group, Ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl- Methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, Propyl-2-methylbutyl group, 1- (1-methylethyl) -1-methylbutyl group, 1- Group, branched chain aliphatic hydrocarbon groups such as a 1- (1-methylethyl) -3-methylbutyl group, a 1,1-diethylbutyl group and a 1,2-diethylbutyl group; And the like.

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 an aromatic hydrocarbon group 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 hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group , Octyloxy group, 2-ethylhexyloxy group, phenoxy group, benzyloxy group, benzoyloxy group and the like.

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

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 a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, an n- An isobutoxycarbonyloxy group, a sec-butoxycarbonyloxy group, an n-pentyloxycarbonyloxy group, and a phenoxycarbonyloxy group.

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-dipropylamino group, N-butylamino group, N, N-dibutylamino group, N-pentylamino group and N-acetylamino group.

R ¹¹ And -NR ¹¹ R ^{12 in} which R ¹² is bonded to each other to form a ring containing a nitrogen atom include, for example, a 1-pyrazolyl group, a pyrrolidino group, a piperidino group and a morpholino group.

Among them, an N-acetylamino group is preferable in view of solubility in an organic solvent.

Examples of R ^4a ~R ^7a and R ⁴ -SO ₂ NR ⁸ R ⁹ in ~R ^7, a non-substituted sulfamoyl group may be mentioned, N-1 substituted sulfamoyl and 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, N-butylsulfamoyl group, N Butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1 N- (2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl 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- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N- N-allyl sulfamoyl group and the like Substituted N-1 substituted hydrocarbon group bangjok sulfamoyl group;

(3-hydroxypropyl) sulfamoyl group, N- (2-hydroxypropyl) sulfamoyl group, N- (2,3-dihydroxypropyl) sulfamoyl group, N- ) Having a hydroxy group such as a sulfamoyl group, an N- (2-hydroxybutyl) sulfamoyl group, an N- (4-hydroxybutyl) sulfamoyl group and an N- (1-hydroxymethylethyl) sulfamoyl group. An N-1 substituted sulfamoyl group substituted with an aliphatic hydrocarbon group;

(Methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- An N-isopropoxypropylsulfamoyl group, an N-hexyloxypropylsulfamoyl group, an N- (2-ethylhexyloxypropyl) sulfamoyl group, an N- An alkyl group having an alkoxy group such as N- (3-tert-butoxypropyl) sulfamoyl group, N- (4,4-dimethoxybutyl) sulfamoyl group, N-methoxyhexylsulfamoyl group, etc. or cycloalkyl group- N-1 substituted sulfamoyl group;

An N-1 substituted sulfamoyl group substituted with an aliphatic hydrocarbon group having an alkoxyalkyl group such as N- [1- (2-ethoxyethoxy) propyl] sulfamoyl group;

An N-1 substituted pamoyl group substituted with an aryl group such as an N-phenylsulfamoyl group and an N- (1-naphthyl) sulfamoyl group;

(2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl group, N- ) Sulfamoyl group, N- (2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) An N-1 substituted sulfamoyl group substituted with an aralkyl group such as a pamoyl group and N- (3-phenyl-1-methylpropyl) sulfamoyl group;

N- [2- (3,4-dimethoxyphenyl) ethyl] sulfamoyl group, N- [2- (2-ethoxyphenyl) Ethyl] sulfamoyl group and the like; an N-1 substituted sulfamoyl group substituted with an aralkyl group having a substituent group;

Examples of the N, N-2 substituted sulfamoyl group include N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, An N, N-substituted sulfamoyl group substituted with two aliphatic hydrocarbon groups such as a methyl group, a N, N-heptylmethylsulfamoyl group and the like;

Substitution of N, N-bis (2-hydroxyethyl) sulfamoyl group, N, N-bis (2-methoxyethyl) sulfamoyl group, N, N-bis (2-ethoxyethyl) sulfamoyl group and the like And an N, N-2-substituted sulfamoyl group substituted by an aliphatic hydrocarbon group having a substituent.

Examples of R ⁸ and R ⁹ contained in -SO ₂ NR ⁸ R ⁹ include a branched chain alkyl group having 6 to 8 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, an alkyl group having 2 to 8 carbon atoms Or an aryl group, or an alkyl group or aryl group containing an alkoxy group having 2 to 8 carbon atoms, and particularly preferably a 2-ethylhexyl group.

A ⁺ is a hydron, sodium cation, potassium cation or tetraalkylammonium cation with 1 to 4 carbon atoms.

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

Examples of the tetraalkylammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, dimethyldibutylammonium cation and the like, preferably tetrabutylammonium cation to be.

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

Of these, compounds (I-1) to (I-4) and (I-97) are preferred because of their high spectral density.

 As a method for producing the compound of the present invention, a method for producing the compound (I) will be described. Compounds other than the compound (I) in the compound (O) can also be produced by the same method as the method for producing the compound (I) shown below.

Compound (I) can be produced by forming a complex with 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 have the same meanings 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 Japanese Examined Patent Publication No. 7-88633, or diazonium coupling of a diazonium salt and a pyridone compound.

The diazonium salt represented by the formula (a2) can be obtained, for example, by diazotizing an amine represented by the formula (a1) with a nitrite, a nitrite or a nitrite ester.

[In formulas (a1) and (a2), R ⁴ to R ⁷ have the same meanings as in formula (I). A ¹ represents an inorganic or organic anion.]

Examples of the inorganic anion include a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a perchlorate ion, a hypochlorite ion, and the like.

Examples of the organic anions include CH ₃ COO ^- , C ₆ H ₅ COO ^- and the like.

Preferable examples thereof include chloride ion, bromide ion, CH ₃ COO ^- and the like.

(D1) (hereinafter sometimes referred to as "compound (d1)") in which X ¹ is * -O-CO-, wherein * represents a bond with L ¹ , The manufacturing method will be described.

[In formula (d1), R ¹ to R ⁷ , L ¹ , L ² and X ² have the same meanings as in formula (I).]

The diazonium salt represented by the formula (a2) and the compound represented by the formula (b1) are diazotically coupled in an aqueous solvent to give a compound represented by the formula (c1) [hereinafter referred to as "the compound (c1)") Can 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 the formulas (b1) and (c1), R ² to R ⁷ And L < ¹ > have the same meanings as in formula (I).

Subsequently, the compound (d1) can be obtained by reacting the compound (c1) with a compound represented by the formula (e1) [hereinafter referred to as "compound (e1)") in the presence of an organic solvent. The reaction temperature is preferably 30 占 폚 to 180 占 폚, more preferably 50 占 폚 to 120 占 폚. 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 have the same meanings 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; nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as butyl ketone, and amide solvents such as 1-methyl-2-pyrrolidone.

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

Next, the case where the compound (d) wherein X ¹ is * -CO-O- (* represents a bond with L ¹ ), that is, the compound represented by the formula (d2) Will be described.

[In formula (d2), R ¹ to R ⁷ , L ¹ , L ² and X ² have the same meanings as in formula (I).]

Compound (c2) (hereinafter referred to as " compound (c2) ") may be obtained by diazotizing a diazonium salt represented by formula (a2) and a compound represented by formula There may be cases where the " 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. As the above-mentioned aqueous solvent, the same solvents as those exemplified above can be mentioned.

In the formulas (b2) and (c2), R ² to R ⁷ and L ¹ have the same meanings as in formula (I).

Subsequently, the compound (d2) can be obtained by reacting the compound (c2) with a compound represented by the formula (e2) (hereinafter sometimes referred to as "compound (b4)") in the presence of an organic solvent. The reaction temperature is preferably 30 占 폚 to 180 占 폚, more preferably 50 占 폚 to 120 占 폚. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

[In formula (b4), R ¹ , X ² and L ² have the same meanings as in formula (I).]

Examples of the organic solvent used herein include the same solvents as those used in the reaction of the compound (c1) and the compound (e1).

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

In the course of the reaction, it is more preferable to add an acidic catalyst in order to proceed the reaction smoothly. Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.

The amount of these catalysts to be used is arbitrary, but is preferably 0.01 mol or more and 4 mol or less, more preferably 0.8 to 2 mol, based on 1 mol of the compound (e2).

The method of obtaining the desired compound (d) (i.e., the compound (d1) or the compound (d2)) from the reaction mixture is not particularly limited and various known methods can be employed. For example, it is preferable that the reaction mixture is mixed with an acid (e.g., acetic acid etc.) and water, and the precipitated crystals are collected by filtration. It is preferable that the acid is prepared by preparing an aqueous solution of an acid in advance and then adding the reaction mixture to the aqueous solution. The temperature at the time of adding the reaction mixture is preferably from 10 캜 to 50 캜, more preferably from 20 캜 to 50 캜, further preferably from 20 캜 to 30 캜. Further, after the reaction mixture is added to the aqueous solution of the acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known method such as recrystallization.

The compound (I) can be produced by reacting the compound (d) and the chromium compound in an aqueous solvent (for example, N, N-dimethylformamide, N-methylpyrrolidone, etc.) , And the reaction is carried out for 3 to 10 hours.

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

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

In order to accelerate the reaction, an inorganic base may be coexistent.

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

The method for obtaining the desired compound (I) from the reaction mixture is not particularly limited and various known methods can be employed. For example, it is preferable that the reaction mixture is mixed with an inorganic salt (e.g., salt, etc.) and water, and the precipitated crystals are collected by filtration. It is preferable that the inorganic salt is 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 more and 50 ° C or less, preferably 10 ° C or more and 40 ° C or less, preferably 10 ° C or more and 25 ° C or less. Further, after the reaction mixture is added to the aqueous solution of the inorganic salt, stirring is preferably carried out at the same temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known method such as recrystallization.

The compound of the present invention thus obtained is useful as a dye. In particular, the compounds of the present invention are useful as dyes for use in color filters and fiber materials of display devices such as liquid crystal displays that display color by using reflected or transmitted light because of their high spectral density.

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

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

As the dyes other than the dyes of the present invention, there may be mentioned dyes such as Solvent, Acid, Basic, Reactive, Direct in the Color Index (published by The Society of Dyers and Colourists) ), Disperse, or Vat. [0043] The term " dye " More specifically, the dyes of the following color index (C.I.) numbers are exemplified, but are 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 1st.

As the pigment, an organic pigment or an inorganic pigment usually used for a pigment-dispersed resist can be mentioned. Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specific examples thereof include oxides or complexes of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, Metal oxides. Specific examples of organic pigments and inorganic pigments include compounds classified in Pigment in the Color Index (published by The Society of Dyers and Co-Investors). More specifically, pigments having the following color index (C.I.) numbers can be mentioned, but the present invention is not limited thereto.

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 and the like.

The content of the colorant (A) is preferably 5 to 60 mass% with respect to the solid content in the colored resin composition. Here, the solid content refers to the sum of components excluding the solvent in the colored resin composition.

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

The dyes and pigments which are different from the dyes of the present invention may be used alone or in combination with two or more kinds of dyes 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, 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 of the resin (B) in terms of polystyrene is preferably 5,000 to 35,000, and 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 mass%, more preferably from 13 to 60 mass%, based on the solid content of the colored resin composition.

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

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

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 an active radical generator and an acid generator. The active radical generator generates 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- -1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan- .

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propoxyoctanoate 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- Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] -1,3 , 5-triazine, and the like.

Examples of the above oxime compounds include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one- N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy- 1- [ Yl] ethan-1-imine, N-acetoxy-1- [9-ethyl- 6- {2- methyl- 4- (3,3- Benzoyl} -9H-carbazol-3-yl] ethan-1-imine.

Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphaquinone, methyl phenylglyoxylate, Or the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- Triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluene, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- Onium salts such as diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate and the like, nitrobenzyltosylates, benzoin tosylates and the like.

The above-mentioned 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 by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator is in the above-mentioned range, it is preferable because a high sensitivity is obtained and 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 ethers such as tetrahydrofuran, tetrahydropyrane, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Ethylene 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 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 monoethyl ether acetate, diethylene glycol monoethyl ether acetate, And a monobutyl ether acetate.

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

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl- - 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, ethyl butyrate, butyl esters, alkyl esters , Methyl lactate, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxy Ethyl acetate, and 3-methyl-3-methoxybutyl acetate, butyl γ- lactone ol.

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

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

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

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

The compounds of the present invention are useful as dyes. The compound of the present invention is useful as a dye used in a color filter of a display device such as a liquid crystal display device because of its high molar extinction coefficient and high spectral density.

The colored resin composition of the present invention can be applied to a device related to various colored images such as a display device (for example, a known liquid crystal display device, an organic EL device, etc.) and a solid- , In a known form.

Example

EXAMPLES Next, the present invention will be described more specifically by way of examples.

In Examples and Comparative Examples,% and parts representing the content and amount of use are on a mass basis unless otherwise specified.

In the following examples, the structure of the compound was NMR [JMM-ECA-500; (Manufactured by Nihon Denshi Co., Ltd.) and mass analysis (LC: Agilent 1200 type, MASS: Agilent LC / MSD type).

[Example 1]

80 parts of water was added to 13.7 parts of anthranilic acid (manufactured by Tokyo Kasei Kogyo K.K.), and 0.4 part of sodium hydroxide was added to dissolve it. Under ice cooling, 19.7 parts of a 35% aqueous solution of sodium nitrite was added, followed by dissolving 26.2 parts of 35% hydrochloric acid in small portions, followed by stirring for 2 hours to obtain a suspension containing the diazonium salt.

On the other hand, 26.0 parts of acetoacetic acid ethyl ester (manufactured by Tokyo Kasei Kogyo K.K.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Kasei) and 24.4 parts of 2-aminoethanol (manufactured by Wako Pure Chemical Industries, C < / RTI > 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 the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected as a residue of suction filtration and dried to obtain 20.4 parts represented by the formula (b1a).

Subsequently, 20.4 parts of the compound represented by the formula (b1a) was suspended in 100 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 15 minutes. After completion of the dropwise addition, stirring was continued for another 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 DEG 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 the formula (c1a), and the resulting mixture was stirred in a solvent of N-methylpyrrolidone at 70 占 폚 for 3 hours. After completion of the reaction, the mixture was charged with water to obtain 42.35 parts of a compound represented by the formula (d1a). ^The structure was confirmed by ¹ H-NMR.

Identification of the compound represented by the formula (d1a)

^{1 H-NMR (500 MHz,} δ value (ppm, TMS standard), DMSO-d _6); (1H, t), 8.02 (3H, s), 2.57 (3H, s), 4.13 (2H, t), 4.31 (1H, d), 8.04 (1H, d), 15.7 (1H, s).

Next, to 2.0 parts of the compound represented by the formula (d1a), 50 parts of N-methylpyrrolidone was added and the mixture was heated to 80 DEG C to dissolve it. Then, 1.2 parts of chromium formate n hydrate (manufactured by Nacalai Tesque K.K.) And stirred 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-colored solid was filtered and vacuum-dried at 60 ° C to obtain 1.6 parts (yield: 76%) of a compound represented by the formula (I-1).

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

(Mass analysis) Ionization mode = ESI-: m / z = 932.2 [MH] ^-

                         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 the compound represented by the formula (d1b)

^{1 H-NMR (500 MHz,} δ value (ppm, TMS standard), DMSO-d _6); (2H, t), 7.37 (1H, t), 7.74 (1H, t), 2.50 (2H, 2H, overlapped), 2.55 (3H, s), 3.51 , 8.02 (1 H, d), 8.03 (1 H, d), 15.6 (1 H, s).

Next, 93 parts of N-methylpyrrolidone was added to 3.7 parts of the compound represented by the formula (d1b), and the mixture was heated to 80 DEG C to dissolve it. Then, 1.8 parts of chromium formate n-hydrate was added and stirred at 120 DEG C for about 7 hours, . This solution was poured into 210 parts of a 20% saline solution, and the resulting orangeish solid was filtered and vacuum-dried at 60 占 폚 to obtain 3.2 parts (yield: 82%) of a compound represented by the formula (I-2).

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

(Mass analysis) Ionization mode = ESI-: m / z = 960.0 [MH] ^-

                       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 Kasei Kogyo Co., Ltd.), 2.2 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of sodium nitrite was added, followed by the addition of 23.1 parts of 35% hydrochloric acid little by little. Thereafter, the mixture was stirred for 2.5 hours under ice-cooling. To quench excess nitrite, 70 parts of a 9% aqueous solution of amidic sulfuric acid was added slowly and stirred for about 10 minutes to obtain a suspension containing the diazonium salt.

Then, 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 by 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 DEG C under reduced pressure to obtain 9.3 parts of a compound represented by the formula (c1c).

Next, to 4.2 parts of the compound represented by the formula (c1c), 3.1 parts of the acid chloride (e1b) was added and the mixture was stirred in a solvent of N-methylpyrrolidone at 70 占 폚 for 3 hours. After completion of the reaction, the mixture was charged with 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 the compound represented by the formula (d1c)

^{1 H-NMR (500 MHz,} δ value (ppm, TMS standard), DMSO-d _6); (2H, t, 2H), 2.53 (3H, s), 3.83 (3H, s), 3.93 t), 7.43 (1H, s), 7.48 (1H, s), 15.7 (1H, s).

Next, to 11.0 parts of the compound represented by the formula (d1c), 120 parts of N-methylpyrrolidone was added and dissolved by heating to 80 DEG C, followed by the addition of 1.0 part of chromium formate n hydrate and the mixture was stirred at 110 DEG C for about 1 hour. Subsequently, the temperature was lowered to 80 DEG C, and 2.3 parts of sodium carbonate was added, followed by stirring at 110 DEG 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-colored solid was filtered and vacuum-dried at 60 ° C to obtain 7.6 parts of a compound represented by the formula (I-3) (yield 65%).

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

(Mass spectrometry) Ionization mode = ESI-: m / z = 1080.2 [M-Na] ^-

Exact Mass: 1103.2

[Example 4]

After adding 90 parts of water to 5.5 parts of 2-amino-5-hydroxybenzoic acid (manufactured by Tokyo Kasei Kogyo K.K.), 2.9 parts of sodium hydroxide was added and dissolved. Under ice cooling, 8.0 parts of sodium nitrite was added, followed by the addition of 29.7 parts of 35% hydrochloric acid little by little. Thereafter, the mixture was stirred for 2 hours under ice-cooling. 87 parts of a 9% aqueous solution of sulfuric acid was added slowly to quench excess nitrite, and the mixture was stirred for about 10 minutes to obtain a suspension containing the diazonium salt.

Then, 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. Then, 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 less. 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 캜 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 the compound represented by the formula (c1d)

^{1 H-NMR (500 MHz,} δ value (ppm, TMS standard), DMSO-d _6); (1H, d), 7.76 (1H, d), 7.92 (1H, d) (1 H, s), 15.5 (1 H, s).

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

Identification of the compound represented by the formula (d1d)

^{1 H-NMR (500 MHz,} δ value (ppm, TMS standard), DMSO-d _6); (2H, t), 7.12 (1H, dd), 7.37 (1H, d), 7.82 (2H, 1H, d), 10.2 (1H, s), 15.6 (1H, s).

Then, 98 parts of N-methylpyrrolidone was added to 6.5 parts of the compound represented by the formula (d1d), and the mixture was heated to 80 DEG C to dissolve it. Then, 1.6 parts of chromium formate n-hydrate was added and stirred at 110 DEG C for about 1 hour. Subsequently, the temperature was lowered to 80 ° C, 2 parts of sodium carbonate was added, and the mixture was further stirred 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-colored solid was filtered and vacuum-dried at 60 占 폚 to obtain 4.1 parts (yield: 59%) of a compound represented by the formula (I-4).

Identification of the compound represented by the 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 Kasei Kogyo Co., Ltd.), 0.4 part of sodium hydroxide was added to dissolve the mixture. Under ice cooling, 19.7 parts of a 35% aqueous solution of sodium nitrite was added, followed by dissolving 26.2 parts of 35% hydrochloric acid in small portions, followed by stirring for 2 hours to obtain a suspension containing the diazonium salt.

Subsequently, 20.4 parts of the compound represented by the formula (b1a) was suspended in 100 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 15 minutes. After completion of the dropwise addition, stirring was continued for another 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 DEG C under reduced pressure to obtain 39.1 parts of a compound represented by the formula (c1e).

Next, 30.1 parts of an acid chloride represented by the formula (elb) (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 39.9 parts of the compound represented by the formula (c1e), and the mixture was stirred in N-methylpyrrolidone at 70 占 폚 for 3 hours Respectively. After completion of the reaction, the mixture was charged with water to obtain 50.1 parts of a compound represented by the formula (d1e). The obtained compound showed an orange color, and the maximum absorption wavelength (? Max) was measured in an ethyl lactate solvent and found to be 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

Then, 98 parts of N-methylpyrrolidone was added to 7.0 parts of the compound represented by the formula (d1e), and the mixture was heated to 80 DEG C to dissolve it. Then, 1.6 parts of chromium formate n-hydrate was added and stirred at 110 DEG C for about 1 hour. Subsequently, the temperature was lowered to 80 ° C, 2 parts of sodium carbonate was added, and the mixture was further stirred 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. The obtained dark colored solid was filtered and vacuum-dried at 60 ° C to obtain 2.7 parts (yield 40%) of a compound represented by the formula (I-97).

Identification of the compound represented by the formula (I-97)

(Mass spectrometry) Ionization mode = ESI-: m / z = 1074.2 [M-Na] ^-

Exact Mass: 1097.2

(Measurement of absorbance)

0.35 g of the compound was dissolved in ethyl lactate to adjust its volume to 250 cm 3, and 2 cm 3 of the solution was diluted with ethyl lactate to 100 cm 3 to prepare a solution having a concentration of 0.028 g / L. For this solution, a spectrophotometer [V-650 DS; Absorbance at a maximum absorption wavelength (? Max) and a maximum absorption wavelength (? Max) were measured using a spectrophotometer (manufactured by Nihon Bunko Co., Ltd., (quartz cell, optical path length: 1 cm) The results are shown in Table 2.

In the table, the compound (R-1) Solvent Yellow 21 [Oleosol Fast Yellow 2G; (Manufactured by Dao Kagaku Kogyo Co., Ltd.).

Example 6

[Preparation of colored photosensitive resin composition]

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

(B-1) Resin: methacrylic acid / benzyl methacrylate copolymer (molar ratio: 30/70

; Weight average molecular weight: 10700, acid value: 70 mgKOH / g) 70 parts

(C-1) Polymerizable compound: dipentaerythritol hexaacrylate

                      (Manufactured by Nippon Kayaku Co., Ltd.) 30 parts

(D-1) Photopolymerization initiator: benzyl dimethyl ketal (Irgacure 651; manufactured by Chiba Japan)

                                                                Part 15

(E-1) Solvent: Ethyl lactate 680 parts

Are mixed to obtain a colored resin composition.

[Production of color filter]

On the glass, the colored resin composition obtained above is applied by spin coating to volatilize the volatile components. After cooling, light is irradiated using a quartz glass photomask having a pattern and an exposure machine. After irradiation with light, the resultant was developed with an aqueous solution of potassium hydroxide and heated in an oven at 200 DEG C to obtain a color filter.

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 by 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 by the compound (I-3) synthesized in Example 3.

Example 9

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

Example 10

A colored resin composition and a color filter were obtained in the same manner as in Example 6 except that the compound (I-1) synthesized in Example 1 was replaced by 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 exhibits a high spectral density because of its high absorbance. In addition, the colored resin composition containing the compound can produce a color filter of high quality with excellent color performance.

The compounds of the present invention are useful as dyes. The compound of the present invention is useful as a dye used in a color filter of a display device such as a liquid crystal display device because of its high molar extinction coefficient and high spectral density.

Claims (6)

A compound represented by the formula (O).

[In the formula (O), X ¹ and X ² independently represent -CO-O- or -O-CO-.
L ¹ and L ² 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 group.
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 independently represent -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, -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 combine with each other to form a 6- to 7-membered ring containing a carbon of a benzene ring.
R ⁸ and R ⁹ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the aliphatic hydrocarbon group , The hydrogen atom contained in 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 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 combine with each other to form a ring containing a nitrogen atom.
A ⁺ represents a hydronone, sodium cation, potassium cation or tetraalkylammonium cation of 1 to 4 carbon atoms. A compound represented by formula (I).

[In the formula (I), X ¹ and X ² independently represent -CO-O- or -O-CO-.
L ¹ and L ² 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 group.
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 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 .
R ⁸ and R ⁹ independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the aliphatic hydrocarbon group , The hydrogen atom contained in 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 hydronone, sodium cation, potassium cation or tetraalkylammonium cation of 1 to 4 carbon atoms. 3. The method according to claim 1 or 2,
X < ^{1 >} is * -O-CO-.
[* Represents the bonding position with L < ¹ >]. 3. The method according to claim 1 or 2,
R ² is -CN. A dye comprising the compound of claim 1 or 2 as an active ingredient. A colored resin composition comprising the dye, the resin and the solvent according to claim 5.