JP2002226724A - Azo compound or its salt, and their application to fibrous material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactive dye useful for dyeing cellulose fibers red. SOLUTION: The reactive dye comprises an azo compound represented by formula (1) (wherein a, b, c and d are each 0 or 1, provided that c is 0 and d is 1 when b is 0, and at least one of a and d is 1 when b is 1; D1 and D2 are each an optionally substituted phenylene, an optionally substituted naphthylene, or the like; R1 is H or alkyl; R2 is phenyl or the like; and Z1 and Z2 are each a specified fiber-reactive group) or its salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azo compound or a salt thereof which is particularly useful for dyeing or printing a cellulose fiber material or the like in red.

[0002]

2. Description of the Related Art As a reactive dye for dyeing or printing a cellulose fiber material or the like in red, an amino group is substituted at the 2-position of a 6-sulfo-8-naphthol ring, and the same is used. 1
At the -position, the 2-position of the triazine ring is bonded via an aminophenylazo group, and at the 4- and 6-positions of the triazine ring, chloro or fluoro, and other than chloro and fluoro, respectively. A reactive dye in which an amino group substituted with a fiber reactivity-imparting group is bonded is known (Japanese Patent Application Laid-Open No. 9-1 / 1991).
No. 76504).

[0003]

However, the above-mentioned known reactive dyes do not always have sufficient water solubility and build-up property, and the fastness of the obtained dyed product is not always satisfactory.

[0004]

Means for Solving the Problems The present inventor has proposed a red dye which gives a dyed product or a printed product which is excellent in water solubility and build-up properties and excellent in various fastnesses as compared with the above known reactive dyes. As a result of intensive research to develop a reactive dye of the formula (1), an amino group substituted with phenyl or an amino group substituted with phenyl and alkyl was placed at the 2-position of the 6-sulfo-8-naphthol ring. The present inventors have found that the azo compound having the compound or a salt thereof achieves the above object, and have completed the present invention.

That is, the present invention provides a bisazo compound represented by the formula (1) or a salt thereof, and a method for dyeing or printing a fiber material using the compound or a salt thereof.

[0006]

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Wherein a, b, c and d are the same or different and represent 0 or 1. D ¹ represents a phenylene group which may be substituted with a non-fiber reactive group or a naphthylene group which may be substituted with a non-fiber reactive group when a is 1, and when a is 0, A phenyl group which may be substituted with a non-fiber reactive group or a naphthyl group which may be substituted with a non-fiber reactive group. D ² represents a phenylene group which may be substituted with a non-fiber reactive group or a naphthylene group which may be substituted with a non-fiber reactive group when d is 1, and when d is 0, A phenyl group which may be substituted with a non-fiber reactive group or a naphthyl group which may be substituted with a non-fiber reactive group. R ¹ represents hydrogen or alkyl optionally substituted with a non-fiber reactive group;
² represents hydrogen, alkyl optionally substituted with a non-fiber reactive group, or phenyl optionally substituted with a non-fiber reactive group, and Z ¹ and Z ² are the same or different and are represented by the following formula (2a ), (2b), (2c), (2d) or (2e)

[0008]

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Wherein Z is -N (R ⁶ ) -A ² -SO ₂
It represents -Y ³ and -N (R ⁸⁾ -A ³ does not contain -SO ₂ -Y ⁴ heterocyclic fiber-reactive ^{group, R 3, R 4, R} 5, R 6, R 7
And R ⁸ are the same or different and represent hydrogen, alkyl optionally substituted with a non-fiber reactive group or phenyl optionally substituted with a non-fiber reactive group, and A ¹ and A ² are the same or different Differently, represents an aliphatic linking group, A ³ represents an aromatic linking group, Y ¹ , Y ² , Y ³ and Y ⁴ are the same or different, and —CH ＝ CH ₂ or —CH ₂ CH ₂ L, wherein L is a group capable of leaving under the action of an alkali, and X ¹ and X ² are the same or different and are fluoro, chloro, optionally substituted pyridinio, or a compound represented by the following formula (3a) ),
(3b), (3c) or (3d)

[0010]

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(R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted phenyl or substituted Represents naphthyl which may be
Q is _{-CH 2 -, - O -,} - S -, - SO 2 - or -NR
¹³ - represents, R ¹³ represents an alkyl which may be hydrogen or substituted, e is 1, 2 or 3. ).繊 維 represents a fiber reactive group. Where b is 0
In the case of, c is 0, d is 1, and Z ² is a fiber reactive group represented by the above formula (2d) or (2e), and when b is 1, when a and d are At least one is 1, and at least one of Z ¹ and Z ² is the above formula (2
It is a fiber reactive group represented by d) or (2e). Hereinafter, the present invention will be described in detail.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION a in the azo compound (1),
b, c and d are the same or different and represent 0 or 1, but when b is 0, c is 0, d is 1 and Z ² is the above formula (2d) or ( This is a fiber reactive group represented by 2e). When b is 1, at least one of a and d is 1, and at least one of Z ¹ and Z ² is a fiber reactive group represented by the above formula (2d) or (2e).

When a in the azo compound (1) is 1, D ¹ represents a phenylene group optionally substituted with a non-fiber reactive group or a naphthylene group optionally substituted with a non-fiber reactive group. When a is 0, D ¹ represents a phenyl group optionally substituted with a non-fiber reactive group or a naphthyl group optionally substituted with a non-fiber reactive group. When d in the azo compound (1) is 1, D ² represents a phenylene group optionally substituted with a non-fiber reactive group or a naphthylene group optionally substituted with a non-fiber reactive group.
When d is 0, D ² represents a phenyl group optionally substituted with a non-fiber reactive group or a naphthyl group optionally substituted with a non-fiber reactive group.

Examples of the phenyl group which may be substituted with a non-fiber reactive group represented by D ¹ and D ² or the phenylene group which may be substituted with a non-fiber reactive group include, for example, a compound represented by the formula (4)
a)

[0015]

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Wherein R ¹⁴ and R ¹⁵ are the same or different and are hydrogen, sulfo, halogeno, alkyl optionally substituted by a non-fiber reactive group, or alkoxy optionally substituted by a non-fiber reactive group And f represents 0 or 1, and * represents a bond connected to a -N = N- group. And a — (CH ₂ ) f in formula (4a)
And a phenyl group in which-is not substituted.

The substitutable alkyl represented by R ¹⁴ and R ¹⁵ preferably has 1 to 4 carbon atoms and may be linear or branched. Examples of the substituent of the alkyl include hydroxy, cyano, alkoxy having 1 to 4 carbons,
Examples thereof include halogeno, carbamoyl, carboxy, alkoxy (1 to 4 carbon atoms) carbonyl, alkyl (1 to 4 carbon atoms) carbonyloxy, sulfo, and sulfamoyl. Alkoxy having 1 to 4 carbon atoms, alkoxy (1 to 4 carbon atoms) carbonyl and alkyl (1 to 4 carbon atoms) carbonyloxy, which are substituents of the above alkyl, may be linear or branched.

The substitutable alkyl represented by R ¹⁴ and R ¹⁵ includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl
-Butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl,
2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl , 2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl,
-Bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, Methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-E Tylcarbonyloxypropyl, 4
-Methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3
-Sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like.

As the substitutable alkyl represented by R ¹⁴ and R ¹⁵ , methyl or ethyl is preferable, and methyl is particularly preferable.

The substitutable alkoxy represented by R ¹⁴ and R ¹⁵ preferably has 1 to 4 carbon atoms, and may be linear or branched. Examples of the substituent of the alkoxy include the groups exemplified as the substituents of the substitutable alkyl represented by R ¹⁴ and R ¹⁵ . R
The replaceable alkoxy, denoted by ¹⁴ and R ^15, methoxy or ethoxy are preferred, with methoxy being especially preferred.

Specific examples of the group represented by the above formula (4a) include, for example,

[0022]

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[In the formula, an asterisk means a bond connected to a -N = N- group. And a phenyl group having no unmarked bond in these phenylene groups. Among these groups, unsubstituted phenyl, unsubstituted phenylene, sulfo, phenyl substituted with 1 to 2 substituents selected from methyl and methoxy, or 1 to 2 phenyl selected from sulfo, methyl and methoxy Phenylene substituted with a substituent is particularly preferred.

Examples of the naphthyl group which may be substituted with a non-fiber reactive group represented by D ¹ and D ² or the naphthylene group which may be substituted with a non-fiber reactive group include, for example, the following formula (4)
b)

[0025]

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[In the formula, * represents a bond connected to the -N = N- group, g represents 0, 1, 2 or 3, and h represents 0 or 1. And a naphthylene group represented by the formula (4)
Examples include a naphthyl group in which-(CH2) h- in b) is not substituted. Examples of these groups include the following naphthylene and naphthyl groups.

[0027]

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[In the formula, an asterisk means a bond connected to a -N = N- group. ]

As a combination of D ¹ and D ² , it is preferable that both are phenyl groups or phenylene groups, and one or two substituents selected from unsubstituted phenyl, unsubstituted phenylene, sulfo, methyl and methoxy are preferable. Particularly preferred is substituted phenyl or phenylene substituted with one or two substituents selected from sulfo, methyl and methoxy.

R ¹ represents hydrogen or alkyl optionally substituted with a non-fiber reactive group, and R ² represents phenyl optionally substituted with a non-fiber reactive group. Examples of the substitutable alkyl represented by R ¹ include the same groups as the substitutable alkyl represented by R ¹⁴ and R ¹⁵ . The substitutable phenyl represented by R ² includes alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, sulfo, carboxy, halogeno, hydroxy, cyano, carbamoyl, sulfamoyl, alkoxy (1 to 4 carbons) ) From the group of carbonyl, alkyl (1 to 4 carbon atoms) carbonyloxy, amino, acylamino [preferably alkyl (1 to 4 carbon atoms) carbonylamino], alkylamino (1 to 4 carbon atoms) and 2-hydroxyethylsulfonyl Examples include phenyl which may be substituted by one or two selected substituents. Alkyl having 1 to 4 carbon atoms, 1 to 4 carbon atoms as a substituent of the phenyl
Of alkoxy, alkyl (C1-4) carbonylamino, alkoxy (C1-4) carbonyl, alkyl (C1-4) carbonyloxy and alkylamino (C1-4) Well, it may be branched.

The substitutable phenyl represented by R ² includes phenyl, 2-, 3- or 4-methylphenyl,
2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isopropylphenyl, 2
-, 3- or 4-carboxyphenyl, 2-, 3- or 4-carbamoylphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-sulfophenyl, 2-,
3- or 4-hydroxyphenyl, 2-sulfo-4-methoxyphenyl, 2-sulfo-4-acetylaminophenyl, 2-carboxy-4-acetylaminophenyl,
Examples include 2-methoxy-5-methylphenyl, 2,4-dimethoxyphenyl, and 2,5-dimethoxyphenyl.

As R ¹ , hydrogen, methyl or ethyl is preferable, and hydrogen is particularly preferable. R ² is hydrogen,
Phenyl is preferred, and phenyl is particularly preferred.

Z ¹ and Z ² are the same or different, and have the formula (2)
a) represents a fiber reactive group represented by (2b), (2c), (2d) or (2e).

Equations (2a), (2c), (2d) and (2
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in e) are the same or different and are hydrogen, alkyl optionally substituted with a non-fiber reactive group, or substituted with a non-fiber reactive group. Represents an optionally substituted phenyl. As the above-mentioned substitutable alkyl,
The same groups as the substitutable alkyl represented by R ¹⁴ and R ¹⁵ can be mentioned. Examples of the above-mentioned substitutable phenyl include the same groups as the above-mentioned substitutable phenyl represented by R ² .

In the formula (2a), Z is -N (R ⁶ )-
Represents a heterocyclic fiber-reactive group containing no A _² -SO ² -Y ³ and ^{-N (R 8) -A 3 -SO} 2 -Y 4. Examples of such a heterocyclic fiber reactive group include a group in which a 5- or 6-membered heterocyclic ring or an aromatic carbon condensed cyclic heterocyclic ring is substituted with one or more fiber-reactivity imparting groups. can do.

As the 5- or 6-membered heterocyclic ring, for example,
Monoazine, diazine, triazine, pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine and the like can be mentioned. Examples of the fused aromatic carbon heterocycle include quinoline, phthalazine, quinazoline, quinoxaline, acridine, phenazine and phenanthridine. Examples of the fiber reactivity imparting group on the heterocyclic ring, for example, fluoro, chloro, bromo, pyridinio,
Examples thereof include carbonylpyridinio, carbamoylpyridinio, sulfonium, and thiocyanate.

As Z in the above formula (2a), for example, monochlorotriazinyl, monopyridiniotriazinyl, 4,6-dichlorotriazin-2-yl, monofluorotriazinyl, di- or tri-halo Pyrimidinyl and 2,3-dichloroquinoxaline-5- or-
6-carbonyl and the like can be mentioned.

Specific examples of the above monochlorotriazinyl are as follows. 4-chloro-6-aminotriazine-
2-yl, 4-chloro-6-cyanoaminotriazine-
2-yl, 4-chloro-6-methylaminotriazine-
2-yl, 4-chloro-6-ethylaminotriazine-
2-yl, 4-chloro-6- (2-hydroxyethyl)
Aminotriazin-2-yl, 4-chloro-6- (2-
Sulfoethyl) aminotriazin-2-yl, 4-chloro-6- (2-methoxyethyl) aminotriazine-2
-Yl, 4-chloro-6- (2-ethoxyethyl) aminotriazin-2-yl, 4-chloro-6- (2- (2
-Hydroxyethylsulfonyl) ethyl) aminotriazin-2-yl, 4-chloro-6-dimethylaminotriazin-2-yl, 4-chloro-6-diethylaminotriazin-2-yl, 4-chloro-6-pyrrolidinotriazine -2-yl, 4-chloro-6-piperidinotriazin-2-yl, 4-chloro-6-piperazinotriazin-2-yl, 4-chloro-6-morpholinotriazin-2-yl, 4- Chloro-6-benzylaminotriazin-2-yl, 4-chloro-6-phenethylaminotriazin-2-yl, 4-chloro-6-anilinotriazin-2-yl, 4-chloro-6- (2-, 3- or 4-
Sulfoanilino) triazin-2-yl, 4-chloro-
6- (N-, 2-, 3- or 4-methylanilino) triazin-2-yl, 4-chloro-6- (N-, 2-, 3
-Or 4-ethylanilino) triazin-2-yl, 4
-Chloro-6- (2-, 3- or 4-methoxyanilino) triazin-2-yl, 4-chloro-6- (2-,
3- or 4-carboxyanilino) triazin-2-yl, 4-chloro-6- (2-, 3- or 4-carbamoylanilino) triazin-2-yl, 4-chloro-6-
(2-, 3- or 4-acetylanilino) triazine-
2-yl, 4-chloro-6- (2-, 3- or 4-chloroanilino) triazin-2-yl, 4-chloro-6-
(2,4- or 2,5-disulfoanilino) triazine-
2-yl, 4-chloro-6- (3 or 4- (2-hydroxyethylsulfonyl) anilino) triazin-2-yl, 4-chloro-6- (N-ethyl-3 or 4- (2-
Hydroxyethylsulfonyl) anilino) triazine-
2-yl, 4-chloro-6-hydroxytriazine-2
-Yl, 4-chloro-6-methoxytriazin-2-yl, 4-chloro-6-ethoxytriazin-2-yl,
And 4-chloro-6-phenoxytriazin-2-yl and the like.

As specific examples of monopyridiniotriazinyl, in the group exemplified as monochlorotriazinyl, chloro is replaced with pyridinio, 2-, 3- or 4-carbonylpyridinio, or 2-, 3- Or a group changed to 4-carbamoylpyridinio.

Specific examples of monofluorotriazinyl include groups exemplified as monochlorotriazinyl in which chloro is changed to fluoro.

Specific examples of di- or tri-halopyrimidinyl include 2,4-dichloropyrimidin-6-yl, 4,5
-Dichloropyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 2,4-difluoropyrimidin-6-yl, 4,5-difluoropyrimidin-6-yl, 4-fluoro-5-chloro Pyrimidin-6-yl,
And 2,4-difluoro-5-chloropyrimidine-6
And the like.

In the formula (2a), R ³ is hydrogen, methyl or ethyl, and Z is monochlorotriazinyl, monopyridiniotriazinyl, monofluorotriazinyl,
Alternatively, a group that is di- or tri-halopyrimidinyl is
preferable.

In formulas (2b) to (2e), Y ¹ , Y ² ,
Y ³ and Y ⁴ are the same or different and represent —CH ＝ CH ₂ or —CH ₂ CH ₂ L, where L is a group that is eliminated by the action of an alkali. Examples of the group capable of leaving by the action of an alkali represented by L include groups such as sulfate, thiosulfate, phosphate, acetate, and halogeno. Among them, a sulfate group and chloro are preferred. As Y ^{1 to} Y ⁴ , -CH = CH ₂ , -C
_{H 2 CH 2 Cl, -CH 2} CH 2 OSO 3 H and the like are preferable,
-CH = CH ₂ and -CH ₂ CH ₂ OSO ₃ H is particularly preferred.

A ¹ and A ² in the formulas (2c) and (2d) are the same or different and represent an aliphatic linking group.
The linking group of aliphatic, for example, -O -, - S- or -NR ¹⁶ - alkylene which may be interrupted by (which may also be branched be linear) can be exemplified such as,
Further, they may be substituted with the groups exemplified as the substituents of the substitutable alkyl represented by R ¹⁴ and R ¹⁵ .
R ¹⁶ represents hydrogen, optionally substituted alkyl, or optionally substituted phenyl. Examples of the substitutable alkyl represented by R ¹⁶ include the same groups as the substitutable alkyl represented by R ¹⁴ and R ¹⁵ . The substitutable phenyl represented by R ¹⁶ includes:
The same groups as those of the substitutable phenyl represented by R ¹ and R ² can be mentioned. As R ¹⁶ , hydrogen, methyl or ethyl is preferable, and hydrogen is particularly preferable.

The aliphatic linking group represented by A ¹ and A ² includes the following formula (5a) or (5b)

[0046]

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[Wherein, i represents an integer of 2 to 6, and j and k are the same or different and represent 2 or 3. Are preferable, and ethylene, trimethylene and ethyleneoxyethylene are particularly preferable.

Examples of the aromatic linking group represented by A ³ in the formula (2e) include the linking groups shown in the formulas (4a) and (4b), provided that the formula (4a) )
And the symbol * in (4b) represents a bond connected to —NR ⁸ —. A ³ is preferably unsubstituted phenylene or phenylene substituted with one or two substituents selected from sulfo, methyl and methoxy.

X ¹ and X ² in formulas (2d) and (2e) are the same or different and are fluoro, chloro, optionally substituted pyridinio, or formulas (3a), (3
b) represents a group represented by (3c) or (3d).

The substitutable pyridinio represented by X ¹ and X ² include, for example, pyridinio, 2-, 3- or 4-
Carboxypyridinio, 2-, 3- or 4-carbamoylpyridinio, 3-sulfopyridinio, 4- (2-sulfoethyl) pyridinio, 3- (2-hydroxyethyl)
Examples thereof include pyridinio, 4-chloropyridinio, 3-methylpyridinio, and 3,5-dicarboxypyridinio, and 3- or 4-carboxypyridinio is more preferable.

R ⁹ , R ¹⁰ , R ¹¹ and R ¹² in the formulas (3a), (3c) and (3d) are the same or different and are hydrogen, optionally substituted alkyl, or optionally substituted. Represents cycloalkyl, optionally substituted phenyl or optionally substituted naphthyl. The alkyl may be linear or branched, but is preferably an alkyl having 1 to 4 carbon atoms.

Examples of the substitutable alkyl or substitutable cycloalkyl represented by R ^{9 to} R ¹² include, for example, hydroxy, cyano, alkoxy having 1 to 4 carbons, halogeno, carbamoyl, carboxy, alkoxy (1 carbon atoms)
4) carbonyl, alkyl (1 to 4 carbon atoms) carbonyloxy, sulfo, sulfamoyl, optionally substituted phenyl, sulfate, 2-sulfatoethylsulfonyl, vinylsulfonyl, 2-chloroethylsulfonyl and 2 -Hydroxyethylsulfonyl include alkyl having 1 to 4 carbon atoms which may be substituted by one or two substituents selected from the group of -hydroxyethylsulfonyl, cyclopentyl, cyclohexyl and the like. Alkoxy having 1 to 4 carbon atoms, alkoxy (1 to 4 carbon atoms) carbonyl and alkyl (1 to 4 carbon atoms) as a substituent of the alkyl
Carbonyloxy may be linear or branched. Examples of the optionally substituted phenyl which is a substituent of the alkyl include, for example, selected from the group consisting of alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, sulfo, and halogeno (chloro, bromo, etc.). And phenyl which may be substituted by one or two substituents.

Specific examples of the substitutable alkyl represented by R ^{9 to} R ¹² include the same groups as those exemplified as the substitutable alkyl represented by R ¹⁴ and R ¹⁵ . Further, as substitutable alkyls represented by R ^{9 to} R ¹² , 2- (2-sulfo-ethylsulfonyl) ethyl, 2- (2-chloroethylsulfonyl) ethyl, 2-vinylsulfonylethyl, 2- ( 2-hydroxyethylsulfonyl) ethyl, 3- (2-sulfo-ethylsulfonyl) propyl, 3- (2-chloroethylsulfonyl) propyl, 3-vinylsulfonylpropyl, 3- (2-hydroxyethylsulfonyl) propyl, 2 -(2- (2-sulfo-ethylsulfonyl)
Ethyloxy) ethyl, 2- (2- (2-chloroethylsulfonyl) ethyloxy) ethyl, 2- (2- (2-
Examples thereof include hydroxyethylsulfonyl) ethyloxy) ethyl and benzyl which may be substituted.

The substitutable alkyl represented by R ^{9 to} R ¹² includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-hydroxyethyl, 2-sulfoethyl, 2-sulfoethyl, Methoxyethyl, 2-carboxyethyl, 2-carbamoylethyl,
Preferred are 2-sulfamoylethyl, benzyl, 2-, 3- or 4-sulfobenzyl, 2- (2-sulfatoethylsulfonyl) ethyl and the like.

The substitutable cycloalkyl represented by R ^{9 to} R ¹² is preferably an unsubstituted cycloalkyl,
Cyclopentyl and cyclohexyl are more preferred.

The substitutable phenyl represented by R ^{9 to} R ¹² includes, for example, alkyl having 1 to 4 carbons and 1
To 4, alkoxy, sulfo, carboxy, halogeno, hydroxy, cyano, carbamoyl, sulfamoyl, alkoxy (1 to 4 carbon atoms) carbonyl, alkyl (1 to 4 carbon atoms) carbonyloxy, amino, acylamino,
Alkylamino (1-4 carbon atoms), sulfate, 2-
Sulfatoethylsulfonyl, vinylsulfonyl, 2
And phenyl which may be substituted with one or two substituents selected from the group consisting of -chloroethylsulfonyl and 2-hydroxyethylsulfonyl. Alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkoxy (1 to 4 carbon atoms) carbonyl, alkyl (1 to 4 carbon atoms) carbonyloxy, and alkylamino (1 carbon atom) ~ 4) may be linear or branched

[0057] As the substitutable phenyl, denoted by R ⁹ to R ^12, there may be mentioned the same as the groups exemplified as substitutable phenyl, denoted by R ¹ and R ^2, further 2-, 3- or 4- (2-sulfo-ethylsulfonyl) phenyl, 2-, 3- or 4- (2-chloroethylsulfonyl) phenyl, 2-, 3- or 4-vinylsulfonylphenyl, and 2-, 3- or 4- (2-
Hydroxyethylsulfonyl) phenyl and the like are also exemplified.

The substitutable naphthyl represented by R ^{9 to} R ¹² is, for example, selected from the group consisting of alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, sulfo, carboxy, halogeno and hydroxy. And naphthyl which may be substituted by one, two or three substituents.

Substitutable naphthyls represented by R ^{9 to} R ¹² include 2-, 3-, 4-, 5-, 6-, 7- or 8-sulfo-1-naphthyl, 1-, 5- , 6-, 7- or 8-sulfo-2-naphthyl, 1,5-, 5,7-, 6,
8-, 4,8-, 4,7-, 3,8-, 4,6-, 3,7-
Or 3,6-disulfo-2-naphthyl, 4,6,8-, 2,
Examples thereof include 4,7- or 3,6,8-trisulfo-1-naphthyl, and 1,5,7-, 4,6,8- or 3,6,8-trisulfo-2-naphthyl.

Q in the formula (3b) is -CH_Two−, −
O-, -S-, -SO_Two-Or -NR ¹³-Represents R¹³
Represents hydrogen or an optionally substituted alkyl, e
Is 1, 2 or 3. R¹³Can be replaced by
As the alkyl, R¹⁴And R¹⁵Can be replaced by
And the same groups as the above-mentioned alkyl. R¹³age
Represents hydrogen, linear or branched alkyl having 1 to 4 carbon atoms
And the like, and hydrogen, methyl and ethyl are preferred.

As the group represented by the formula (3a), when R ⁹ is hydrogen or an optionally substituted alkyl, and R ¹⁰ is an optionally substituted alkyl or an optionally substituted phenyl. Is preferred. In particular, R ⁹ is hydroxy, cyano, methoxy, ethoxy, chloro, carbamoyl, carboxy, sulfo, sulfamoyl, phenyl, sulfate, 2-sulfatoethylsulfonyl, vinylsulfonyl, 2-chloroethylsulfonyl or 2-hydroxyethyl Alkyl having 1 to 4 carbon atoms which may be substituted with sulfonyl, or hydrogen,
R ¹⁰ is hydroxy, cyano, methoxy, ethoxy, chloro, carbamoyl, carboxy, sulfo, sulfamoyl, phenyl, sulfate, 2-sulfatoethylsulfonyl, vinylsulfonyl, 2-chloroethylsulfonyl or 2-hydroxyethylsulfonyl Alkyl having 1 to 4 carbon atoms which may be substituted, or methyl, ethyl, methoxy, ethoxy, sulfo, carboxy, chloro, hydroxy, cyano, carbamoyl, sulfamoyl, sulfate, 2-sulfatoethylsulfonyl Particularly preferred is phenyl which may be substituted with 1 to 2 substituents selected from the group consisting of vinylsulfonyl, 2-chloroethylsulfonyl and 2-hydroxyethylsulfonyl.

Examples of the group represented by the formula (3b) include pyrrolidino, piperidino, piperazino, n-alkylpiperazino, morpholino and thiomorpholino, and morpholino is particularly preferred.

The group represented by the above formula (3c) includes R
^It is preferred that ¹¹ is hydrogen, optionally substituted alkyl or optionally substituted phenyl, and R ¹¹ is hydrogen, methyl, ethyl or phenyl optionally substituted with sulfo or carboxy. Is particularly preferred.

Examples of the group represented by [0064] formula (3d), preferably when R ¹² is hydrogen, phenyl which is also alkyl or substituted optionally be substituted, R ¹² is hydrogen,
Particularly preferred is methyl, ethyl or phenyl optionally substituted by sulfo or carboxy.

When X ¹ and X ² in the formulas (2d) and (2e) are groups represented by the formula (3a), the amine compound represented by HNR ⁹ R ¹⁰ used to form this group is For example, the following can be mentioned.

A) ammonia;

B) The following aromatic amines: 1-aminobenzene, 1-amino-2-, -3- or -4-methylbenzene, 1-amino-2,4-, -3,4- or- 3,5
-Dimethylbenzene, 1-amino-2-, -3- or-
4-ethylbenzene, 1-amino-2-, -3- or-
4-methoxybenzene, 1-amino-2-, -3- or -4-ethoxybenzene, 1-amino-2-, -3- or -4-propylbenzene, 1-amino-2-, -3-
Or -4-isopropylbenzene, 1-amino-2-,
-3- or -4-chlorobenzene, 1-amino-2-,
-3- or -4-bromobenzene, 1-amino-2-,
-3- or -4-fluorobenzene, 1-amino-2,
4- or -2,5-dimethoxybenzene, 1-amino-
2-methoxy-5-methylbenzene, 3- or 4-aminophenylmethanesulfonic acid, 2-, 3- or 4-aminobenzenesulfonic acid, 3- or 4-methylaminobenzenesulfonic acid, 3- or 4-ethyl Aminobenzenesulfonic acid, 5-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,3- or -1,4-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid,
4-amino-5-methylbenzene-1,2-disulfonic acid, 1-amino-2-sulfo-4-methoxybenzene,
1-amino-2-sulfo-4-acetylaminobenzene, 2-, 3- or 4-aminobenzoic acid, 2-, 3- or 4-carbamoylaniline, 1-amino-2-carboxy-4-acetylaminobenzene , 5-aminobenzene-1,3-dicarboxylic acid, 5-amino-2-hydroxybenzenesulfonic acid, 4-amino-2-hydroxybenzenesulfonic acid, 5-amino-2-ethoxybenzenesulfonic acid, N-methylamino Benzene, N-ethylaminobenzene, 1-methylamino-3- or -4-methylbenzene, 1-ethylamino-3- or -4-methylbenzene, 1-methylamino-2-, -3- or -4 −
Chlorobenzene, 1-ethylamino-2-, -3- or -4-chlorobenzene, 1- (2-hydroxyethyl)
Amino-3-methylbenzene, 3- or -methylaminobenzoic acid, 1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethoxybenzene, 2
-, 3- or 4-aminophenol, 1-amino-3-
Or -4-acetylaminobenzene, 2,4- or 2,5
-Diaminobenzenesulfonic acid, 1-amino-2-,-
3- or -4- (2-sulfatoethylsulfonyl)
Benzene, 1-amino-2-, -3- or -4- (2-
Chloroethylsulfonyl) benzene, 1-amino-2
-, -3- or -4-vinylsulfonylbenzene, 1-
Amino-2-, -3- or -4- (2-hydroxyethylsulfonyl) benzene, 1-ethylamino-2-,-
3- or -4- (2-sulfatoethylsulfonyl)
Benzene, 1-ethylamino-2-, -3- or -4-
(2-chloroethylsulfonyl) benzene, 1-ethylamino-2-, -3- or -4-vinylsulfonylbenzene, 1-ethylamino-2-, -3- or -4- (2
-Hydroxyethylsulfonyl) benzene.

C) The following aliphatic amines: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, dimethylamine, diethylamine, methylethylamine, allylamine, 2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol, 2-methylaminoethanol, bis (2-
(Hydroxyethyl) amine, 2-acetylaminoethylamine, 1-amino-2-propanol, 3-methoxypropylamine, 1-amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid amide, 2-aminoethanesulfone Acid, aminomethanesulfonic acid, 2-methylaminoethanesulfonic acid amide, 2-methylaminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, 3- Aminopropionic acid, 3-aminopropionic amide, 3-methylaminopropionic acid, 3
-Methylaminopropionic acid amide, 3-aminocaproic acid, benzylamine, 2-, 3- or 4-sulfobenzylamine, 2-, 3- or 4-chlorobenzylamine, 2-, 3- or 4-methylbenzylamine , N-methylbenzylamine, 1-phenylethylamine, 2-
Phenylethylamine, 1-phenyl-2-propylamine, 2- (2-sulfo-ethylsulfonyl) ethylamine, 2- (2-chloroethylsulfonyl) ethylamine, 2-vinylsulfonylethylamine, 2- (2
-Hydroxyethylsulfonyl) ethylamine, 3-
(2-sulfo-ethylsulfonyl) propylamine, 3- (2-chloroethylsulfonyl) propylamine, 3-vinylsulfonylpropylamine, 3- (2-
(Hydroxyethylsulfonyl) propylamine, 2-
(2- (2-sulfatoethylsulfonyl) ethyloxy) ethylamine, 2- (2- (2-chloroethylsulfonyl) ethyloxy) ethylamine, 2- (2-
(2-Hydroxyethylsulfonyl) ethyloxy) ethylamine.

Among the above amine compounds a) to c), preferred are, for example, aniline, N-methylaniline, N-ethylaniline, 2-, 3- or 4-chloroaniline, N-methyl-2-amine. , -3- or -4-chloroaniline, N-ethyl-2-, -3- or -4-chloroaniline, 2-, 3- or 4-methylaniline, 2-,
3- or 4-ethylaniline, 2-, 3- or 4-methoxyaniline, 2-, 3- or 4-ethoxyaniline,
2-, 3- or 4-propylaniline, 2-, 3- or 4-isopropylaniline, 2-, 3- or 4-hydroxyaniline, aniline-2-, -3- or -4-sulfonic acid, 3- Or 4-methylaminobenzenesulfonic acid, 3- or 4-ethylaminobenzenesulfonic acid, 2
-, 3- or 4-carboxyaniline, 2-, 3- or 4-carbamoylaniline, 2,4- or 2,5-dimethoxyaniline, 2-sulfo-4-methoxyaniline, 2
-Sulfo-4-acetylaminoaniline, 2-carboxy-4-acetylaminoaniline, 2-methoxy-5-
Methylaniline, 1-amino-2-, 3- or 4- (2
-Sulfatoethylsulfonyl) benzene, 1-ethylamino-2-, 3- or 4- (2-sulfatoethylsulfonyl) benzene, ammonia, methylamine,
Ethylamine, dimethylamine, taurine, N-methyltaurine, mono- or di-ethanolamine, 2-sulfamoylethylamine, 2-carbamoylethylamine, 2- (2-sulfatoethylsulfonyl) ethylamine and the like can be mentioned. it can. Among these, aniline, N-methylaniline, N-ethylaniline, N-
Ethyl-2-, -3- or -4-chloroaniline, 2
-, 3- or 4-ethylaniline, 2-, 3- or 4-
Methoxyaniline, 2-, 3- or 4-propylaniline, 2-, 3- or 4-isopropylaniline, 2-,
3- or 4-hydroxyaniline, aniline-2-,-
3- or -4-sulfonic acid, 2-, 3- or 4-carboxyaniline, 2-, 3- or 4-carbamoylaniline, 2,4- or 2,5-dimethoxyaniline, 2-sulfo-4-methoxy Aniline, 2-sulfo-4-acetylaminoaniline, 2-carboxy-4-acetylaminoaniline, 2-methoxy-5-methylaniline, 1-amino-3- or 4- (2-sulfatoethylsulfonyl) benzene And 2- (2-sulfatoethylsulfonyl) ethylamine and the like are particularly preferred.

When X ¹ and X ² in the formulas (2d) and (2e) are a group represented by the formula (3c), examples of the compound represented by HOR ¹¹ used to form this group include: The following can be mentioned.

D) The following phenols: phenol, 1-hydroxy-2-, -3- or -4-
Methylbenzene, 1-hydroxy-3,4- or -3,5
-Dimethylbenzene, 1-hydroxy-2-, -3- or -4-ethylbenzene, 1-hydroxy-2-, -3
-Or-4-methoxybenzene, 1-hydroxy-2
-, -3- or -4-ethoxybenzene, 1-hydroxy-2-, -3- or -4-chlorobenzene, 3- or 4-hydroxyphenylmethanesulfonic acid, 3- or 4
-Hydroxybenzenesulfonic acid, 5-hydroxybenzene-1,3-disulfonic acid, 2-hydroxybenzene-1,4-disulfonic acid, 4-hydroxybenzene-1,
2-disulfonic acid, 4-hydroxy-5-methylbenzene-1,2-disulfonic acid, 3- or 4-hydroxybenzoic acid, 5-hydroxybenzene-1,3-dicarboxylic acid, 5-hydroxy-2-ethoxybenzene Sulfonic acid

E) The following aliphatic alcohols: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, 2-chloroethanol -2-methoxyethanol, 2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol, 2-hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2-cyanoethanol, 2-sulfatoethanol
, Glycolic acid, 3-hydroxypropionic acid, benzyl alcohol, 2-, 3- or 4-chlorobenzyl alcohol, 4-methylbenzyl alcohol, 2-, 3-
Or 4-sulfobenzyl alcohol, 2-phenylethanol, and 1-phenyl-2-propanol.

X ¹ in the above formulas (2d) and (2e)
And when X ² is a group represented by the above formula (3d), the compound represented by HSR ¹² used to form this group may be a mercapto group And the like.

In the above formula (2c), it is preferred that R ⁴ is hydrogen, methyl or ethyl, and A ¹ is ethylene, trimethylene or ethyleneoxyethylene.

In the formula (2d), R ⁵ is hydrogen, methyl or ethyl, R ⁶ is hydrogen, methyl, ethyl or phenyl, and A ² is ethylene, trimethylene or ethyleneoxyethylene; X ¹ is fluoro,
Preferred is chloro, optionally substituted pyridinio or a group represented by the above formula (3a).

In the above formula (2e), R ⁷ is hydrogen, methyl or ethyl, R ⁸ is hydrogen, methyl or ethyl, and A ³ is selected from unsubstituted phenylene or sulfo, methyl and methoxy. Preferred is phenylene substituted with one or two substituents, wherein X ² is fluoro, chloro, optionally substituted pyridinio, or a group represented by the above formula (3a).

Z ¹ in the azo compound (1) is represented by the formula (2)
It is preferably a fiber reactive group represented by b), (2d) or (2e), and particularly preferably a fiber reactive group represented by the formula (2b). Z in the azo compound (1)
² is preferably a fiber reactive group represented by the formula (2a), (2d) or (2e);
Particularly preferred is the fiber reactive group represented by e).

The azo compound of the present invention may be in the form of a free acid, a salt thereof, or a mixture thereof. It is preferably in the form of an alkali metal salt, an alkaline earth metal salt, or a mixture containing them, and among them, a sodium salt, a potassium salt, a lithium salt and a mixture containing them are preferred.

As the azo compound (1), the following formula (1a)
And the compounds represented by (1b) are particularly preferred.

[0080]

Embedded image [Z ² in the formula (1a) represents a fiber reactive group represented by the formula (2d). ]

[0081]

Embedded image [R ² in the formula (1b) is phenyl which may be substituted with a non-fiber reactive group, Z ¹ in the formula (1b) is a fiber reactive group represented by the formula (2b), and in the formula (1b) Z ² is a fiber reactive group represented by the formula (2d) or (2e). ]

The method for producing the azo compound (1) is not particularly limited. In the case of a compound in which b is 0, for example, the following formula (6)

[0083]

Embedded image

Wherein D ² , Z ² and d have the meanings as defined in claim 1. The compound represented by the following formula (7) is obtained by diazotizing a compound represented by the following formula (7):

[0085]

Embedded image

Wherein R ¹ , R ² and c have the meanings as defined in claim 1. And a compound represented by the following formula (1c):

[0087]

Embedded image

Wherein D ² , R ¹ , R ² , Z ² , c and d
Has the meaning of claim 1. The azo compound represented by the following formula can be obtained.

The azo compound wherein b in the formula (1) is 1 is, for example, a compound represented by the following formula (8)

[0090]

Embedded image

Wherein D ¹ , Z ¹ and a have the meanings as defined in claim 1. The compound of formula (1c) can be obtained by diazotizing the compound of formula (1) according to a conventional method, and subjecting the resulting diazo compound to a coupling reaction with the compound of formula (1c).

The conditions for the above-mentioned coupling reaction are not particularly limited.
PH 0-5 at 0 ° C, secondary temperature 0 ° C + 4
It can be carried out while adjusting the pH to 2 to 8 at 0 ° C.

Further, when Z ¹ and / or Z ² are the formulas (2a) and (2
In the case of the fiber reactive group represented by d) or (2e), the introduction of these groups may be performed after the above coupling reaction. That is, in the method described above, instead of the compound represented by the above formula (6) and / or (8),
The following formula (9) and / or (10)

[0094]

Embedded image

Wherein D ¹ , D ² , a and d are as defined in claim 1
It has the meaning described. R ¹⁷ and R ¹⁸ are R ³ , R ⁵ or R
Synonymous with ⁷ . The compound represented by the formula (11), the compound represented by the formula (12) or the compound represented by the formula (12) is subjected to a diazotization reaction and a coupling reaction using the compound represented by the formula (11). By condensing the compound represented by 13) by a conventional method,
An azo compound (1) can be obtained.

[0096]

Embedded image

Wherein Z, R ⁶ , R ⁸ , A ² , A ³ , Y ³ ,
Y ⁴ , X ¹ and X ² have the meaning of claim 1 and Ha
1 represents halogeno. ]

Further, when Z ¹ and / or Z ² is a fiber reactive group represented by the formula (2d) or (2e), introduction of a substituent into the triazine ring may be performed after the above coupling reaction. . That is, in the method described above, instead of the compound represented by the formula (6) and / or (8),
Formula (14) and / or (15) below

[0099]

Embedded image

[Wherein D ¹ , D ² , a and d have the same meanings as in claim 1, and R ¹⁷ , R ¹⁸ and Hal have the same meanings as described above. Is carried out by using the compound represented by the formula (1), and the resulting coupling reaction product is added to the following formula (16) and / or (17)

[0101]

Embedded image

Wherein R ⁶ , R ⁸ , A ² , A ³ , Y ³ and Y ⁴
Has the meaning of claim 1. Is condensed by a conventional method, and if necessary, the following formula (18)
And / or (19)

[0103]

Embedded image

[Where X is the formula (3a), (3b), (3
represents a group represented by c) or (3d), wherein R is methyl, ethyl, sulfoethyl, hydroxyethyl, carboxy,
Represents carbamoyl or chloro, and l represents 0, 1 or 2. The azo compound (1) can also be obtained by condensing the compound represented by the formula (1) by a conventional method.

In the above condensation reaction with the compound having a triazine ring, the condensation order may be reversed.
That is, the product of the coupling reaction using the compound represented by the formula (14) and / or (15) is added to the product represented by the formula (18)
And / or condensing the compound represented by (19) first,
Thereafter, the azo compound (1) can also be obtained by condensing the compound represented by the formula (16) and / or (17).

Further, in obtaining the azo compound (1),
The group represented by Y ¹ and Y ² in the fiber reactive groups represented by the formulas (2b), (2c), (2d) and (2e) is —CH ₂ C
When the group L which is H ₂ L and which leaves by the action of an alkali is, for example, an ester such as a sulfate or a phosphate, the formation of the ester group is carried out after the coupling reaction and / or the condensation reaction. You may.

The azo compound (1) or a salt thereof is, for example,
It is useful as a dye for dyeing or printing fiber materials. The fiber material is not particularly limited as long as it contains a hydroxy group and / or a carboxamide group. For example, natural or regenerated cellulose fiber material, natural or synthetic polyamide fiber material, polyurethane fiber material, leather, And blended materials containing these.

Examples of natural cellulose fiber materials include cotton and other plant fibers such as linen,
Hemp, jute and laminating fibers can be mentioned.

Specific examples of the regenerated cellulose fiber material include rayon, polynosic, cupra fiber, and trade names “TENCEL”, “Toughcell”, “Modal”, “Certima” and the like. it can.

As the natural or synthetic polyamide fiber material,
Specifically, wool, other animal hair, silk, polyamide
6, 6, polyamide-6, polyamide-11, polyamide-4 and the like.

Examples of the blended material containing these include, in addition to the blended material of these fiber materials, a blended material of these fiber materials and synthetic fibers such as polyester, nylon and acrylic. .

The azo compound (1) or a salt thereof can be dyed or printed on the above-mentioned material, especially on the above-mentioned fiber material by a method according to the physicochemical properties. Specifically, for example, a method of dyeing or printing on the above-described fiber material by an exhaust dyeing method, a cold batch-up method, a continuous dyeing method, a printing method, or the like can be mentioned. For example, in the case of exhaustion dyeing on a cellulose fiber material, sodium carbonate,
In the presence of an acid binder such as tertiary sodium phosphate, sodium bicarbonate, and caustic soda, a neutral salt such as sodium sulfate and sodium chloride are added, if necessary, and further dissolved, if necessary. A method of dyeing at a temperature of 30 ° C. to 100 ° C. using an auxiliary agent, a penetrating agent, a leveling agent or the like in combination is exemplified. Here, the addition of the acid binder, the neutral salt, and the like may be performed all at once, or may be performed in a divided manner by a conventional method.

In the case of dyeing a cellulose fiber by a cold batch-up method, neutral dyes such as sodium sulfate and salt may be used.
Further, a method of padding using an acid binder such as caustic soda or sodium silicate, followed by treatment in a hermetically sealed packaging material left at a constant temperature, or the like is exemplified.

In the case of dyeing cellulose fibers by the continuous dyeing method, padding is carried out at room temperature or at an elevated temperature by a known method in the presence of an acid binder such as sodium carbonate or sodium bicarbonate. After that, the fiber is immersed in a padding solution in which the compound of the present invention is dissolved, or after the fiber is immersed in a padding solution in which the compound of the present invention is dissolved, neutral salts such as sodium sulfate and sodium chloride, and caustic soda or the like. Examples thereof include a two-phase padding method in which an acid binder such as sodium silicate is padded and treated by steaming or drying.

In the case of printing on cellulose fibers, a method of printing in a single phase with a printing paste containing a binder such as baking soda and then steaming at a high temperature of 80 ° C. or higher may be used. , Two-phase printing, for example, with a neutral or weakly acidic printing paste and passing it through an electrolyte-containing alkaline bath, or with an alkaline electrolyte-containing padding solution.
A method of treating by padding, followed by steaming or dry heat is exemplified. Here, the printing paste may contain a sizing agent and / or an emulsifier such as sodium alginate and starch ether, and if necessary, a printing aid such as urea and / or Alternatively, it may contain a dispersant.

When the compound of the present invention is dyed or printed on cellulose fibers, the acid binder used is not particularly limited. For example, an alkali metal hydroxide, an alkali metal or an alkaline earth metal and an inorganic or organic Examples thereof include a water-soluble basic salt with an acid and a compound that releases an alkali under heating. In particular, mention may be made of alkali metal hydroxides and alkali metal salts of inorganic acids or organic acids of weak to moderate strength, of which sodium or potassium hydroxides, sodium salts and potassium salts are preferred. Specific examples of such an acid binder include the above-mentioned sodium carbonate.
Sodium, tertiary sodium phosphate, sodium bicarbonate, caustic soda, sodium carbonate, sodium silicate, sodium bicarbonate, caustic potash, sodium formate, potash, primary or secondary Sodium diphosphate and soda trichloroacetate are also included.

In the case of exhaustion dyeing on synthetic or natural polyamide fibers or polyurethane fibers, acidic to
Examples of the method include a method in which the compound of the present invention is exhausted in a weakly acidic dyeing bath while controlling the pH value, and then the pH is changed to a neutral to alkaline pH value at a temperature of about 60 to 120 ° C. If necessary, a leveling agent such as cyanuric chloride and 3
A leveling agent such as a condensation product of a double molar amount of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or an addition product of, for example, stearylamine and ethylene oxide may be used.

The azo compound of the present invention or a salt thereof has good water solubility, and particularly when dyeing or printing a cellulose fiber material, reproducibility, leveling property, build-up property and wash-off property are obtained. It is good and has a high effective dyeing rate. In addition, there is an advantage that dyeing can be performed at a low salt concentration.

Further, by using the azo compound of the present invention or a salt thereof, various fastnesses, in particular, chlorine resistance, light resistance, sweat resistance, sweat sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance A dyed product and a printed product having good resistance and washing resistance to peroxide washing can be obtained.

The azo compound of the present invention or a salt thereof can be used by mixing with other dyes, if necessary, in order to obtain a desired hue, as long as the characteristics of the present invention are not impaired. The dye used in combination is not particularly limited as long as it is a reactive dye.For example, as a reactive group, a sulfatoethyl sulfone group, a vinyl sulfone group, a monochlorotriazine group, a monofluorotriazine group, a mononicotinic acid triazine group, Dyes having at least one of dichlorotriazine, difluoromonochloropyrimidine and trichloropyrimidine groups, or Sumifix, Sumfix Supra, S
umfix HF, Remazol, Levafi
x, Procion, Cibacron, Basile
n, Drimarene, Kayacation, Kaya
Dyes which are commercially available under the titles such as Celon React, and further, JP-A-50-178, JP-A-51-17538,
JP-A-56-9483, JP-A-56-15481, JP-A-56-118
No. 976, JP-A-56-128380, JP-A-57-2365, JP-A-57-89679, JP-A-57-143360, JP-A-58-19175
No. 5, JP-A-59-15451, JP-A-59-96174, JP-A-5
9-161463, JP-A-60-6754, JP-A-60-123559
JP-A-60-229957, JP-A-60-260654, JP-A-61-126175, JP-A-61-155469, JP-A-61-2252
No. 56, JP-A-63-77974, JP-A-63-225664, JP-A-1-185370, JP-A-3-770, JP-A-5-247366,
The dyes described in JP-A-6-287463 and C.I. I. Reactive Blue 19, C.I. I. Re
Dyes represented by active Black 5 are exemplified.

[0121]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, "parts" represents parts by weight. Example 1 According to a conventional method, 3.69 parts of cyanuric chloride and 4.66 parts of 2- (2-sulfatoethylsulfonyl) ethylamine are condensed in an aqueous medium at a pH of 1 to 4 and a temperature of -5 ° C to + 20 ° C, Next, 3.76 parts of 2,4-diaminobenzenesulfonic acid was added at pH 2.5 to 7, at a temperature of 0 to 30 ° C.
To form the free acid in the following formula (20)

[0122]

Embedded image

The compound represented by the following formula was obtained. The compound of the above formula (20) is diazotized by a conventional method, and the obtained diazotized product is mixed with 4.79 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid, pH 1 to 3.5, and 0 ° C to 30 ° C. And the form of the free acid is represented by the following formula (21)

[0124]

Embedded image

A monoazo compound represented by the formula (λmax = 5
18 nm in an aqueous medium).

Example 2 2- (2-sulfatoethylsulfonyl) ethylamine, 2,4-diaminobenzenesulfonic acid and 2-
In place of amino-8-hydroxynaphthalene-6-sulfonic acid, columns 2, 3 and 4 of Tables 1 and 2 below were used in that order.
Synthesizing in the same manner as in Example 1 except that the compounds in the column are used, each gives a corresponding monoazo compound.

[0127]

[Table 1]

[0128]

[Table 2]

Example 3 By a conventional method, 3.69 parts of cyanuric chloride and 4.66 parts of 2- (2-sulfatoethylsulfonyl) ethylamine were added in an aqueous medium at a pH of 1 to 4 and a temperature of -5 to + 20 ° C. And then condensed with 3.76 parts of 2,4-diaminobenzenesulfonic acid at a pH of 2.5 to 7,
Condensate at a temperature between 0 ° C and 30 ° C. In the obtained condensate,
Further, 1.86 parts of aniline were added at pH 2 to 7 at a temperature of 30 ° C.
To 70 ° C., the free acid form is represented by the following formula (2)
2)

[0130]

Embedded image

The compound represented by the following formula is obtained. The above equation (2
The compound shown in 2) is diazotized by a conventional method, and the obtained diazotized product is obtained by mixing 4.79 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid with a pH of 1 to 3.5 at 0 ° C.
When the coupling reaction is carried out under the condition of ３０30 ° C., the form of the free acid becomes

[0132]

Embedded image

A monoazo compound represented by the following formula is obtained.

Example 4 2- (2-sulfatoethylsulfonyl) ethylamine, 2,4-diaminobenzenesulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, and
Instead of aniline, in order, the second column of Tables 3-10, the third column
By synthesizing in the same manner as in Example 3 except that the compounds in the columns, columns 4 and 5, are used, the corresponding monoazo compounds are obtained. In the above synthesis, even if the order of the primary condensation, the secondary condensation and the tertiary condensation of the compounds in the second column, the third column and the fifth column of Tables 3 to 10 with respect to cyanuric chloride was changed, The same compound is obtained.

[0135]

[Table 3]

[0136]

[Table 4]

[0137]

[Table 5]

[0138]

[Table 6]

[0139]

[Table 7]

[0140]

[Table 8]

[0141]

[Table 9]

[0142]

[Table 10]

Example 5 By a conventional method, 3.69 parts of cyanuric chloride and 4.66 parts of 2- (2-sulfatoethylsulfonyl) ethylamine were added in an aqueous medium at a pH of 1 to 4 and a temperature of -5 to + 20 ° C. And then condensed with 3.76 parts of 2,4-diaminobenzenesulfonic acid at a pH of 2.5 to 7,
The compound was condensed at a temperature of 0 ° C. to 30 ° C. to obtain a compound represented by the above formula (20). The compound represented by the formula (20) is diazotized by a conventional method, and the obtained diazotized product is obtained by 4.7-amino-8-hydroxynaphthalene-6-sulfonic acid 4.7
Nine parts were subjected to a coupling reaction under the conditions of pH 1 to 3.5 and 0 ° C to 30 ° C to obtain a compound represented by the above formula (21). Separately, 4- (2-sulfo-ethylsulfonyl)
5.63 parts of aniline were diazotized by a conventional method. The obtained diazotized product is combined with the above-mentioned coupling reaction product at pH 4
To 8, 0 ° C to 30 ° C, and after completion of the reaction, salting out and the form of the free acid is represented by the following formula (25)

[0144]

Embedded image

The compound represented by the following formula was obtained. (Λmax = 5
26 nm in an aqueous medium)

Example 6 2- (2-sulfatoethylsulfonyl) ethylamine, 2,4-diaminobenzenesulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, and
A compound was synthesized in the same manner as in Example 5 except that the compounds in the second, third, and fourth columns of Tables 11 to 14 below were used instead of 4- (2-sulfo-ethylsulfonyl) aniline in order. Respectively, to obtain the corresponding monoazo compounds.

[0147]

[Table 11]

[0148]

[Table 12]

[0149]

[Table 13]

[0150]

[Table 14]

Example 7 By a conventional method, 3.69 parts of cyanuric chloride and 4.66 parts of 2- (2-sulfatoethylsulfonyl) ethylamine were added in an aqueous medium at a pH of 1 to 4 and a temperature of -5 to + 20 ° C. Condensation and then 3.76 parts of 2,4-diaminobenzenesulfonic acid, pH 2.5 to 7, temperature 0 to 30 ° C
When 1.86 parts of aniline are further condensed at a pH of 2 to 7 and a temperature of 30 to 70 ° C., the above formula (2)
The compound represented by 2) is obtained. The compound represented by the formula (22) is diazotized by a conventional method, and the resulting diazotized product is obtained by mixing 4.79 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid with a pH of 1 to 3.5 and a temperature of 0 ° C to 30 ° C. To give a compound of the above formula (23).

Separately, 5.63 parts of 4- (2-sulfatoethylsulfonyl) aniline was diazotized by a conventional method,
This diazotized product is combined with the above coupling reaction product at pH 4
~ 8, the coupling reaction at 0 ° C to 30 ° C,
When salting out, the form of the free acid is represented by the following formula (26)

[0153]

Embedded image

The compound represented by the following formula is obtained.

Example 8 2- (2-Sulfatoethylsulfonyl) ethylamine, 2,4-diaminobenzenesulfonic acid, aniline,
2-amino-8-hydroxynaphthalene-6-sulfonic acid and 4- (2-sulfatoethylsulfonyl)
The synthesis was performed in the same manner as in Example 7 except that the compounds in columns 2, 3, 4, 5, and 6 of Tables 15 to 18 were used in place of aniline. Is obtained. In the above synthesis, even if the order of the primary condensation, the secondary condensation, and the tertiary condensation of the compounds in the second column, the third column, and the fourth column of Tables 15 to 18 with respect to cyanuric chloride was changed, The same compound is obtained.

[0156]

[Table 15]

[0157]

[Table 16]

[0158]

[Table 17]

[0159]

[Table 18]

Dyeing Example 1 0.3 part of the compound obtained in Example 1 is dissolved in 200 parts of water, 20 parts of sodium sulfate are added, 10 parts of cotton are further added, and the temperature is raised to 60 ° C. 30 minutes after the temperature reached 60 ° C., 4 parts of soda carbonate was added, dyed at the same temperature for 1 hour, washed with water, and soaped. The wash-off property at the time of washing and soaping was good, and the coloring amount of the dyeing wastewater was slight. The resulting dyed product was uniform and dark red. In addition, the resulting dyed product has various fastnesses of chlorine resistance, light resistance, sweat resistance, sweat sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance, and peroxide washing resistance.
All were good.

Dyeing Example 2 The procedure of Dyeing Example 1 was repeated except that the amount of sodium sulfate was changed from 20 parts to 10 parts. The dyeing obtained is of the same quality as the dyeing of Dyeing Example 1.

Dyeing Example 3 The procedure of Dyeing Example 1 is repeated except that the amount of sodium sulfate used is changed from 20 parts to 4 parts. The dyeing obtained is of the same quality as the dyeing of Dyeing Example 1.

Dyeing Example 4 The procedure was the same as in Dyeing Examples 1 to 3, except that the dyeing temperature was changed from 60 ° C. to 70 ° C. The dyed product obtained is dyeing examples 1 to
The quality is equivalent to that of the dyed product No. 3.

Dyeing Example 5 The procedure of Dyeing Examples 1 to 3 was repeated except that the dyeing temperature was changed from 60 ° C. to 80 ° C. The dyed matter obtained is dyeing examples 1 to
The quality is equivalent to that of the dyed product No. 3.

Dyeing Example 6 Instead of 0.3 part of the compound obtained in Example 1, 0.3 part of the compound obtained in Example 1 and a condensate of methylnaphthalenesulfonic acid and formaldehyde (Na salt, sulfone Except that a mixture having a degree of polymerization of 110% and an average degree of polymerization of 1.8) of 0.06 parts was used, the same procedures as in Dyeing Examples 1 to 5 were carried out. The resulting dyed product has the same quality as the dyed products of Dyeing Examples 1 to 5.

Printing Example 1 Using the monoazo compound obtained in Example 1, a color paste having the following composition is prepared.

Color paste composition Monoazo compound 5 parts Urea 5 parts Sodium alginate (5%) Original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance (water) 13 parts

This color paste was printed on mercerized cotton cloth, intermediate dried, steamed at 100 ° C. for 5 minutes, washed with hot water, soaped, washed with hot water, and dried.
Finish. The print is uniform and dark red. All of the fastnesses of the printed matter are good.

Dyeing Example 8 Instead of the monoazo compound obtained in Example 1, Examples 2 to 8
Is performed using the compound or the compound of the formula (1). The obtained dyed product has the same quality as the dyed product obtained in Dyeing Examples 1 to 6.

[0170]

The azo compound of the present invention or a salt thereof is useful as a red reactive dye and has excellent build-up properties, wash-off properties and water solubility. Further, according to the method of the present invention, a dyed product or a printed product excellent in various fastnesses can be obtained with good reproducibility.

Claims (15)

[Claims] An azo compound represented by the following formula (1) or a salt thereof. Embedded image [Wherein a, b, c and d are the same or different and represent 0 or 1. D ¹ represents a phenylene group which may be substituted with a non-fiber reactive group or a naphthylene group which may be substituted with a non-fiber reactive group when a is 1, and
Represents a phenyl group optionally substituted with a non-fiber reactive group or a naphthyl group optionally substituted with a non-fiber reactive group. D ² represents a phenylene group which may be substituted with a non-fiber reactive group or a naphthylene group which may be substituted with a non-fiber reactive group when d is 1, and when d is 0, A phenyl group which may be substituted with a non-fiber reactive group or a naphthyl group which may be substituted with a non-fiber reactive group. R ¹ represents hydrogen or an alkyl optionally substituted with a non-fiber reactive group, and R ² represents hydrogen, an alkyl optionally substituted with a non-fiber reactive group, or substituted with a non-fiber reactive group. Represents phenyl, Z ¹
And Z ² are the same or different, and have the following formulas (2a), (2
b), (2c), (2d) or (2e) 中 In the formula, Z represents —N (R ⁶ ) —A ² —SO ₂ —Y ³ and —N
(R ⁸ ) —A ³ —SO ₂ —Represents a heterocyclic fiber reactive group not containing Y ⁴ , wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different, Hydrogen, alkyl which may be substituted with a non-fiber reactive group or phenyl which may be substituted with a non-fiber reactive group, A ¹ and A ² are the same or different and represent an aliphatic linking group , A ³ represents an aromatic linking group, and Y ¹ , Y ² , Y ³ and Y ⁴ are the same or different, and
H = CH ₂ or —CH ₂ CH ₂ L, wherein L is a group capable of leaving under the action of an alkali, and X ¹ and X ² are the same or different and are fluoro, chloro, optionally substituted pyridinio Or the following formula (3a), (3b), (3c) or (3d): (R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted phenyl or substituted represents also a naphthyl, Q is -CH ₂
-, - O -, - S -, - SO 2 - or -NR ¹³ - represents, R ¹³ represents an alkyl which may be hydrogen or substituted, e is 1, 2 or 3. ).繊 維 represents a fiber reactive group. However, when b is 0, c is 0, d is 1, and Z ² is a fiber reactive group represented by the above formula (2d) or (2e);
Is 1, at least one of a and d is 1.
At least one of Z ¹ and Z ² is a fiber reactive group represented by the above formula (2d) or (2e). ] 2. The azo compound according to claim 1, wherein b is 1, or a salt thereof. 3. The azo compound according to claim 2, wherein a is 0, or a salt thereof. 4. The azo compound according to claim 2, wherein a is 1, or a salt thereof. 5. A group in which b is 1 and at least one of D ¹ and D ² is a phenyl group optionally substituted with a non-fiber reactive group or a phenylene group optionally substituted with a non-fiber reactive group. The azo compound according to any one of claims 1 to 4, or a salt thereof. 6. The azo compound or a salt thereof according to claim 1, wherein c is 0. 7. The azo compound according to claim 1, wherein d is 1, or a salt thereof. 8. The method according to claim ¹ , wherein R ¹ is hydrogen and R ² is phenyl optionally substituted with a non-fiber reactive group.
Or the salt thereof. 9. When a and b are 1 and Z ¹ is a formula (2)
The azo compound or a salt thereof according to any one of claims 1, 2 and 4 to 8, which is a fiber reactive group represented by b), (2d) or (2e). 10. The azo compound or a salt thereof according to claim 9, wherein Z ¹ is a fiber reactive group represented by the formula (2b). 11. The azo compound or a salt thereof according to claim 9, wherein a, b and d are 1, and Z ² is a fiber reactive group represented by the formula (2d) or (2e). 12. A phenylene group wherein a, b and d are 1, c is 0, D ¹ is a phenylene group optionally substituted with a non-fiber reactive group, and D ² is a phenylene group substituted with a sulfo. R ¹ is hydrogen, R ² is phenyl optionally substituted with a non-fiber reactive group, Z ² is a fiber reactive group represented by the formula (2d) or (2e), and The azo compound or a salt thereof according to claim 11, wherein Z ¹ is a fiber reactive group represented by the formula (2b). 13. A a, b and c is 0, d is 1, a fiber-reactive group Z ² is represented by formula (2d), D ²
Is a phenylene group substituted with a sulfo, R ¹ is hydrogen, and R ² is phenyl optionally substituted with a non-fiber reactive group, or an azo compound or a salt thereof. 14. The azo compound or a salt thereof according to claim 12, wherein X ¹ or X ² is chloro, optionally substituted pyridinio, or a group represented by the formula (3a). 15. A method for dyeing or printing a fiber material, comprising using the azo compound according to claim 1 or a salt thereof.