JP2003231823A - Disperse dye composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a disperse dye composition having good clarity and high light fastness. <P>SOLUTION: The disperse dye composition containing at least one kind of dispersant contains an azo dye having a specific structure. Concretely, the azo dye having the structure of the formula is exemplified. <P>COPYRIGHT: (C)2003,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disperse dye composition which gives a clear hue useful for coloring a hydrophobic fiber material and has excellent light fastness, and its application. Is. Recently, as automobile seats and interior materials,
A lot of polyester fiber is used,
In recent years, as the interior of automobiles has become fashionable, the color of the seats has been required to be colorful. However, in the case of an automobile seat, it is often exposed to direct sunlight at a high temperature in a sealed room, so that the seat is likely to fade, and it is difficult to maintain a beautiful color for a long time. Accordingly, it is desirable to use a dye having a clear hue and excellent light fastness as a dye for dyeing polyester fibers for automobile seats. In addition, with the recent development of new synthetic fiber materials, there is a high demand for dyes having a bright hue and excellent light fastness from the viewpoint of fashionability in the field of sports clothing that employs these materials. However, no disperse dye has been found that can sufficiently satisfy these requirements. As red disperse dyes for use in these fields, those described in JP-A-61-39347 and JP-A-3-2275 are known. However, although these dyes are excellent in terms of light fastness, their sharpness is insufficient. [0004] The present invention solves the above-mentioned problems of sharpness and light fastness and has good sharpness,
A disperse dye composition having high light fastness is provided. Means for Solving the Problems The inventors of the present invention have studied in detail a dye having high sharpness and light fastness, and found that the above-mentioned problems can be solved by an azo dye comprising a pyridine coupler. I found. (1) A disperse dye composition containing at least one dispersant, which contains a compound represented by the following general formula (1). ## STR2 ## General formula (1) In the above general formula (1), A represents a pyrazole ring group. B ¹ and B ² each represent = CR ^1- , -CR ² =, or either one is a nitrogen atom and the other is = CR
¹ - or an -CR ² =. R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent, and the substituent is an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl Represents a group, an arylsulfonyl group, or a sulfamoyl group, and the hydrogen atom of each substituent may be substituted. G, R ¹ and R ² each independently represents a hydrogen atom or a substituent, which includes a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, An alkoxycarbonyl group,
Aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkylthio group, arylthio group , Heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, or It represents a sulfo group, a hydrogen atom of each substituent may be substituted. R ¹ and R ⁵ or R ⁵
And R ⁶ may combine to form a 5- to 6-membered ring. (2) A method for coloring a fiber material, characterized by using the disperse dye composition described in (1) above. DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described in detail below. [Azo dye] The compound represented by the general formula (1) (also referred to as compound (1)) used in the disperse dye composition of the present invention is an azo dye. The compound (1) is described in detail below. General formula (1) In the above general formula (1), A represents a pyrazole ring group. In the general formula (1), B ¹ and B ² are each
CR ¹ - and represent a -CR ² =, or either one nitrogen atom and the other = CR ¹ - or represents a -CR ² =, respectively ^{= CR 1 -, - CR 2} = more those representing the preferable. R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent, and the substituent is an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl Represents a group, an arylsulfonyl group, or a sulfamoyl group, and the hydrogen atom of each substituent may be substituted. R ⁵ , R ⁶
Preferable examples include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkyl group, or an arylsulfonyl group. More preferably, they are a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group. Most preferably, they are a hydrogen atom, an aryl group, and a heterocyclic group. The hydrogen atom of each substituent may be substituted. However, R ⁵ and R ⁶ are not simultaneously hydrogen atoms. G, R ¹ and R ² each independently represents a hydrogen atom or a substituent, which includes a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, Carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group , Aryloxycarbonyloxy group, amino group,
Acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group,
Nitro group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group,
It represents a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, and the hydrogen atom of each substituent may be substituted. G is a hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group, acylamino group, ureido group, sulfamoylamino group, An alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylthio group, or a heterocyclic thio group is preferable, and a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group is more preferable. A hydrogen atom, an amino group (preferably an anilino group), and an acylamino group. The hydrogen atom of each substituent may be substituted. Preferred as R ¹ and R ² are hydrogen atom, alkyl group, halogen atom, alkoxycarbonyl group, carboxyl group, carbamoyl group, hydroxy group,
An alkoxy group and a cyano group can be mentioned. The hydrogen atom of each substituent may be substituted. R ¹ and R ⁵ , or R ⁵ and R ⁶ may combine to form a 5- to 6-membered ring.
When A has a substituent, or when the substituent of R ¹ , R ² , R ⁵ , R ⁶ or G further has a substituent, the substituents mentioned for G, R ¹ and R ² above You can give a group. The terms (substituents) used in this specification will be explained. These terms are common even between different symbols in the general formula (1) and the general formula (1a) described later. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. The aliphatic group is an alkyl group, a substituted alkyl group,
An alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group are meant. In this specification, “substituted” used for “substituted alkyl group” and the like means that a hydrogen atom existing in “alkyl group” or the like is substituted with the substituents mentioned in G, R ¹ and R ² above. Indicates. The aliphatic group may have a branch and may form a ring. The aliphatic group has 1 to 2 carbon atoms
0 is preferable, and 1 to 16 is more preferable. The aryl moiety of the aralkyl group and the substituted aralkyl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl,
t-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3-sulfopropyl group, 4-sulfobutyl group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group. Can be mentioned. An aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The number of carbon atoms in the aromatic group is preferably 6 to 20, and more preferably 6 to 16. Examples of the aromatic group include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and an m- (3-sulfopropylamino) phenyl group. The heterocyclic group includes a substituted heterocyclic group.
In the heterocyclic group, an aliphatic ring, an aromatic ring or another heterocyclic ring may be condensed with the heterocyclic ring. Examples of the heterocyclic group include 5
A membered or 6-membered heterocyclic group is preferred. Examples of the substituent include an aliphatic group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, an ionic hydrophilic group, and the like. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group and 2-
A furyl group is included. The carbamoyl group includes a substituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group. The alkoxycarbonyl group includes a substituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. The aryloxycarbonyl group includes a substituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group. The heterocyclic oxycarbonyl group includes a substituted heterocyclic oxycarbonyl group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group. The acyl group includes a substituted acyl group.
The acyl group is preferably an acyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group. The alkoxy group includes a substituted alkoxy group. The alkoxy group has 1 to 1 carbon atoms.
Twenty alkoxy groups are preferred. Examples of the substituent include
Alkoxy groups, hydroxyl groups, and ionic hydrophilic groups are included. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group. The aryloxy group includes a substituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group. The heterocyclic oxy group includes a substituted heterocyclic oxy group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic oxy group is preferably a heterocyclic oxy group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 3-thienyloxy group. The silyloxy group has 1 carbon atom.
A silyloxy group substituted with -20 aliphatic groups or aromatic groups is preferred. Examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy. The acyloxy group includes a substituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group. The carbamoyloxy group includes a substituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include
N-methylcarbamoyloxy groups are included. The alkoxycarbonyloxy group includes a substituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group has 2 to 2 carbon atoms.
Zero alkoxycarbonyloxy groups are preferred. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group. The aryloxycarbonyloxy group includes
Substituted aryloxycarbonyloxy groups are included. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 20 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group. The amino group includes a substituted amino group.
Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group may further have a substituent. The alkylamino group includes a substituted alkylamino group. As the alkylamino group, an alkylamino group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group. The arylamino group includes a substituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 20 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include a phenylamino group and 2
-A chlorophenylamino group is included. The heterocyclic amino group includes a substituted heterocyclic amino group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic amino group is preferably a heterocyclic amino group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, a halogen atom, and an ionic hydrophilic group. The acylamino group includes a substituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group. The ureido group includes a substituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group. The sulfamoylamino group includes a substituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group. The alkoxycarbonylamino group includes a substituted alkoxycarbonylamino group. The alkoxycarbonylamino group has 2 to 2 carbon atoms.
Zero alkoxycarbonylamino groups are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group. The aryloxycarbonylamino group includes
Substituted aryloxycarbonylamino groups are included. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group. The alkylsulfonylamino group and arylsulfonylamino group include a substituted alkylsulfonylamino group and a substituted arylsulfonylamino group.
The alkylsulfonylamino group and arylsulfonylamino group are preferably an alkylsulfonylamino group having 1 to 20 carbon atoms and an arylsulfonylamino group. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylsulfonylamino group and arylsulfonylamino group include a methylsulfonylamino group, an N-phenyl-methylsulfonylamino group, a phenylsulfonylamino group, and a 3-carboxyphenylsulfonylamino group. The heterocyclic sulfonylamino group includes a substituted heterocyclic sulfonylamino group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonylamino group include a 2-thienylsulfonylamino group and a 3-pyridylsulfonylamino group. The alkylthio group, arylthio group and heterocyclic thio group include a substituted alkylthio group, a substituted arylthio group and a substituted heterocyclic thio group. As a heterocyclic ring,
The heterocyclic ring described in the heterocyclic group is mentioned. As the alkylthio group, arylthio group and heterocyclic thio group,
Those having 1 to 20 carbon atoms are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group, arylthio group and heterocyclic thio group include a methylthio group, a phenylthio group, and a 2-pyridylthio group. The alkylsulfonyl group and arylsulfonyl group include a substituted alkylsulfonyl group and a substituted arylsulfonyl group. Examples of the alkylsulfonyl group and the arylsulfonyl group can include a methylsulfonyl group and a phenylsulfonyl group, respectively. The heterocyclic sulfonyl group includes a substituted heterocyclic sulfonyl group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonyl group include a 2-thienylsulfonyl group and a 3-pyridylsulfonyl group. The alkylsulfinyl group and the arylsulfinyl group include a substituted alkylsulfinyl group and a substituted arylsulfinyl group. Examples of the alkylsulfinyl group and the arylsulfinyl group include a methylsulfinyl group and a phenylsulfinyl group, respectively. The heterocyclic sulfinyl group includes a substituted heterocyclic sulfinyl group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfinyl group include
A 4-pyridylsulfinyl group is included. The sulfamoyl group includes a substituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group. In the present invention, a particularly preferred structure is represented by the following general formula (1a). Formula (1a): embedded image In the formula, R ¹ , R ² , R ⁵ and R ⁶ have the same meaning as in the general formula (1). R ³ and R ⁴ each independently represents a hydrogen atom or a substituent, and the substituent is an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl Represents a group, an arylsulfonyl group, or a sulfamoyl group. Of these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group is preferable, and a hydrogen atom, an aromatic group, or a heterocyclic group is particularly preferable. Z ¹ has Hammett's substituent constant σp value of 0.
Represents 20 or more electron-withdrawing groups. Z ¹ has a σp value of 0.3
It is preferably zero or more electron-withdrawing group, more preferably 0.45 or more electron-withdrawing group, and particularly preferably 0.60 or more electron-withdrawing group, but it is desirable not to exceed 1.0. Specific examples of the preferred substituent include an electron-withdrawing substituent described later. Among them, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, 1-20 carbon atoms
An alkylsulfonyl group, a C6-C20 arylsulfonyl group, a C1-C20 carbamoyl group, and a C1-C20 halogenated alkyl group are preferable. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group. Z ² represents a hydrogen atom or a substituent, and the substituent represents an aliphatic group, an aromatic group, or a heterocyclic group. Z ² is preferably an aliphatic group, more preferably an alkyl group having 1 to 6 carbon atoms. Q represents a hydrogen atom or a substituent, and the substituent represents an aliphatic group, an aromatic group, or a heterocyclic group. Above all, Q is 5
A group consisting of a group of non-metallic atoms necessary to form an ˜8-membered ring is preferred. The 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond.
Of these, aromatic groups and heterocyclic groups are particularly preferred. Preferred nonmetallic atoms include nitrogen atoms, oxygen atoms, sulfur atoms or carbon atoms. Specific examples of such a ring structure include, for example, a benzene ring, a cyclopentane ring,
Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, Examples include an oxan ring, a sulfolane ring, and a thiane ring. The hydrogen atom of each substituent described in the general formula (1a) may be substituted. Examples of the substituent include the substituents described in the general formula (1), the groups exemplified for G, R ¹ and R ² , and ionic hydrophilic groups. Here, Hammett's substituent constant σp value used in this specification will be described. Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange '
s Handbook of Chemistry "12th edition, 1979 (Mc Graw-Hill) and" Area of Chemistry "special edition, 122, 96-103, 19
Detailed in 79 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it can be found in the above-mentioned book and is limited only to a substituent having a known value in the literature. However, it goes without saying that even if the value is unknown, it includes substituents that would be included in the range when measured based on Hammett's rule. In addition, the general formula (1a) of the present invention includes those that are not benzene derivatives, but the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value is used in this sense. Examples of the electron-withdrawing group having a Hammett substituent constant σp value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group (eg, methylsulfonyl group, arylsulfonyl group (eg, phenylsulfonyl group)). As the electron withdrawing group having a Hammett σp value of 0.45 or more, in addition to the above, an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m -Chlorophenoxycarbonyl), alkylsulfinyl groups (eg n-propylsulfinyl), arylsulfinyl groups (eg phenylsulfinyl), sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dimethylsulfamoyl), halogen Alkyl groups (eg For example, the Hammett substituent constant σp value is 0.30.
As the above electron-withdrawing group, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), a halogenated alkoxy group (for example, trifluoromethyloxy) ), Halogenated aryloxy group (for example, pentafluorophenyloxy), sulfonyloxy group (for example, methylsulfonyloxy group), halogenated alkylthio group (for example, difluoromethylthio), two or more σp values of 0.15 or more An aryl group substituted with an electron-withdrawing group (for example, 2,4-dinitrophenyl, pentachlorophenyl) and a heterocycle (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl) Can be mentioned.
Specific examples of the electron-withdrawing group having a σp value of 0.20 or more include a halogen atom in addition to the above. A particularly preferred combination of substituents as the azo dye represented by the general formula (1) is preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by R ⁵ and R ⁶ .
A heterocyclic group, a sulfonyl group, and an acyl group, more preferably a hydrogen atom, an aryl group, a heterocyclic group, and a sulfonyl group, and most preferably a hydrogen atom, an aryl group, and a heterocyclic group. However, R ⁵ and R ⁶ are not both hydrogen atoms. G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group or an acylamino group, more preferably a hydrogen atom, a halogen atom, an amino group or an acylamino group, most preferably a hydrogen atom or an amino group. An acylamino group.
Of A, preferably a pyrazole ring, an imidazole ring,
An isothiazole ring, a thiadiazole ring and a benzothiazole ring, a pyrazole ring and an isothiazole ring, and most preferably a pyrazole ring. B ¹ and B ² are respectively = CR ^1- , -CR ² =, and R ¹ , R 2
² is preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, a hydroxyl group, an alkoxy group, or an alkoxycarbonyl group, more preferably a hydrogen atom, an alkyl group, a carboxyl group, a cyano group, It is a carbamoyl group. As for the preferred combination of substituents of the compound represented by the general formula (1), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are available. Are more preferred compounds, and most preferred are compounds in which all substituents are preferred groups. Specific examples of the azo dye represented by the general formula (1) are shown below. The azo dye used in the present invention is:
It is not limited to the following example. [Table 1] [Table 2] [Table 3] [Table 4] Next, a method for producing compound (1) will be described. Synthesis of dye (a-1) Synthesis Example 1 1) <Synthesis of Intermediate (a-1a)> 8-amino-3-tert-butyl-4-cyanopyrazole (1) 8 g (48.7 mmol), concentrated hydrochloric acid 15 m
l, 50 ml of water was stirred at an internal temperature of 5 ° C., and 3.36 g (48.7 mmol) of sodium nitrite was added in portions over 10 minutes. After stirring for 10 minutes, the coupler component (2)
21.3 g (40.6 mmol) of sodium acetate 50
g, acetic acid 50 ml, water 50 ml was added and stirred.
The diazonium salt was added to the three-necked flask that had been cooled each time in 10 minutes. After adding the diazonium salt, the reaction solution was further stirred for 30 minutes, and then saturated brine 30
0 ml was added, and the precipitated dye (a-1a) was isolated by suction filtration. Yield 24.2 g, 85% yield. 2) <Synthesis of Dye (a-1)> To 14.0 g (20 mmol) of the intermediate (a-1a), 4.4 g (26 mmol) of the heterylating agent (3), 2.8 g of potassium carbonate, and 50 ml of DMAc were added. And stirred for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, 200 ml of saturated brine was added, and the precipitated dye (a-1) was isolated by suction filtration. Further, the crude crystals were recrystallized with an acetonitrile solvent. Yield 16.7 g, yield 80%. λ
max = 545 nm (DMF solution) m / z (posi)
= 834 Since the compound (1) used in the present invention is insoluble or hardly soluble in water, the disperse dye composition of the present invention is dispersed by a dispersant and a solvent. Examples of the dispersant include a condensate of naphthalenesulfonic acid and formaldehyde, a higher alcohol sulfate, a higher alkylbenzene printing paste, and the like. Examples of the solvent include water. In the disperse dye composition of the present invention, the mass ratio of the compound (1) to the dispersant is preferably 1: 5, more preferably 1: 3, and particularly preferably 1: 1. Examples of other components include ultraviolet absorbers and surfactants, and appropriate amounts are used. The dyeing of fibers can be carried out by dip dyeing or printing using the disperse dye composition of the present invention. For example, in the case of printing, if ordinary dyeing methods such as high-temperature dyeing, carrier dyeing, and thermosol dyeing are applied, dyeing with excellent fastness will be given to fibers such as polyester fibers or their mixtures. Can do. At that time, if a known acidic substance such as formic acid, acetic acid, phosphoric acid or ammonium sulfate is added to the dyeing bath, a better result can be obtained. The pH of the dyeing bath is usually 5.0 to
It is preferable to adjust to the range of 9.5. And the dyeing | staining temperature is about 120-140 degreeC, for example. The dyeing conditions in exhaust dyeing are not particularly limited. For example, the dyeing temperature is about 120 to 140 ° C., and the dyeing time is about 30 to 60 minutes.
H is about 4 to 9.5. In dyeing, various leveling agents and / or ultraviolet absorbers may be used in combination. The fiber that can be dyed by the disperse dye composition of the present invention is not particularly limited, but usually from polyethylene terephthalate, polycondensate of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, or the like. And polyester fiber, or a blend or woven product of the above-mentioned polyester fiber with cotton, silk, wool, rayon, polyamide polyurethane or the like. Among them, a hydrophobic fiber material is preferable, and particularly when the fiber is a polyester fiber for an automobile sheet, the thickness is 2 to 2.
In the case where the 5 denier polyester fiber is a fine denier polyester fabric for clothing, a polyester fiber having a thickness of 0.1 to 1 denier is preferred. Examples of the present invention will be described below, but the present invention is not limited thereto. [Example 1] Polyester fabric 100 g was added to disperse dye composition A prepared by dispersing 1.8 g of dye (a-1) in 3 liters of water containing 1 g of naphthalenesulfonic acid-formaldehyde condensate and 2 g of higher alcohol sulfate.
Is soaked, dyed at 130 ° C. for 60 minutes, and then soaped, washed with water and dried to obtain a red dyed fabric.
The polyester fabric of the hydrophobic fiber material is colored in the same manner as the disperse dye composition A except that a disperse dye composition prepared by changing the dye (a-1) as shown in Table 5 below is used. The hue of the resulting dyed cloth was evaluated by three stages: best, good and poor visually. Light fastness is JIS
Test method modified for automobiles based on the specified test method (JIS L-8043) (temperature is 89 ° C ± 5 ° C,
A flexible urethane foam (10 mm) is pasted on the back side of the test cloth, and the color is determined by a discoloration scale defined by JIS). The evaluation results are shown in Table 5 below. Table 5 below
Medium, ○ indicates the best hue;
Indicates that the hue is poor. In addition, as for light fastness, ○ indicates the best; Δ indicates good × indicates poor. [Table 5] Embedded image Example 2 Disperse dye composition A prepared by dispersing 1.8 g of dye (a-1) in 3 liters of water containing 1 g of naphthalenesulfonic acid-formaldehyde condensate and 2 g of higher alcohol sulfate, After 100 g of fine denier polyester fabric is immersed and dyed at 135 ° C. for 60 minutes, a red dyeing cloth is obtained by performing reduction cleaning, washing with water and drying according to conventional methods. Dye (a-
The polyester fabric of the hydrophobic fiber material is colored in the same manner as the disperse dye composition A except that a disperse dye composition prepared by changing 1) as shown in Table 6 below is used. The hue and light fastness of the resulting dyed fabric were evaluated in the same manner as in Example 1. [Table 6] As shown in Tables 5 and 6, the red dyeing fabrics obtained from the disperse dye compositions A to D were disperse dye compositions E and F.
It is clearer than the red dyeing cloth obtained from By using the novel azo dye of the present invention, it is possible to provide a disperse dye composition and a coloring method for obtaining a hydrophobic fiber material having a clear hue and high light fastness. .

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Naoyuki Hanaki             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd. (72) Inventor Shigeaki Tanaka             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd.

Claims (1)

What is claimed is: 1. A disperse dye composition containing at least one dispersant, comprising a compound represented by the following general formula (1): . General formula (1) In the general formula (1), A represents a pyrazole ring group. B
¹ and B ² are each ^{= CR 1 -, - CR 2} = or represents, or either one nitrogen atom and the other = CR ¹ - or an -CR ² =. R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent, and the substituent is an aliphatic group, an aromatic group,
It represents a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and the hydrogen atom of each substituent may be substituted. G, R ¹ and R ² each independently represents a hydrogen atom or a substituent, which includes a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group,
Carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group,
Heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group,
Aryloxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group , Alkylthio group, arylthio group, heterocyclic thio group,
It represents an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, and the hydrogen atom of each substituent may be substituted. R ¹ and R ⁵ , or R ⁵ and R ⁶ may combine to form a 5- to 6-membered ring.