JP2005213518A - Bisazo compound or its salt - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bisazo compound or its salt which shows a good dyeing property, dyeing reproducibility and level dyeability at a low salt concentration and yields a navy dyed product excellent in various fastness properties. <P>SOLUTION: The bisazo compound of formula (1) (wherein R<SP>1</SP>and R<SP>2</SP>are each an alkyl or a hydrogen atom optionally substituted by a substituent chosen from the group consisting of hydroxy, cyano, alkoxy, halogeno, carboxy and sulfo; U is a group of formula (2b) or (2c) (wherein R<SP>4</SP>-R<SP>5</SP>are each a phenyl group optionally substituted by a substituent chosen from the group consisting of hydroxy, cyano, alkoxy and sulfo; A<SB>2</SB>is a 2-4C alkylene optionally substituted by a substituent chosen from the group consisting of alkyl, halogeno, hydroxy, sulfo or alkoxy; Q<SB>1</SB>is -O-, -S- or -NR<SP>6</SP>-; r-s are each 2-4; and Z<SP>2</SP>-Z<SP>3</SP>are each a fiber-reactive group of formulae (3a)-(3b)); X<SP>1</SP>and X<SP>2</SP>are each an optionally substituted pyridinio, fluoro or chloro; and T is a group which is non-reactive with fibers) or its salt is used in a dyeing or printing method of a fibrous material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an amber bisazo compound or a salt thereof useful for dyeing or printing cellulosic fiber materials and the like, and application to those fiber materials.

  Amber reactive dyes used in the field of dyeing and printing of cellulosic fiber materials and the like are known from Patent Document 1 and Patent Document 2, for example.

  However, in dyeing or printing cellulosic fiber materials, etc., the dyeability at low salt concentration, dyeing reproducibility, leveling and dyeing performance (build-up property, effective dyeing rate, wash-off property, etc.) are better. Amber dyeing with excellent fastness (chlorine resistance, light resistance, sweat resistance, sweat sun resistance, acid hydrolysis resistance, alkali resistance, washing resistance, and peroxidation washing resistance, etc.) A bisazo compound or a salt thereof that gives the above has not been found.

JP-A-57-78458 JP-A-57-198757

  In the dyeing or printing of cellulosic fiber materials, the present inventors have better dyeability at low salt concentrations, dye reproducibility, levelness and the above dyeing performance, and excellent fastness. As a result of diligent research to provide a bisazo compound or a salt thereof that gives an amber dyed dye, one vinyl sulfone system having two triazine rings and a divalent linking group on either of the rings The present invention has been completed by finding that a compound having a specific structure having a fiber reactive group or a salt thereof achieves the above object.

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

[Wherein, R ¹ and R ² each independently represents 1 to 1 carbon atoms which may be substituted with a substituent selected from the group consisting of hydroxy, cyano, alkoxy having 1 to 4 carbon atoms, halogeno, carboxy and sulfo. 4 represents an alkyl or hydrogen atom, and U represents a group represented by the following formula (2b) or (2c).

{Wherein R ⁴ and R ⁵ each independently represent a hydrogen atom or substituted with a substituent selected from the group consisting of hydroxy, cyano, alkoxy having 1 to 4 carbon atoms, halogeno, carboxy and sulfo. Or an alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl group.
A ₂ represents alkylene having 2 to 4 carbon atoms which may be substituted with a substituent selected from the group consisting of alkyl having 1 to 4 carbon atoms, halogeno, hydroxy, sulfo, cyano and alkoxy having 1 to 4 carbon atoms.
Q ₁ represents —O—, —S—, or —NR ⁶ —.
R ⁶ is hydroxy, cyano, C 1-4 alkoxy, halogeno, carboxy and sulfo which may be substituted with a substituent selected from the group consisting of sulfo and phenyl which may be substituted with sulfo Or represents a hydrogen atom.
r and s each independently represent 2, 3 or 4.
Z ² and Z ³ each independently represent a fiber reactive group represented by the following formula (3a) or (3b). }

［式中、Ｙ¹及びＹ²は−ＣＨ＝ＣＨ₂又は−ＣＨ₂ＣＨ₂Ｌを表し、Ｌはアルカリの作用で脱離する基であり、Ｒ⁷は水素又は炭素数１〜４のアルキルを表し、ｍは１〜６の整数である。］
Ｘ¹及びＸ²は、それぞれ独立に置換されてもよいピリジニオ、フルオロ又はクロロであり、Ｔは下式（４ａ）、（４ｂ）又は（４ｃ）で示される非繊維反応性基を表す。

[Wherein Y ¹ and Y ² represent —CH═CH ₂ or —CH ₂ CH ₂ L, L represents a group capable of leaving by the action of an alkali, and R ⁷ represents hydrogen or an alkyl having 1 to 4 carbon atoms. M is an integer of 1-6. ]
X ¹ and X ² are each independently pyridinio, fluoro or chloro, and T represents a non-fiber reactive group represented by the following formula (4a), (4b) or (4c).

{Wherein R ⁸ is alkyl having 1 to 4 carbon atoms which may be substituted with one or two substituents selected from the group consisting of hydroxy, cyano, alkoxy having 1 to 4 carbon atoms, halogeno, carboxy and sulfo. Or a hydrogen atom.
R ⁹ represents hydroxy, cyano, alkyl having 1 to 4 carbons, alkyl having 1 to 4 carbons which may be substituted with 1 or 2 substituents selected from the group consisting of alkoxy, halogeno, carboxy and sulfo; Or R ⁹ is alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, carboxy, halogeno, hydroxy, cyano, carbamoyl, carboxylic acid ester, amino, acylamino and alkyl (1 to 4 carbons) amino Represents phenyl which may be substituted by 1 or 2 substituents selected from:
R ¹⁰ represents hydroxy, cyano, alkyl having 1 to 4 carbons, alkyl having 1 to 4 carbons which may be substituted with 1 or 2 substituents selected from the group consisting of alkoxy, halogeno, carboxy and sulfo; Alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, halogeno, hydroxy, cyano, carbamoyl, sulfamoyl, carboxylic acid ester, 2-hydroxyethylsulfonyl, amino, alkylcarbonyl having 2 to 5 carbon atoms Amino, alkyl (C1-4) represents phenyl optionally substituted with 1 or 2 substituents selected from the group of amino, or represents a hydrogen atom.
Q ² represents —CH ₂ —, —O—, —S—, —SO ₂ — or —NR ¹¹ —.
R ¹¹ represents halogeno, alkyl optionally substituted with 1 to 4 carbon atoms, or a hydrogen atom. n is 1, 2 or 3. }
However, two * marks shown in [] represent one bond with -U, and the other represents a bond with -T. ]

The compound of the present invention is particularly excellent in reproducibility when dyeing or printing cellulose fiber materials, has good leveling and wash-off properties, has high build-up properties, and has an effective dyeing rate. It is expensive. Moreover, there is an advantage that it can be dyed at a low salt concentration.
Furthermore, by using the compound of the present invention, various fastnesses, particularly chlorine resistance, light resistance, sweat resistance, sweat sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance and peroxidation washing resistance can be obtained. Good dyeings and prints can be obtained.

The bisazo compound (1) or a salt thereof in the present invention will be described below.
R ¹ and R ² in formula (1) each independently represent hydrogen or optionally substituted alkyl.
Said alkyl is a C1-C4 thing, As a C1-C4 alkyl substituent, hydroxy, cyano, a C1-C4 alkoxy, halogeno, carboxy, and sulfo are mentioned, for example. .
The alkyl having 1 to 4 carbon atoms and the alkoxy having 1 to 4 carbon atoms which is a substituent of the alkyl having 1 to 4 carbon atoms may be linear or branched.

Examples of the alkyl represented by R ¹ and R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3 -Hydroxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 1-hydroxymethyl-1-methylethyl, 1,1-di (hydroxymethyl) ethyl, 1,1-di (Hydroxymethyl) -2-hydroxyethyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl 2-ethoxyethyl, 3-methoxypropyl, 3- Toxipropyl, 2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl , 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl and the like.

R ¹ and R ² are preferably a hydrogen atom, methyl or ethyl, and particularly preferably a hydrogen atom.

In the bisazo compound (1) or a salt thereof of the present invention, U is a group represented by the above formula (2b) or (2c).
R ⁴ and R ⁵ in the above formulas (2b) and (2c) each independently represent a hydrogen atom or a substituent selected from the group consisting of hydroxy, alkoxy having 1 to 4 carbon atoms, halogeno, carboxy and sulfo. Represents an optionally substituted alkyl group having 1 to 4 carbon atoms or optionally substituted phenyl.
R ⁴ and R ⁵ are preferably a hydrogen atom, methyl or ethyl.

A ² in formula (2b) represents alkylene having 2 to 4 carbon atoms, and the alkylene is selected from the group consisting of alkyl having 1 to 4 carbon atoms, halogeno, hydroxy, sulfo, cyano, and alkoxy having 1 to 4 carbon atoms. It may be substituted with a substituent.
As the alkylene represented by A ² , unsubstituted alkylene having 2 to 4 carbon atoms is preferable, and ethylene and trimethylene are particularly preferable.

Q ₁ in the formula (2c) represents —O—, —S—, or —NR ⁶ —, and R ⁶ represents a hydrogen atom, optionally substituted alkyl, or optionally substituted phenyl.
Examples of the alkyl represented by R ⁶ include substitutable alkyl having 1 to 4 carbon atoms. Specific examples of the substitutable alkyl having 1 to 4 carbon atoms are the same as those exemplified for R ¹ and R ² .
Examples of the substitutable phenyl represented by R ⁶ include phenyl optionally substituted with sulfo. Preferred R ⁶ is a hydrogen atom, methyl or ethyl.

In formula (2c), r and s are each independently 2, 3 or 4. A group in which r and s are each independently 2 or 3, and Q ₁ is —O— is preferable. In particular,
_{** - CH 2 CH 2 -O-} CH 2 CH 2 -
_{** - CH 2 CH 2 -O-} CH 2 CH 2 CH 2 -
_{** - CH 2 CH 2 CH 2} -O-CH 2 CH 2 -
_{** - CH 2 CH 2 CH 2} -O-CH 2 CH 2 CH 2 -
[In the formula, ** represents a bond connected to —NR ⁵ —. R ⁵ has the above-mentioned meaning. ]
In particular, a group represented by ** — CH ₂ CH ₂ —O—CH ₂ CH ₂ — is particularly preferred.

The group represented by U is preferably a group represented by the formula (2b). In addition, when U is a group represented by the formula (2b), a group in which A ² is ethylene or trimethylene and R ⁴ is a hydrogen atom, methyl or ethyl is preferable.

Z ² and Z ³ in the formula (2b) or (2c) represent a fiber reactive group represented by the formula (3a) or (3b), and Y ¹ and Y ² are —SO ₂ CH═CH ₂ and —SO ₂ CH ₂ CH ₂ L (L is a group capable of leaving by the action of an alkali), and examples of L include groups such as sulfate ester, thiosulfate ester, phosphate ester, and acetate ester, and halogeno. Can do. Of these, sulfate groups and chloro are preferred.
The Z ² and _{^{Z 3, -CH = CH 2,}} -CH 2 CH 2 Cl or -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 .

M in the above formula (3b) is an integer of 1 to 6, and R ⁷ represents a hydrogen atom or an optionally substituted alkyl. Examples of the alkyl which may be substituted include the same alkyl having 1 to 4 carbon atoms as exemplified for R ¹ and R ² .

As the group represented by the formula (3b), those in which R ⁷ is hydrogen and m is 2 or 3 are particularly preferable.

As the group represented by Z ² and Z ³ , the group represented by the above formula (3a) is particularly preferable.

X ¹ and X ² in the above formula (1) each independently represent fluoro, chloro, or optionally substituted pyridinio.
Examples of the pyridinio which may be substituted include pyridinio, 2-, 3- or 4-carboxypyridinio, 2-, 3- or 4-carbamoylpyridinio, 3-sulfopyridinio, and 4- (2-sulfoethyl). Examples include pyridinio, 3- (2-hydroxyethyl) pyridinio, 4-chloropyridinio, 3-methylpyridinio and 3,5-dicarboxypyridinio. Of these, 3- or 4-carboxypyridinio is particularly preferred.
X ¹ and X ² are particularly preferably fluoro and chloro.

T in the above formula (1) represents a non-fiber reactive group represented by the above formula (4a), (4b) or (4c). R ⁸ in formula (4a) represents hydrogen or an optionally substituted alkyl, and the alkyl is preferably a linear or branched one having 1 to 4 carbon atoms.
The alkyl which may be substituted is substituted with 1 or 2 substituents selected from the group of alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, hydroxy, halogeno (chloro, bromo, etc.) and cyano. Examples thereof include alkyl having 1 to 4 carbon atoms.
Specific examples of the optionally substituted alkyl in R ⁸ include the same groups as those exemplified for R ¹ and R ² . Examples of the alkyl which may be substituted include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-hydroxyethyl, 2-sulfoethyl, 2-methoxyethyl and 2-carboxyethyl. Is preferred.

R ⁹ in the above formula (4a) is alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carboxy, halogeno, hydroxy, cyano, carbamoyl, carboxylic acid ester, amino, acylamino and alkylamino (1 carbon atom). To 4) represents phenyl which may be substituted with one or two substituents selected from the group of 4) or alkyl which may be substituted.
Examples of the optionally substituted alkyl for R ⁹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-hydroxyethyl, and 2- (2-hydroxyethoxy) ethyl. 1-hydroxymethyl-1-methylethyl, 1,1-di (hydroxymethyl) ethyl, 1,1-di (hydroxymethyl) -2-hydroxyethyl, 2-sulfoethyl, 2-methoxyethyl, 2-carboxyethyl Etc. are preferred.

R ⁹ alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carboxy, halogeno, hydroxy, cyano, carbamoyl, carboxylic acid ester, amino, acylamino [preferably alkyl (1 to 4 carbon atoms) carbonylamino And phenyl optionally substituted with 1 or 2 substituents selected from the group of alkylamino having 1 to 4 carbon atoms include 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-hydroxyphenyl, 2-carbo Shi-4-acetylamino phenyl, 2-methoxy-5-methylphenyl, 2,4-dimethoxyphenyl or 2,5-dimethoxyphenyl and the like are preferable.

In the formula (4a), it is preferable that R ⁸ is hydrogen, methyl or ethyl, and R ⁹ is alkyl which may be substituted.

R ¹⁰ in the above formula (4c) represents a hydrogen atom, an optionally substituted alkyl or an optionally substituted phenyl. As said alkyl which may be substituted, the group similar to what was illustrated by said R < ⁸ > is mentioned.

Examples of the phenyl represented by R ¹⁰ include alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, halogeno, hydroxy, cyano, carbamoyl, sulfamoyl, carboxylic acid ester, 2 -Hydroxyethylsulfonyl, amino, acylamino [preferably alkyl (1 to 4 carbon atoms) carbonylamino] and 1 or 2 substituents selected from the group of alkylamino having 1 to 4 carbon atoms may be substituted. And phenyl.

  Examples of the optionally substituted phenyl include 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 2-methoxy-5-methylphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl and the like are preferable.

When T in the above formula (1) is a group represented by the formula (4a), examples of the amine compound represented by the formula HNR ⁸ R ⁹ used to form this group include the following compounds.

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, 2-, 3- or 4-amino Benzoic acid, 2-, 3- or 4-carbamoylaniline, 1-amino-2-carboxy-4-acetylaminobenzene, 5-aminobenzene-1,3-dicarboxylic acid, N-methylaminobenzene, N-ethylamino Benzene, 1-methylamino-3- or -4-methylbenzene, 1-ethylamino-3- or -4-methylbenzene, 1-methylamino-2-, -3- or -4-chlorobenzene, 1-ethyl Amino-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.

B) The following aliphatic amines:
Methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, dimethylamine, diethylamine, methylethylamine, allylamine, 2-chloroethylamine, 2-methoxyethylamine, 2- Aminoethanol, 2-methylaminoethanol, bis (2-hydroxyethyl) amine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl -1,3-propanediol, 1-amino-2-propanol, 3-methoxypropylamine, 1-amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid, aminomethanesulfonic acid, (2-methylamino) D Nsuruhon acid, 3-amino-1-propanesulfonic acid, amino acid, methylamino acetic acid, 3-aminopropionic acid.

Examples of the amines of the above a) and b) include 1-aminobenzene, N-methylaminobenzene, N-ethylaminobenzene, 1-amino-2-, -3- or -4-chlorobenzene, 1-methylamino- 2-, -3- or -4-chlorobenzene, 1-ethylamino-2-, -3- or -4-chlorobenzene, 1-amino-2-, -3- or -4-methylbenzene, 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, 2-, 3- or 4-aminophenol, 2-, 3- or 4-amino Benzoic acid, 2-, 3- Is 4-carbamoylaniline, 1-amino-2,4- or -2,5-dimethoxybenzene, 1-amino-2-carboxy-4-acetylaminobenzene, 1-amino-2-methoxy-5-methylbenzene, Methylamine, ethylamine, dimethylamine, isobutylamine, sec-butylamine, tert-butylamine, diethylamine, methylethylamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, 2- Amino-2-hydroxymethyl-1,3-propanediol, 2-aminoethanesulfonic acid, (2-methylamino) ethanesulfonic acid, 2-methylaminoethanol, bis (2-hydroxyethyl) amine, aminoacetic acid, methyl Aminoacetic acid and 3-aminopropionic acid are preferred. There.
Of these, 1-aminobenzene, N-methylaminobenzene, N-ethylaminobenzene, 1-amino-2-, -3- or -4-ethylbenzene, 2-, 3- or 4-aminobenzoic acid, methyl Amine, ethylamine, dimethylamine, tert-butylamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol 2-aminoethanesulfonic acid, (2-methylamino) ethanesulfonic acid, 2-methylaminoethanol, bis (2-hydroxyethyl) amine, aminoacetic acid and the like are particularly preferable.

R ¹⁰ is preferably hydrogen or alkyl having 1 to 4 carbon atoms, and particularly preferably methyl or ethyl.

When T in Formula (1) is a group represented by Formula (4c), examples of the compound represented by HOR ¹⁰ used to form this group include the following.

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-hydroxy Benzene-1,2-disulfonic acid, 4-hydroxy-5-methylbenzene-1,2-disulfonic acid, 3- or 4-hydroxybenzoic acid, 5-hydroxy Rokishibenzen 1,3-dicarboxylic acid and 5-hydroxy-2-ethoxy-benzenesulfonic 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-hydroxyethane Sulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2-cyanoethanol, 2-sulfate ethanol, glycolic acid, 3-hydroxypropionic acid, benzyl alcohol, 2-, 3- or 4-chlorobenzyl alcohol, 4- Methylbenzyl alcohol, 2-, 3- or 4-sulfobenzyl alcohol, 2-phenylethanol or 1-phenyl-2-propanol.

Q ² in the above formula (4b) represents —CH ₂ —, —O—, —S—, —SO ₂ — or —NR ¹¹ —, R ¹¹ represents a hydrogen atom or an optionally substituted alkyl, n is 1, 2 or 3.
The alkyl represented by R ¹¹ is preferably one having 1 to 4 carbon atoms.
Examples of the substituent for the alkyl represented by R ¹¹ include halogeno (chloro, bromo, etc.) and alkoxy having 1 to 4 carbon atoms.
R ¹¹ is preferably a hydrogen atom or a linear or branched alkyl having 1 to 4 carbon atoms, particularly preferably hydrogen, methyl or ethyl.
Examples of the group represented by the formula (4b) include residues such as pyrrolidine, piperidine, piperazine, n-alkylpiperazine and morpholine. Among these, morpholino or piperidino is particularly preferable.

  As the group represented by T, the above formula (4a) or (4c) is particularly preferable.

  The bisazo compound (1) or a salt thereof of the present invention may be in the form of a mixture thereof. Preferred are alkali metal salts, alkaline earth metal salts and mixtures containing these, and particularly preferred are sodium salts, potassium salts, lithium salts and mixtures containing them.

  As the bisazo compound (1) in the present invention, those represented by the following formula (1a-1) or (1a-2) are preferable.

[Wherein, *, R ¹ , R ² , X ¹ , X ² , U and T represent the above-mentioned meanings. ]

Of the compounds of formula (1a-1) or (1a-2), (1) R ¹ and R ² are hydrogen, (2) X ¹ and X ² are fluoro or chloro, and (3) T is A compound of formula (4a) or (4c), wherein R ⁸ in formula (4a) is hydrogen, or T is formula (4c) and R ^{10 in} the formula is methyl or ethyl Particularly preferred.

The bisazo compound (1) or a salt thereof of the present invention can be produced, for example, as follows.
First, among the bisazo compounds (1), in which X ¹ and X ² are chloro or fluoro, for example, the form of the free acid is represented by the following formula (5)
HT (5)
[Wherein T has the above-mentioned meaning. ]
And a compound represented by the following formula (6)

［式中、Ｒ¹は前記の意味を有する。］
で示されるジアミン化合物を、２,４,６−トリハロゲノ−ｓ−トリアジンと公知の方法に準じて縮合させることにより、下式（７）

[Wherein R ¹ has the above-mentioned meaning. ]
Is condensed with 2,4,6-trihalogeno-s-triazine according to a known method to obtain the following formula (7):

[Wherein, R ¹ and T represent the above-mentioned meanings, and X ¹ a represents fluoro or chloro. ]
Can be obtained.

On the other hand, the following formula (8)
HU (8)
[Wherein U has the above-mentioned meaning. ]
And a compound of the following formula (9)

[Wherein R ² has the above-mentioned meaning. ]
Is condensed with 2,4,6-trihalogeno-s-triazine according to a known method to give the following formula (10):

[Wherein R ² and U represent the above-mentioned meanings, and X ² a represents fluoro or chloro. ]
Can be obtained.

  When each of the amine compounds represented by the above formulas (7) and (10) is diazotized according to a conventional method and the latter diazotized product is expressed in the form of a free acid, the following formula (11)

With the 1-amino-8-naphthol compound represented by formula (1) at a temperature of −10 ° C. to 30 ° C. while adjusting the pH to 0 to 4, and then the former diazotate was added to the resulting coupling reaction product. A compound represented by the following formula (12) or a salt thereof can be obtained by coupling while adjusting the pH to 2 to 8 at -40C.

[Wherein R ¹ , R ² , T and U represent the above-mentioned meanings, and X ¹ a and X ² a represent fluoro or chloro. ]
Can be obtained.

Moreover, the bisazo compound (1) of this invention can also be manufactured as follows, for example.
First, in the form of the free acid, the compounds represented by the above formulas (6) and (8) are condensed with 2,4,6-trihalogeno-s-triazine according to a known method to give the following formula ( 13)

[Wherein, R ¹ and U represent the above-mentioned meanings, and X ¹ a represents fluoro or chloro. ]
To obtain a compound represented by
Separately, the amine compounds represented by the above formulas (5) and (9) are each condensed with 2,4,6-trihalogeno-s-triazine according to a known method to obtain the following formula (14):

[Wherein R ² and T represent the above-mentioned meanings, and X ² a represents fluoro or chloro. ]
To obtain a compound of

  The amine compounds represented by the above formulas (13) and (14) are each diazotized according to a conventional method, and the latter diazotized compound is first converted to a 1-amino-8-naphthol compound represented by the above formula (11) at a temperature of −10 ° C. By coupling while adjusting to pH 0 to 4 at -30 ° C, and then coupling the obtained product with the former diazotate while adjusting to pH 2 to 8 at 0 ° C to 40 ° C, the following formula ( 15) or a salt thereof can be obtained.

[Wherein R ¹ , R ² , T and U represent the above-mentioned meanings, and X ¹ a and X ² a represent fluoro or chloro. ]
Can be obtained.

Further, among the bisazo compounds (1) of the present invention, those in which X ¹ and X ² are optionally substituted pyridinio are, for example, represented by the above formula (12) in the form of a free acid. A compound of the following formula (16) can be obtained by reacting a pyridine compound corresponding to pyridinio, which is synthesized by the same method, at a temperature of 10 ° C. to 100 ° C. under a pH of 2-9. it can.

[Wherein, R ¹ , R ² , T and U represent the above-mentioned meanings, and X ¹ b and X ² b represent an optionally substituted pyridinio. ]

  In the above-described production method, in the condensation reaction with 2,4,6-trihalogeno-s-triazine, the order and reaction conditions are not particularly limited. For example, the first condensation reaction is performed at a temperature of −10 ° C. to 40 ° C. The reaction is carried out under conditions of pH 1 to 10, and the second condensation reaction can be carried out under conditions of a temperature of 0 ° C to 70 ° C and a pH of 2 to 10.

In the bisazo compound (1) or a salt thereof of the present invention, the groups represented by Y ¹ and Y ² in the formulas (3a) and (3b) are —CH ₂ CH ₂ L, and the L is a sulfate ester. A bisazo compound or a salt thereof, which is an ester group such as phosphoric acid ester, is obtained by, for example, esterification reaction of a precursor compound having a β-hydroxyethylsulfonyl group obtained after the condensation reaction with sulfuric acid or phosphoric acid. The compound of the above formula (1) or a salt thereof can also be obtained by converting into

As 2,4,6-trihalogeno-s-triazine, cyanuric chloride or cyanuric fluoride is preferable.
As the 1-amino-8-naphthol compound represented by the above formula (11), H acid and K acid are preferable, and H acid is particularly preferable.

  The bisazo compound (1) or a salt thereof of the present invention can be used, for example, as a dye for dyeing or printing fiber materials. Such a material is not particularly limited as long as it contains a hydroxy group and / or a carbonamide group. For example, natural or regenerated cellulose fiber material, natural or synthetic polyamide fiber material, polyurethane fiber material, leather, and these are used. Examples thereof include a blended material to be contained.

Specific examples of the natural cellulose fiber material include cotton or other plant fibers such as linen, hemp, jute and ramie fibers.
Examples of the regenerated cellulose fiber material include rayon, polynosic, cupra fiber, and trade names “Tencel”, “Toughcel”, “Modal”, “Celtima”, and the like.
Specific examples of natural or synthetic polyamide fiber materials include wool, other animal hair, silk, polyamide-6,6, polyamide-6, polyamide-11, polyamide-4, and the like.
Moreover, as a blended material containing these, the blended material of these fiber materials and synthetic fibers, such as polyester, nylon, an acrylic other than these blended materials of these fiber materials, etc. can be illustrated.

The compound of the present invention can be dyed or printed on the above-mentioned material, particularly on the above-mentioned fiber material by a method according to the physicochemical properties.
Specific examples include a method of dyeing or printing on the above-described fiber material by a method such as an exhaust dyeing method, a cold batch up method, a continuous dyeing method, or a printing method.
For example, in the case of exhaust dyeing on a cellulose fiber material, in the presence of an acid binder such as sodium carbonate, tribasic sodium phosphate, sodium bicarbonate, caustic soda, if necessary, add neutral salt such as salt cake and salt, Examples include a method of dyeing at a temperature of about 30 to 100 ° C. using a solubilizing agent, a penetrating agent, a leveling agent, or the like as necessary. Here, addition of an acid binder, a neutral salt, or the like may be performed at once, or may be performed in a divided manner by a conventional method.

In case of dyeing on cellulose fiber by cold batch up method, after padding with neutral salt such as mirabilite and salt, and acid binder such as caustic soda and sodium silicate, it is kept at a constant temperature in the sealed packaging material. Examples of such a method include processing by leaving it alone.
In the case of dyeing on cellulose fibers by continuous dyeing, padding is performed at room temperature or elevated temperature by a known method in the presence of an acid binder such as sodium carbonate or sodium bicarbonate, followed by treatment by steaming or dry heat. After immersing the fiber in the phase padding method or the padding solution in which the compound of the present invention is dissolved, neutral salt such as mirabilite and salt, and acid binder such as caustic soda and sodium silicate are padded, and steaming or Examples thereof include a two-phase padding method in which treatment is performed by dry heat.

  When printing on cellulose fibers, one phase is printed with a printing paste containing a binder such as baking soda, followed by steaming at a high temperature of 80 ° C. or higher, or two phases, for example neutral or Examples include a method of printing with a weakly acidic printing paste and passing it through an alkaline bath containing an electrolyte, or overpassing with an alkaline electrolyte-containing padding solution, and then processing by steaming or dry heating. Is done. Here, the printing paste may contain, for example, a paste and / or an emulsifier such as sodium alginate and starch ether, and if necessary, a printing aid such as urea and / or a dispersant. May be.

When the compound of the present invention is dyed or printed on cellulose fiber, the acid binder used is not particularly limited. For example, water solubility of alkali metal hydroxide, alkali metal or alkaline earth metal and inorganic or organic acid Examples thereof include a basic salt or a compound that liberates alkali when heated. In particular, alkali metal hydroxides and alkali metal salts of weak or moderate strength inorganic or organic acids can be mentioned. Among these, sodium or potassium hydroxides, sodium salts and potassium salts are preferred. Specific examples of such an acid binder include sodium carbonate, tertiary sodium phosphate, sodium bicarbonate, caustic soda, sodium carbonate, sodium silicate, sodium bicarbonate, caustic potash, sodium formate, potassium carbonate, first or second. Examples thereof include sodium diphosphate and sodium trichloroacetate.
In the case of exhaust dyeing on a synthetic or natural polyamide fiber or polyurethane fiber, the compound of the present invention is exhausted under the control of pH value in an acidic to weakly acidic dye bath, and then 60 to 120 ° C. Examples thereof include a method of changing to a neutral to alkaline pH value at a moderate temperature. If necessary, a leveling agent, for example, a condensation product of cyanuric chloride and 3-fold molar amount of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid, or an addition product of stearylamine and ethylene oxide, etc. Such leveling agents may be used.

  In order to obtain a desired hue, the compound of the present invention can be used by mixing with other dyes as long as it does not impair the characteristics of the present invention. The dye to be used as a mixture 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, Dye having at least one or more of dichlorotriazine group, difluoromonochloropyrimidine group, and trichloropyrimidine group, or Sumifix, Sumifix Supra, Sumifix HF, Remazol, Levafix, Procion, Cibacron, Nes, Basilen, Basilen, Dyes that are commercially available under the titles such as Kayacelon React, and further, JP-A-50-178, JP-A-51-17538, JP-A-56-9483, JP-A-56-15481, JP-A-56-118976, JP-A-56-128380, JP-A-57-2365, JP-A-57-89679 JP, 57-143360, JP-A 58-191755, JP-A 59-15451, JP-A 59-96174, JP-A 59-161463, JP 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-61-225256, JP-A-63-77974, JP-A-63-225664, JP-A-1-185370, JP-A-3-770. Dyes described in JP-A-5-247366 and JP-A-6-287463, and C.I. I. Reactive Blue 19, C.I. I. Examples include dyes represented by Reactive Black5.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples. In the examples, parts represent parts by weight.

Reference example 1
3.69 parts of cyanuric chloride and 5.63 parts of 1-aminobenzene-4-β-sulfatoethylsulfone are condensed in an aqueous medium at a pH of 2-6 and at a temperature of -5 ° C to 20 ° C. , 3.76 parts of 2,4-diaminobenzenesulfonic acid were condensed at pH 3 to 7, 10 ° C. to 40 ° C. to obtain a compound of the following formula (17).

  Next, 3.69 parts of cyanuric chloride and 3.76 parts of 2,4-diaminobenzenesulfonic acid are condensed at a pH of 1-4 and −10 ° C. to 20 ° C. by a conventional method. By condensing 42 parts at pH 2.5-7 and 0 ° C.-30 ° C., a compound of the following formula (18) was obtained.

The compound of the above formula (17) is diazotized by a conventional method, and the resulting diazotized product is 6.39 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, pH 1 to 3.5, 0 ° C to Coupling at 30 ° C. gave the coupling product.
Separately, the compound of formula (18) is diazotized by a conventional method, and the diazotized product is subjected to a coupling reaction with the above-mentioned coupling product at pH 4 to 8 at 0 ° C. to 30 ° C. When salted out or evaporated to dryness and expressed in the form of a free acid, a compound represented by the following formula (19) was obtained.

（λｍａｘ＝６０６ｎｍ、水性媒体中）

(Λmax = 606 nm in an aqueous medium)

Reference example 2
3.69 parts of cyanuric chloride and 5.63 parts of 1-aminobenzene-4-β-sulfatoethylsulfone are condensed in an aqueous medium at a pH of 2-6 and at a temperature of -5 ° C to 20 ° C. The compound of the above formula (17) was obtained by condensing 3.76 parts of 2,4-diaminobenzenesulfonic acid at pH 3 to 7, 10 ° C to 40 ° C.

  Next, 3.69 parts of cyanuric chloride and 3.76 parts of 2,4-diaminobenzenesulfonic acid are condensed at a pH of 1-4 and −10 ° C. to 20 ° C. by a conventional method, and then 0.84 part of cyanamide is added. By condensing at pH 8 to 11 and 20 ° C. to 60 ° C., a compound of the following formula (20) was obtained.

The compound of the above formula (17) is diazotized by a conventional method, and the resulting diazotized product is 6.39 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, pH 1 to 3.5, 0 ° C to Coupling at 30 ° C. gave the coupling product.
Separately, the compound of formula (20) is diazotized by a conventional method, and the diazotized product is subjected to a coupling reaction with the above-mentioned coupling product at pH 4 to 8 at 0 ° C. to 30 ° C. Then, the resulting product is converted into a conventional method. When salted out or evaporated to dryness and expressed in the form of the free acid, a compound represented by the following formula (21) was obtained.

（λｍａｘ＝６０６ｎｍ、水性媒体中）

(Λmax = 606 nm in an aqueous medium)

Reference example 3
3.69 parts of cyanuric chloride and 5.63 parts of 1-aminobenzene-4-β-sulfatoethylsulfone are condensed in an aqueous medium at a pH of 2-6 and at a temperature of -5 ° C to 20 ° C. The compound of the above formula (17) was obtained by condensing 3.76 parts of 2,4-diaminobenzenesulfonic acid at pH 3 to 7, 10 ° C to 40 ° C.
Next, 3.69 parts of cyanuric chloride and 3.76 parts of 2,4-diaminobenzenesulfonic acid are condensed at a pH of 1-4 and -10 ° C to 20 ° C by a conventional method, and then tert-butylamine 1.46. By condensing a part at pH 7-11 and 20-60 degreeC, the compound of the following Formula (22) was obtained.

The compound of the above formula (17) is diazotized by a conventional method, and the resulting diazotized product is 6.39 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, pH 1 to 3.5, 0 ° C to Coupling at 30 ° C. gave the coupling product.
Separately, the compound of formula (22) is diazotized by a conventional method, and the diazotized product is subjected to a coupling reaction with the above-mentioned coupling product at pH 4 to 8 at 0 ° C. to 30 ° C. Then, the obtained product is converted into a conventional method. When salted out or evaporated to dryness and expressed in the form of the free acid, a compound represented by the following formula (23) was obtained.

（λｍａｘ＝６０８ｎｍ、水性媒体中）

(Λmax = 608 nm, in aqueous medium)

Examples 1-7
Instead of the compound of the formula (17), the compound in the fourth column in Table 1 below, the compound in the third column of the same table instead of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, The corresponding bisazo compound can be obtained by synthesizing in the same manner as in Reference Example 1 except that each of the compounds in the second column of the same table is used instead of the compound of the formula (18).

Reference example 4
In the same manner as in Example 1, the compounds of the above formulas (17) and (18) are synthesized. A diazotized product obtained by diazotizing the compound of the above formula (18) by a conventional method and 6.39 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are pH 1 to 3.5, 0 ° C. to 30 ° C. A coupling reaction is performed at 0 ° C. to obtain a reaction product.
Separately, the compound of the above formula (17) is diazotized by a conventional method to obtain a diazo compound.
The coupling reaction product obtained above is subjected to a coupling reaction with the diazotized product of the above compound (17) at pH 4-8 and 0 ° C-30 ° C. The resulting product is salted out or evaporated to dryness. When expressed in the form of a free acid, a bisazo compound represented by the following formula (24) is obtained.

Examples 8-10
Instead of the compound of the formula (17), the compound in the second column in Table 2 below, the compound in the third column of the same table instead of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, The corresponding bisazo compounds are obtained by synthesizing in the same manner as in Reference Example 4 except that the compounds in the fourth column of the same table are used in place of the compounds of the formula (18), respectively.

Reference Example 5
Compound (19) was synthesized in the same manner as in Example 1, and the product obtained by condensing 4.92 parts of 3-carboxypyridine at pH 2 to 4 at 40 ° C. to 100 ° C. was salted out or evaporated to dryness. When expressed in the form of an acid, the following compound (25) is obtained.

  When each of the corresponding compounds described in Examples 1 to 10 is used instead of the compound (19) and synthesized in the same manner as in Reference Example 5, the corresponding bisazo compounds are obtained.

Dyeing example 1
Each 0.3 part of the compound obtained in Example 7 is dissolved in 200 parts of water, 20 parts of sodium sulfate is added, 10 parts of cotton is further added, and then the temperature is raised to 60 ° C. After maintaining at 60 ° C. for 30 minutes, 4 parts of sodium carbonate was added, dyed at 60 ° C. for 1 hour, washed with water and soaped. The wash-off property during washing and soaping was good, and the coloring amount of the dye wastewater was slight. The dyed product obtained was uniform and dark amber. In addition, various fastnesses (chlorine resistance, light resistance, sweat resistance, sweat sun resistance, acid hydrolysis resistance, alkali resistance, washing resistance, and peroxide washing resistance) of the dyed material obtained are all good. Met.

Dyeing example 2
Dyeing is performed in the same manner as Dyeing Example 1 except that the amount of sodium sulfate used is changed from 20 parts to 10 parts. The obtained dyed articles each have the same quality as the dyed article obtained in Dyeing Example 1.

Dyeing example 3
Dyeing is performed in the same manner as Dyeing Example 1 except that the amount of sodium sulfate used is changed from 20 parts to 4 parts.
The obtained dyed articles each have the same quality as the dyed article obtained in Dyeing Example 1.

Dyeing example 4
Dyeing is performed in the same manner as dyeing examples 1 to 3, except that the dyeing temperature is changed from 60 ° C to 70 ° C. The obtained dyed articles are of the same quality as dyeing examples 1 to 3, respectively.

Dyeing example 5
Dyeing is performed in the same manner as Dyeing Examples 1 to 3, except that the dyeing temperature is changed from 60 ° C to 80 ° C. The obtained dyed articles have the same quality as the dyed articles of Dyeing Examples 1 to 3, respectively.

Dyeing example 6
Instead of using 0.3 part of each compound, a mixture of 0.3 part of each compound and 0.06 part of a sodium salt of a condensate of methylnaphthalenesulfonic acid and formaldehyde (sulfonation degree 110%, average polymerization degree 1.8) Dyeing is performed in the same manner as in Dyeing Examples 1 to 5, except that The obtained dyed articles have the same quality as the dyed articles of Dyeing Examples 1 to 5, respectively.

Printing example 1
Using each bisazo compound obtained in Example 7, a color paste having the following composition is prepared.

Color paste composition 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 is printed on mercerized cotton broad, and after intermediate drying, steaming is performed at 100 ° C. for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying to finish. This print is uniform and has a dark amber color. In addition, the various fastnesses (chlorine resistance, light resistance, sweat resistance, sweat sun resistance, acid hydrolysis resistance, alkali resistance, washing resistance, and peroxide washing resistance) of the printed matter are all good. is there.

  Dyeing or printing is carried out in the same manner as Dyeing Examples 1 to 6 or Printing Example 1 except that the bisazo compounds of Examples 1 to 6 and 8 to 10 or mixtures are used instead of the bisazo compound of Example 7. The obtained dyed or printed matter has a quality equivalent to that of the dyed or printed matter obtained in the above example.

The dyed product obtained by the dyeing method of the present invention is useful as clothing.

Claims (11)

A bisazo compound represented by the following formula (1) or a salt thereof.

[Wherein, R ¹ and R ² each independently represents 1 to 1 carbon atoms which may be substituted with a substituent selected from the group consisting of hydroxy, cyano, alkoxy having 1 to 4 carbon atoms, halogeno, carboxy and sulfo. 4 represents an alkyl group or a hydrogen atom, and U represents a group represented by the following formula (2b) or (2c).

{Wherein R ₄ and R ₅ each independently represent a hydrogen atom or substituted with a substituent selected from the group consisting of hydroxy, cyano, alkoxy having 1 to 4 carbon atoms, halogeno, carboxy and sulfo. Or an alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl group.
A ² represents alkylene having 2 to 4 carbon atoms which may be substituted with a substituent selected from the group consisting of alkyl having 1 to 4 carbon atoms, halogeno, hydroxy, sulfo, cyano and alkoxy having 1 to 4 carbon atoms.
Q ¹ represents —O—, —S—, or —NR ⁶ —.
R ⁶ is hydroxy, cyano, C 1-4 alkoxy, halogeno, carboxy and sulfo which may be substituted with a substituent selected from the group consisting of sulfo and phenyl which may be substituted with sulfo Or represents a hydrogen atom.
r and s each independently represent 2, 3, or 4.
Z ₂ and Z ₃ each independently represent a fiber reactive group represented by the following formula (3a) or (3b).

(In the formula, Y ¹ and Y ² represent —CH═CH ₂ or —CH ₂ CH ₂ L, L is a group capable of leaving by the action of an alkali, and R ⁷ is a hydrogen atom or having 1 to 4 carbon atoms. Represents alkyl, and m is an integer of 1 to 6.)}
X ¹ and X ² each independently represents an optionally substituted pyridinio, fluoro or chloro.
T represents a non-fiber reactive group represented by the following formula (4a), (4b) or (4c).

(In the formula, R ⁸ is alkyl having 1 to 4 carbon atoms which may be substituted with one or two substituents selected from the group consisting of hydroxy, cyano, alkoxy having 1 to 4 carbon atoms, halogeno, carboxy and sulfo. Or represents a hydrogen atom.
R ⁹ represents hydroxy, cyano, alkyl having 1 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms which may be substituted with 1 or 2 substituents selected from the group consisting of alkoxy, halogeno, carboxy and sulfo; Or R ⁹ is alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carboxy, halogeno, hydroxy, cyano, carbamoyl, carboxylic acid ester, amino, acylamino, and alkylamino having 1 to 4 carbon atoms. It represents phenyl optionally substituted by 1 or 2 substituents selected from the above.
R ¹⁰ represents hydroxy, cyano, alkyl having 1 to 4 carbons, alkyl having 1 to 4 carbons which may be substituted with 1 or 2 substituents selected from the group consisting of alkoxy, halogeno, carboxy and sulfo; Alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, halogeno, hydroxy, cyano, carbamoyl, sulfamoyl, carboxylic acid ester, 2-hydroxyethylsulfonyl, amino, alkylcarbonyl having 2 to 5 carbon atoms It represents phenyl optionally substituted with 1 or 2 substituents selected from the group consisting of amino and alkylamino having 1 to 4 carbon atoms, or represents a hydrogen atom.
Q ² represents —CH ₂ —, —O—, —S—, —SO ₂ — or —NR ¹¹ —. n is 1, 2 or 3.
R ¹¹ represents halogeno, alkyl optionally substituted with alkoxy having 1 to 4 carbon atoms, or a hydrogen atom. ]]
However, two * marks shown in [] represent one bond with -U, and the other represents a bond with -T. ] The compound or its salt of Claim 1 shown by the following formula (1a).

(In the formula, R ¹ , R ² , X ¹ , X ² , U and T represent the meanings described in claim 1. Also, two * marks shown in [] indicate that one of them is -U. Represents a bond, and the other represents a bond with -T.) R ¹ and R ^2, the compound or a salt thereof according to claim 1 or 2 is a hydrogen atom. X ¹ and X ^2, compound or salt thereof according to any one of claims 1 to 3 are each independently fluoro or chloro. X ¹ and X ^2, compound or salt thereof according to any one of claims 1 to 3 is good pyridinio which may be substituted.   U is group shown by the said Formula (2b), The compound or its salt in any one of Claims 1-5. The compound or a salt thereof according to claim 6, wherein Z ¹ and Z ² are a group represented by the above formula (3a).   T is group shown by Formula (4a), The compound or its salt in any one of Claims 1-7.   T is a group represented by Formula (4b), The compound or its salt in any one of Claims 1-7.   T is a group represented by Formula (4c), The compound or its salt in any one of Claims 1-7. A method for dyeing or printing a fiber material, wherein the compound according to any one of claims 1 to 10 or a salt thereof is used.