JP2000290520A - Bis-azo compound or its salt and application thereof to fiber material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bis-azo compound or its salt useful for obtaining dark- blue dyed and printed materials being excellent in various fastness, in a dyeing or printing treatment for a fiber material, particularly a cellulose fiber material. SOLUTION: A bis-azo compound is represented by formula 1 [wherein one of X1 and X2 is hydroxy and the other of them is amino; R1 and R2 are each H or (substituted)alkyl; R3 and R4 are each H, sulfo, methyl, methoxy or chloro; m and n are each 0 or 1; U is a group represented by formula II or the like; T is the same as or different from U, but has the same definition as U, or T is fluoro, chloro, (substituted)pyridinio or the like; in the formula II, R5 is H or a (substituted)alkyl group; A1 is (substituted)phenylene or (substituted) naphthylene; Z1 is a fiber reactive group represented by formula III or the like; Y1 is -CH=CH2 or -CH2CH2L; and L is a leaving group with an alkali action].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dark blue bisazo compound useful for dyeing or printing fiber materials, especially cellulosic fiber materials.

[0002]

2. Description of the Related Art As dark blue reactive dyes used for dyeing and printing fiber materials, dyes described in JP-A-57-78458 and JP-A-57-198757 are known.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have compared the above-mentioned known dark blue dyes with
Dyeability at low salt concentration, dye reproducibility and dyeing performance (leveling property,
Build-up property, effective dyeing rate, wash-off property, etc.)
And more excellent in various fastnesses (chlorine resistance, light resistance, sweat resistance, sweat sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance, peroxidation washing resistance, etc.). As a result of intensive research to develop a reactive dye that gives a dark blue dye, the molecular structure has two triazine rings at the end, one triazine ring is substituted with two chloro, and the other triazine ring. The present inventors have found that a specific bisazo compound or a salt thereof substituted with at least one vinylsulfone-based fiber-reactive group achieves the above object, and completed the present invention.

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

[0005]

Embedded image

Wherein X ¹ and X ² are hydroxy and the other is amino, and R ¹ and R ² are the same or different and represent hydrogen or optionally substituted alkyl;
R ³ and R ⁴ are the same or different and represent hydrogen, sulfo, methyl, methoxy or chloro, m and n are the same or different and represent 0 or 1, and U is the following formula (2a):
Represents a group represented by (2b) or (2c),

[0007]

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Wherein R ⁵ represents hydrogen or an optionally substituted alkyl, R ⁶ and R ⁷ have the same meaning as R ⁵ or phenyl, and A ¹ is substituted represents an naphthylene be also phenylene or substituted optionally, a ² represents an alkylene optionally substituted, Q ¹ is -O -, - S- or -NR ⁸ - represents the, here, R ⁸ represents hydrogen, optionally substituted alkyl or optionally substituted phenyl, r and s are the same or different and represent 2, 3 or 4, Z ¹ , Z ² and Z
³ are the same or different and are represented by the following formula (3a) or (3b)

[0009]

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(Y ¹ and Y ² 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, R ⁹ represents hydrogen or an optionally substituted alkyl, and p represents 1 to 6 It is an integer. )> Represents a fiber-reactive group, and T is the same or different and has the same meaning as U, or is fluoro, chloro, optionally substituted pyridinio, or the following formula (4)
a), (4b) or (4c).

[0011]

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[0012] {R ¹⁰ and R ¹¹ are the same or different, represent hydrogen, alkyl which may be substituted, the phenyl which may be also be cycloalkyl or substituted optionally be substituted, R ¹² are the same or Is different from R ¹⁰ and R ¹¹ , Q ² is —CH ₂ —, —O—, —S—, —SO ₂
— Or —NR ¹³ —, wherein R ¹³ represents hydrogen or an optionally substituted alkyl, and q is 1, 2 or 3. ｝)

Hereinafter, the present invention will be described in detail.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The bisazo compound of the present invention is represented by the above general formula (1), wherein one of X ¹ and X ² represents hydroxy and the other represents amino, and m and n are the same or different. It represents 0 or 1 differently, and it is preferable that at least one of m and n is 1.

R ¹ and R ² are the same or different and each represents hydrogen or an alkyl which may be substituted, and the alkyl preferably has 1 to 4 carbon atoms. Examples thereof include hydroxy, cyano, alkoxy having 1 to 4 carbon atoms, halogeno, carbamoyl, carboxy, alkoxy (1 to 4 carbon atoms) carbonyl, alkyl (1 to 4 carbon atoms) carbonyloxy, sulfo and sulfamoyl. it can. The above alkyl,
Alkoxy having 1 to 4 carbon atoms, also alkoxy (1 to 4 carbon atoms) carbonyl and alkyl (1 to 4 carbon atoms) carbonyloxy as the substituent of the alkyl are
It may be linear or branched.

Specific examples of the optionally substituted alkyl represented by R ¹ and R ² include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-hydroxy Ethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyano Propyl, methoxymethyl, ethoxymethyl, 2-
Methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 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, 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-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfo Famoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like can be mentioned.

As R ¹ and R ² , hydrogen, methyl or ethyl are more preferred, and hydrogen is particularly preferred.

R ³ and R ⁴ are the same or different and each represents hydrogen,
Represents sulfo, methyl, methoxy or chloro, but hydrogen,
Sulfo, methyl and methoxy are more preferred, and hydrogen or sulfo is particularly preferred.

In the bisazo compound (1), U represents a group represented by the above formula (2a), (2b) or (2c), and R ⁵ in the formula (2a) represents hydrogen or an optionally substituted alkyl. In this case, examples of the alkyl include the same optionally substituted alkyl as those exemplified for R ¹ and R ² above. Equations (2b) and (2c)
R ⁶ and R ^{7 in} have the same meaning as R ⁵ or represent an optionally substituted phenyl. R ⁵ is more preferably hydrogen, methyl and ethyl, and R ⁶ and R ⁷ are more preferably hydrogen, methyl and ethyl.

In the formula (2a), A ¹ represents phenylene which may be substituted or naphthylene which may be substituted. Examples of the phenylene which may be substituted include those having 1 to 4 carbon atoms. And phenylene which may be substituted by 1 to 2 substituents selected from the group consisting of alkyl, alkoxy having 1 to 4 carbons, sulfo and halogeno. Preferred phenylene includes phenylene which may be substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo.

Specific examples of such phenylene include, for example,

[0022]

Embedded image

[Wherein the bond indicated by the symbol # is -NR ^5-
(R ⁵ are each as defined above) refers to a bond that connects to. And the like. Particularly preferably, unsubstituted phenylene or 1 selected from methyl and methoxy
Phenylene substituted with up to two substituents.

In the formula (2a), the optionally substituted naphthylene represented by A ¹ may be, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfo group and a halogeno group. Examples include naphthylene which may be substituted by one or two selected substituents. The optionally substituted naphthylene represented by A ¹ preferably includes naphthylene which may be substituted by one or two sulfo.

Specific examples of such naphthylene include, for example,

[0026]

Embedded image

[In the formula, the bond indicated by # is -N
R ⁵ - (R ⁵ are each as defined above) refers to a bond that connects to. And the like.

Preferred A ¹ is phenylene which may be substituted with one or two groups selected from methyl and methoxy.

In the formula (2b), A ² represents an alkylene which may be substituted, and examples of the alkylene include alkyl having 1 to 4 carbons, halogeno,
Hydroxy, sulfo, cyano, alkoxy having 1 to 4 carbons, alkoxycarbonyl having 1 to 4 carbons, 1 to 1 carbons
4 carbon atoms which may be substituted by a substituent selected from the group consisting of alkylcarbonyloxy and carbamoyl
To 4 alkylenes and the like. As the optionally substituted alkylene represented by A ² , unsubstituted alkylene having 2 to 4 carbon atoms is preferable, and among them, ethylene and trimethylene are particularly preferable.

In the above formula (2c), Q ¹ is —O—,
Represents —S— or —NR ⁸ —, wherein R ⁸ represents hydrogen, optionally substituted alkyl, or optionally substituted phenyl. Examples of the optionally substituted alkyl represented by R ⁸ include the same alkyl having 1 to 4 carbon atoms as exemplified for R ¹ and R ² above. Examples of the optionally substituted phenyl represented by R ⁸ include, for example, phenyl optionally substituted by sulfo. R ⁸ is preferably hydrogen,
Methyl and ethyl.

In the formula (2c), r and s are the same or different and are 2, 3 or 4. In formula (2c),-(C
H ₂₎ r-Q '- The (CH ₂₎ a group represented by s, Q ¹
Is preferably -O-, and r and s are the same or different and are 2 or 3, and specifically,

[0032] _{* - 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 — wherein the bond indicated by * means a bond connected to —NR ⁷ — (R ⁷ has the above-mentioned meaning). Is preferred. Among them, * -CH ₂ CH ₂ -O-CH ₂ CH ₂ -[*
Has the above-mentioned meaning].

The group represented by U is preferably a linking group represented by the above formula (2a) or (2b),
Among them, a group represented by the formula (2a) is particularly preferable.

Further, when U is a group represented by the formula (2a), it is preferable that A ¹ is phenylene which may be substituted and R ⁵ is hydrogen, methyl or ethyl. When U is a group represented by the above formula (2b), it is preferable that A ² is ethylene or trimethylene and R ⁶ is hydrogen, methyl or ethyl.

Formula (2a), (2b) or (2) in U
In c), Z ¹ , Z ² and Z ³ represent a fiber-reactive group represented by the formula (3a) or (3b), but Y ¹ and Y ²
Are the same or different -SO ₂ CH = CH ₂ and -SO
₂ CH ₂ CH ₂ L represents a group capable of leaving 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 preferable. As Z ¹ , Z ² and Z ³ , -CH ＝ C
H _2, is preferable, -CH ₂ CH ₂ Cl or -CH ₂ CH ₂ OSO ₃ H, among others, -CH = CH ₂ and -CH ₂ CH ₂
OSO ₃ H is particularly preferred.

In the above formula (3b), R ⁹ represents hydrogen or an optionally substituted alkyl. Examples of the optionally substituted alkyl include, for example, the aforementioned R ¹
And R exemplified as the same alkyl such having 1 to 4 carbon atoms in the ² and the like.

In the above formula (3b), p is an integer of 1 to 6, and as a group represented by the formula (3b), R ⁹
Is hydrogen, and p is preferably 2 or 3. As such a group represented by Z ¹ , Z ² and Z ³ , a group represented by the above formula (3a) is particularly preferred.

T in the above formula (1) is the same or different and has the same meaning as U, or fluoro, chloro, optionally substituted pyridinio, or formula (4a), (4
b) or (4c).

Examples of the optionally substituted pyridinio represented by T include pyridinio, 2-, 3- or 4
-Carboxypyridinio, 2-, 3- or 4-carbamoylpyridinio, 3-sulfopyridinio, 4- (2-sulfoethyl) pyridinio, 3- (2-hydroxyethyl) pyridinio, 4-chloropyridinio, 3-methylpyridinio, 3,5-dicarboxypyridinio and the like can be mentioned. Preferably, 3- or 4-carboxypyridinio can be mentioned.

R ¹⁰ and R ¹¹ in the above formula (4a) are
The same or different, represents hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted phenyl, wherein the alkyl may be linear or branched; It may be present, but preferably has 1 to 4 carbon atoms.

Such an optionally substituted alkyl or
As the cycloalkyl, for example, an alkyl having 1 to 4 carbon atoms
Coxy, sulfo, carboxy, sulfamoyl, carb
Moyl, hydroxy, halogeno (chloro, bromo, etc.),
Cyano, carboxylic acid ester, sulfonic acid ester,
From the group of optionally substituted phenyl and sulphate
May be substituted by one or two selected substituents
Alkyl and cyclohexyl having 1 to 4 carbon atoms
Can be Here, it is a substituent of the above alkyl
Examples of the optionally substituted phenyl include, for example, carbon
Alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulf
Selected from the group of ho and halogeno (chloro, bromo, etc.)
Phenyl optionally substituted by 1 to 2 substituents
And the like. R^TenAnd R¹¹Replace with
Specific examples of the optionally substituted alkyl include R ¹And R^Two
The same groups as those exemplified in can be mentioned,
Further, benzyl and the like which may be substituted may be mentioned.
it can. As the optionally substituted alkyl,
Preferably, methyl, ethyl, n-propyl, isopropyl
Pill, n-butyl, isobutyl, sec-butyl, 2-
Droxyethyl, 2-sulfoethyl, 2-methoxyethyl
2-carboxyethyl, 2-carbamoylethyl,
2-sulfamoylethyl, benzyl, 2-, 3- or
4-sulfobenzyl and the like are exemplified.

Examples of the optionally substituted phenyl represented by R ¹⁰ and R ¹¹ include, for example, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, sulfo, carboxy,
Halogeno, hydroxy, cyano, carbamoyl, sulfamoyl, carboxylate, 2-hydroxyethylsulfonyl, amino, acylamino and alkylamino (1 to 4 carbon atoms), which are substituted by one or two substituents selected from the group Phenyl and the like.

Specific examples of the optionally substituted phenyl are preferably 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 can be mentioned.

It is preferable that one of R ¹⁰ and R ¹¹ is hydrogen or an optionally substituted alkyl and the other is an optionally substituted phenyl. As particularly preferred R ¹⁰ and R ¹¹ , R ¹⁰ is a hydrogen atom, methyl or ethyl, and R ¹¹ is alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, sulfo, carboxy,
And phenyl which may be substituted with a group selected from the group consisting of halogeno, hydroxy, cyano and acylamino.

Examples of R ¹² in the formula (4c) include the same groups as those exemplified for R ¹⁰ and R ¹¹ in the formula (4a).

[0046] When T in the general formula (1) is a group represented by the formula (4a), as an amine compound of formula HNR ¹⁰ R ¹¹ used to form the group, for example, the following Things 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-aminobenzene-
3- or -4- (β-hydroxyethylsulfone)

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-aminoethanesulfonic 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, e-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.

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-, -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, -Carboxy-
4-acetylaminoaniline, 2-methoxy-5-methylaniline, ammonia, methylamine, ethylamine, dimethylamine, taurine, N-methyltaurine,
Examples thereof include mono- or di-ethanolamine, 2-sulfamoylethylamine, and 2-carbamoylethylamine. Among these, aniline, N-methylaniline, N-ethylaniline, N-ethyl-2-,
-3- or -4-chloroaniline, 2-, 3- or 4-
Ethyl aniline, 2-, 3- or 4-methoxy aniline, 2-, 3- or 4-propyl aniline, 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-methoxyaniline, 2-sulfo-4-acetylaminoaniline, 2-carboxy-4-acetylamino Aniline, 2
-Methoxy-5-methylaniline and the like are particularly preferred.

Preferred as R ¹² is hydrogen or alkyl having 1 to 4 carbon atoms, and particularly preferred among these is methyl or ethyl.

[0052] When T in the formula (1) is a group represented by the formula (4c), examples of the compound represented by HOR ¹² used to form the group, be mentioned, for example, the following Can be.

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- Ethoxybenzenesulfonic acid

E) The following aliphatic alcohols: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, 2-chloroethanol, 2-methoxyethanol, 2-ethoxyethanol, 3-methoxy Propanol, 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, 1-phenyl-2-propanol.

In the general formula (4b), Q ² represents —CH
_{2 -, - O -, -} S -, - SO 2 - or -NR ¹³ - (. Wherein R ¹³ is representative of the alkyl group which may optionally be hydrogen or substituted) represent, p is 1, 2 or 3 is there. The alkyl of R ¹³ is preferably one having 1 to 4 carbon atoms. Examples of the substituent of the alkyl include halogeno (chloro, bromo, etc.) and alkoxy having 1 to 4 carbon atoms. R
Examples of ¹³ include hydrogen, straight-chain or branched C ₁ -C ₄ alkyl and the like, with hydrogen, methyl and ethyl being particularly preferred. Examples of the group represented by the formula (4b) include residues derived from pyrrolidine, piperidine, piperazine, n-alkylpiperazine, morpholine, and the like. Above all, q is 2 and Q is -O
- or -CH ₂ -, i.e., morpholino or piperidino are particularly preferable.

As such a group represented by T, fluoro, chloro, optionally substituted pyridinio or the above formula (4a) are preferable, and among them, fluoro and chloro are particularly preferable.

The bisazo compound (1) in the present invention is
It 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.

Further, the bisazo compound in the present invention is not particularly limited as long as it is represented by the general formula (1), but the compound represented by the general formula (1a) is particularly preferred.

[0059]

Embedded image Wherein R ¹ , R ² , R ³ , R ⁴ , U, T and n have the above-mentioned meaning. ]

Among the compounds exemplified in Chemical formula 12, especially the following first to fourth conditions, ie, first, R ¹ and R
² is, independently of one another, hydrogen, methyl, ethyl; secondly, R ³ and R ⁴ are the same or different and are hydrogen, sulfo,
Methyl and methoxy, thirdly, U is the above formula (2a), and in the formula (2a), A ¹ is phenylene, R ⁵ is hydrogen, methyl, ethyl, and
Z ¹ is _{-SO 2 CH = CH 2, -SO} 2 CH 2 CH 2 OSO 3
Preferred is H, and fourthly, T is fluoro or chloro.

The method for producing the bisazo compound (1) of the present invention is not particularly limited, but for example, it can be produced as follows. First, in the compound (1) of the present invention,
When T is chloro or fluoro, for example, the form of the free acid is represented by the following formula (5)

[0062]

Embedded image [Wherein, R ¹ , R ³ and m have the above-mentioned meaning. ], 2,4,6-trihalogeno-s
-Condensation with triazine to give the following formula (6)

[0063]

Embedded image [Wherein, R ¹ , R ³ and m have the above-mentioned meaning. ] Can be obtained.

On the other hand, the following equation (7)

HU (7) wherein U has the meaning described above. And a compound represented by the following formula (8):

[0066]

Embedded image [Wherein, R ² , R ⁴ and n have the above-mentioned meaning. ] 2,4,6-trihalogeno-
By condensation with s-triazine, the following formula (9)

[0067]

Embedded image [Wherein R ² , R ⁴ , U and n represent the same meaning as above,
a represents chloro or fluoro. ] Can be obtained.

Each of the amine compounds represented by the general formulas (6) and (9) is diazotized according to a conventional method,
The obtained diazotized product is converted into a free acid in the following formula (10)

[0069]

Embedded image

[Wherein X ¹ and X ² have the above-mentioned meanings. And a salt thereof, whereby the bisazo compound represented by the general formula (1) or a salt thereof can be obtained by coupling in any order with the 1-amino-8-naphthol compound represented by the formula: Here, the coupling reaction can be carried out while adjusting the pH to 1 to 4 at a temperature of −10 ° C. to + 30 ° C., and the pH of 2 to 8 at a temperature of 0 ° C. to + 40 ° C. secondarily.

The bisazo compound (1) of the present invention can also be produced, for example, as follows. That is, the compound represented by the formula (7), the diamine compound represented by the formula (8), and the compound represented by the formula H-Tb
(11) [where Tb is calculated by the formulas (2a), (2b), (2c),
(4a), (4b), (4c) or optionally substituted pyridinio. However, in the case of a pyridinio which may be substituted, the formula (11) is represented by Tb. Is converted to a 2,4,6-trihalogeno-
By condensing with s-triazine, the following formula (12)

[0072]

Embedded image [Wherein R ² , R ⁴ , U and n represent the same meaning as above,
b is expressed by the formulas (2a), (2b), (2c), (4a),
(4b), (4c) or optionally substituted pyridinio. ] Can be obtained.

Using the compounds of the above formulas (6) and (12) as the diazo component, the 1-amino-8-
By coupling with a naphthol compound in any order, a bisazo compound represented by the general formula (1) or a salt thereof can be obtained.

Further, the bisazo compound (1) of the present invention
Can alternatively be produced as follows. That is, the compounds of the formulas (7) and (8) are converted to 2,4,
By condensing with 6-trihalogeno-s-triazine, the compound of the above formula (9) is obtained. Using the obtained compound (9) as a diazo component,
By coupling with an amino-8-naphthol compound, the following formula (13)

[0075]

Embedded image [Wherein R ² , R ⁴ , U and n represent the same meaning as above,
a represents chloro or fluoro. ] Can be obtained.

The coupling reaction here is performed while adjusting to the above-mentioned primary coupling reaction conditions, whereby the monoazo compound of the above formula (13) or a salt thereof can be obtained.

By condensing the compound of the formula (11) with the monoazo compound of the formula (13), the following formula (1)
4)

[0078]

Embedded image [Wherein R ² , R ⁴ , U and n represent the same meaning as above,
b is expressed by the formulas (2a), (2b), (2c), (4a),
(4b), (4c) or optionally substituted pyridinio. ] Can be obtained.

Here, the same compound can be obtained by changing the order of the condensation reaction of the compounds of the formulas (7) and (11) with 2,4,6-trihalogeno-s-triazine.

By using the compound of the formula (6) as the diazo component with respect to the compound of the formula (14), the following formula (1) which is a part of the bisazo compound represented by the general formula (1) or a salt thereof is also used. Compound 15) can be obtained. The coupling reaction here can be performed while adjusting to the above-described secondary coupling reaction conditions.

[0081]

Embedded image [Wherein R ¹ , R ² , R ³ , R ⁴ , U, m and n represent the above-mentioned meanings, and Tb represents the formulas (2a), (2b), (2c),
(4a), (4b), (4c) or optionally substituted pyridinio. ]

In the above-mentioned production method, in the condensation reaction involving 2,4,6-trihalogeno-s-triazine, the order of the condensation is not particularly limited. The conditions for the condensation reaction are not particularly limited. For example, the first condensation reaction is carried out at a temperature of -10 ° C to 40 ° C and a pH of 1 to 10, and the second condensation reaction is carried out at a temperature of 0 ° C to 10 ° C. The reaction is carried out at 70 ° C. under conditions of pH 2 to 10, and the third condensation reaction is carried out at a temperature of 10 ° C. to 100 ° C.
And under a condition of pH 2 to 9.

Further, in obtaining the bisazo compound (1) of the present invention, the following formulas (3a) and (3b)
The group represented by Y ¹ and Y ² is —CH ₂ CH ₂ L,
When the group L that is eliminated by the action of an alkali is, for example, an ester such as a sulfate ester or a phosphate ester, the formation of the ester group may be performed after the condensation reaction.

The starting compound 2,4,6-trihalogeno-s
-As triazine, cyanuric chloride and cyanuric fluoride are particularly preferred.

1-amino-8 represented by the above formula (10)
As the naphthol compound, H acid and K acid are preferable, and H acid is particularly preferable.

The bisazo compound (1) of the present invention or a salt thereof is useful, for example, as a dye for dyeing or printing a fiber material. The fiber 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 And the like.

As the natural cellulose fiber material, specifically, cotton or other plant fibers such as linen,
Hemp, jute and ramie 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.

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

The bisazo compound (1) or a salt thereof of the present invention can be dyed or printed on the above-mentioned material, particularly on the above-mentioned fiber material, by a method depending on the physicochemical properties. Specifically, for example, a method of dyeing or printing on the above-mentioned fiber material by a method such as an exhaust dyeing method, a cold batch-up method, a continuous dyeing method, or a printing method can be exemplified. For example, when performing exhaust dyeing on a cellulose fiber material,
Sodium carbonate, tertiary sodium phosphate, sodium bicarbonate, in the presence of an acid binder such as caustic soda, if necessary, add a neutral salt such as sodium sulfate and salt, and if necessary, a dissolution aid,
A method of dyeing at a temperature of 30 ° C. to 100 ° C. using a penetrant or a leveling agent 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 cellulose fibers by the cold batch-up method, neutral dyes such as sodium sulfate and sodium chloride,
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 at a constant temperature and 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, and then steaming or drying heat. One-phase padding method to be treated, or after immersing the fiber in a padding solution in which the compound of the present invention is dissolved, neutral salt such as sodium sulfate and salt, and padding an acid binder such as caustic soda or sodium silicate, Examples include a two-phase padding method in which treatment is performed by steaming or drying.

In the case of printing on cellulose fiber, printing is performed in one phase with a printing paste containing a binder such as baking soda and then steaming at a high temperature of 80 ° C. or higher, or in two phases. For example, printing with a neutral or weakly acidic printing paste and passing it through an electrolyte-containing alkaline bath, or over-padding with an alkaline electrolyte-containing padding solution, and then treating by steaming or drying. A method and the like are exemplified. Here, the printing paste may include a sizing agent and / or an emulsifier such as sodium alginate and starch ether, and may include a printing aid and / or a dispersant such as urea if necessary. May be.

When the compound of the present invention is dyed or printed on cellulose fibers, the acid binder used is not particularly limited. For example, hydroxides of alkali metals, alkali metals or alkaline earth metals and inorganic or organic acids may be used. And a compound which 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 sodium carbonate, tertiary sodium phosphate, sodium bicarbonate, sodium hydroxide, sodium carbonate, sodium silicate, and sodium bicarbonate. Examples include sodium diphosphate and sodium trichloroacetate.

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 bisazo compound or its salt of the present invention is excellent in reproducibility, particularly when dyeing or printing a cellulose fiber material, has good leveling properties and wash-off properties, and has high build-up properties. And the effective dyeing rate is high. In addition, there is an advantage that dyeing can be performed at a low salt concentration.

Further, by using the bisazo compound of the present invention or a salt thereof, various fastnesses, especially chlorine resistance,
Dyeings and prints having good light resistance, sweat resistance, sweat sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance and washing resistance to peroxide can be obtained.

The bisazo 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 triazine mononicotinate group, A dye having at least one of dichlorotriazine group, difluoromonochloropyrimidine group, and trichloropyrimidine group, or Sumifix, Sumixix Supr
a, Sumfix HF, Remazol, Lev
afix, Procion, Cibacron, Bas
ilen, Drimarene, Kayacation, K
Dyes which are commercially available under the titles such as Ayacelon React, and further, JP-A-50-178, JP-A-51-17538
No., JP-A-56-9483, JP-A-56-15481, JP-A-56-11
No. 8976, JP-A-56-128380, JP-A-57-2365, JP-A-57-2365
No. 57-89679, JP-A-57-143360, JP-A-58-191755,
JP-A-59-15451, JP-A-59-96174, JP-A-59-16146
No. 3, JP-A-60-6754, JP-A-60-123559, JP-A-60-
No. 229957, JP-A-60-260654, JP-A-61-126175,
JP-A-61-155469, JP-A-61-225256, JP-A-63-779
No. 74, JP-A-63-225664, JP-A-1-185370, JP-A-3
Dyes described in JP-A-770-770, JP-A-5-247366 and JP-A-6-287463. I. Reactive
Blue 19, C.I. I. Reactive Black5
Are exemplified.

[0100]

The bisazo compound of the present invention or a salt thereof is
It is useful as a reactive dye and has excellent dyeing properties such as build-up property and leveling property. Further, according to the method of the present invention, dark blue dyeings and prints excellent in various fastnesses can be obtained with good reproducibility.

[0101]

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 represent parts by weight.

Example 1 According to a conventional method, 3.69 parts of cyanuric chloride and 3.76 parts of 2,4-diaminobenzenesulfonic acid were adjusted to pH 1 in an aqueous medium.
From 4 to a temperature of -5 ° C to + 20 ° C, then 1-
5.63 parts of aminobenzene-3-β-sulfatoethylsulfone were added at pH 2.5 to 7, at a temperature of 0 ° C to 30 ° C.
By condensation with the following formula (16)

[0103]

Embedded image

The compound represented by the following formula was obtained.

Next, cyanuric chloride (3.69) was obtained in a conventional manner.
And 3.76 parts of 2,4-diaminobenzenesulfonic acid at a pH of 1 to 4 and a temperature of -10 ° C. to 20 ° C., whereby the following formula (17) is obtained.

[0106]

Embedded image

The compound represented by the following formula was obtained. Equation (1)
After diazotization of 6) by a conventional method, it is coupled with 6.39 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid at pH 1 to 3.5 at a temperature of 0 ° C to 30 ° C, and further, The diazo compound of the formula (17) is adjusted to pH
The product obtained by coupling at 4 to 8 at a temperature of 0 ° C. to 30 ° C. is subjected to salting out or evaporation and drying in a conventional manner to give a free acid in the form of the following formula (18)

[0108]

Embedded image (Λmax = 604 nm, in an aqueous medium) was obtained.

Example 2 In place of the formula (17) used in Example 1, the following Table 1 was used.
In the second column in Tables 1 to 6, instead of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, and the compound in the third column of the same table in place of 2,4-diaminobenzenesulfonic acid. The compound of column 4 of the same table was replaced with the compound of column 5 of the same table in place of cyanuric chloride, and the compound of column 6 of the same table was replaced with 1-aminobenzene-3-β-sulfatoethylsulfone. When each is used and synthesized in the same manner as in Example 1, the corresponding bisazo compound is obtained.

In the above synthesis, the same compound can be obtained even if the order of the primary condensation and the secondary condensation with respect to cyanuric chloride is changed. Further, instead of the compound described in column 6 of the same table, the corresponding hydroxy compound [for example, when the compound in column 6 is 1-aminobenzene-3-
In the case of β-sulfatoethylsulfone, 1-aminobenzene-3-β-hydroxyethylsulfone] is used instead, and the same result can be obtained by final sulfuric acid esterification by a conventional method. Is obtained.

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

[Table 3]

[0114]

[Table 4]

[0115]

[Table 5]

[0116]

[Table 6]

Example 3 In the same manner as in Example 1, the compounds of the above formulas (16) and (17) were synthesized, and the formula (17) was diazotized by a conventional method.
6.39 parts of -amino-8-hydroxynaphthalene-3,6-disulfonic acid was coupled at a pH of 1 to 3.5 at a temperature of 0 ° C to 30 ° C, and the diazo compound of the formula (16) was further converted to a pH of 4 8. Coupling at a temperature of 0 ° C. to 30 ° C. and salting-out or evaporating and drying the obtained product by a conventional method to give a free acid in the form of the following formula (1)
9)

[0118]

Embedded image Can be obtained.

Example 4 In place of 1-aminobenzene-3-β-sulfatoethylsulfone used in Example 3, the compound in the second column in Tables 7 to 9 below was replaced with cyanuric chloride instead of cyanuric chloride. The compound in column 3 was replaced with the compound in column 4 in place of 2,4-diaminobenzenesulfonic acid and the compound in column 5 in place of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid. When the compounds in the column are synthesized in the same manner as in Example 3 by using the compounds in the sixth column of the same table in place of the formula (17), the corresponding bisazo compounds are obtained.

In the above synthesis, the same compound can be obtained even if the order of the primary condensation and the secondary condensation with respect to cyanuric chloride is changed. Tables 7-9 above
In place of the compound described in the second column, the corresponding hydroxy compound [for example, when the compound in the sixth column is 1-aminobenzene-3-β-sulfatoethylsulfone, 1-aminobenzene -3- [beta] -hydroxyethylsulfone], and finally sulfated by a conventional method.

[0121]

[Table 7]

[0122]

[Table 8]

[0123]

[Table 9]

Example 5 In a conventional manner, 3.69 parts of cyanuric chloride and 3.76 parts of 2,4-diaminobenzenesulfonic acid were added in an aqueous medium to a pH of 1.
From 4 to a temperature of -5 ° C to + 20 ° C, then 1-
5.63 parts of aminobenzene-3-β-sulfatoethylsulfone are condensed at a pH of 2.5 to 7 and a temperature of 0 to 30 ° C., and 1.86 parts of aniline are further condensed at a pH of 1 to 4,
Condensation at a temperature of 30 ° C. to 80 ° C. for 1 to 8 hours, the following formula (20)

[0125]

Embedded image

The compound represented by the following formula can be obtained. This was diazotized by a conventional method, and then coupled with 6.39 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid at a pH of 1 to 3.5 and a temperature of 0 ° C to 30 ° C. Formula (1) synthesized in the same manner as in Example 1
The diazo compound of 7) was prepared at pH 4 to 8 at a temperature of 0 ° C to 3
The product obtained by coupling at 0 ° C. is salted out or evaporated to dryness by a conventional method to give a free acid in the form of the following formula (2)
1)

[0127]

Embedded image Is obtained.

Example 6 Instead of the formula (17) used in Example 5, the compound in the second column in Tables 10 to 15 below was replaced with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid. The compound in the third column of the same table is replaced with the compound in the fourth column of the same table in place of 2,4-diaminobenzenesulfonic acid.
A method similar to that of Example 5, using the compound in column 5 of the same table in place of 1-aminobenzene-3-β-sulfatoethylsulfone and the compound in column 6 of the same table instead of aniline, respectively. And the corresponding compounds can be obtained.

In the above synthesis, the same compound can be obtained even if the order of the primary condensation and the secondary condensation with respect to cyanuric chloride is changed. Further, among the compounds described in columns 5 and 6 of the same table, those having a sulfate ethylsulfonyl group are those having a corresponding hydroxy compound [for example, the compound in column 5 is 1-aminobenzene- In the case of 3-β-sulfatoethylsulfone, 1-aminobenzene-3-β-hydroxyethylsulfone is used instead, and the compound in column 6 is 2- (β
-Sulfatoethylsulfonyl) ethylamine, instead of 2- (β-hydroxyethylsulfonyl) ethylamine] and the same synthesis, followed by sulfuric esterification by a conventional method. can get. Furthermore, the same result can be obtained by changing cyanuric chloride to cyanuric fluoride.

[0130]

[Table 10]

[0131]

[Table 11]

[0132]

[Table 12]

[0133]

[Table 13]

[0134]

[Table 14]

[0135]

[Table 15]

Example 7 In the same manner as in Example 5, the compounds of the above formulas (20) and (17) were synthesized, and the compound of the formula (17) was diazotized by a conventional method, and then 1-amino-8-hydroxynaphthalene- 3,6
6.39 parts of disulfonic acid, pH 1 to 3.5, temperature 0
C. to 30.degree. C., and the above formula (1)
The diazo compound of 6) was prepared at pH 4 to 8 at a temperature of 0 ° C to 30.
The product obtained by coupling at ℃ is salted out or evaporated to dryness by a conventional method to give the following formula (2)
2)

[0137]

Embedded image Can be obtained.

Example 8 In place of the aniline used in Example 7, the following Table 16
-17, the compound in the third column of the same table was used in place of 1-aminobenzene-3-β-sulfatoethylsulfone, and the same compound was used in place of 2,4-diaminobenzenesulfonic acid. Of the fourth column of the same table in place of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, and the compound of the fifth column of the same table instead of the compound of the formula (17). Using each of the compounds in column 6,
When synthesized in the same manner as in Example 7, each corresponding compound is obtained.

In the above synthesis, the same compound can be obtained even if the order of the primary condensation and the secondary condensation with cyanuric chloride is changed. Further, among the compounds described in the third and second columns of the same table, those having a sulfate ethylsulfonyl group are the corresponding hydroxy compounds [for example, the compound in the third column is 1-aminobenzene- In the case of 3-β-sulfatoethylsulfone, 1-aminobenzene-3-β-hydroxyethylsulfone is used instead, and the compound in column 2 is 2- (β
-Sulfatoethylsulfonyl) ethylamine, instead of 2- (β-hydroxyethylsulfonyl) ethylamine] and the same synthesis, followed by sulfuric esterification by a conventional method. can get. Further, the same result can be obtained even when cyanuric chloride is changed to cyanuric fluoride.

[0140]

[Table 16]

[0141]

[Table 17]

Example 9 In a conventional manner, 3.69 parts of cyanuric chloride and 4.67 parts of 2- (β-sulfatoethylsulfonyl) ethylamine were placed in an aqueous medium at a pH of 5 to 8 and a temperature of -5 ° C to + 10 ° C.
C. and then 3.76 parts of 2,4-diaminobenzenesulfonic acid at pH 2 to 6, temperature 0 to + 25.degree.
To condense. After diazotizing this, 1-amino-8
-Hydroxynaphthalene-3,6-disulfonic acid 6.3
9 parts with a pH of 1 to 3.5 and a temperature of 0 ° C. to + 15 ° C. and then 2.46 parts of 3-carboxypyridinio at a pH of 2 to 4 and a temperature of + 40 ° C. to +1.
Condensate at 00 ° C. Further, the product obtained by coupling the diazo compound of the formula (17) synthesized in the same manner as in Example 1 at a pH of 4 to 8 and a temperature of 0 ° C. to 30 ° C. is subjected to salting out or drying by a conventional method. In the form of the free acid, the following formula (23)

[0143]

Embedded image

A bisazo compound represented by the following formula can be obtained.

Example 10 Instead of the above formula (17) used in Example 9, the compound in the second column in the following Tables 18 to 19 was replaced with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid. The compound in the third column of the same table is replaced with the compound in the fourth column of the same table in place of 2,4-diaminobenzenesulfonic acid.
Same as Example 9 except that 2- (β-sulfatoethylsulfonyl) ethylamine was replaced with the compound in column 5 of the same table and 3-carboxypyridinio was replaced with the compound in column 6 of the same table. And the corresponding compounds can be obtained.

In the above synthesis, the same compound can be obtained even if the order of the primary condensation and the secondary condensation with cyanuric chloride is changed. Further, among the compounds described in columns 4 and 5 of the same table, those having a sulfate ethylsulfonyl group are represented by the corresponding hydroxy compounds [for example, when the compound in column 4 is 2- (β-sulfatoethyl) In the case of sulfonyl) ethylamine, 2- (β-hydroxyethylsulfonyl) ethylamine is used instead, and the compound in column 5 is 1-aminobenzene-3-β
In the case of -sulfatoethylsulfone, 1-aminobenzene-3-β-hydroxyethylsulfone is used in place of the above, and the same result can be obtained by final sulfuric acid esterification in a conventional manner. can get. Furthermore, the same result can be obtained by changing cyanuric chloride to cyanuric fluoride.

[0147]

[Table 18]

[0148]

[Table 19]

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 sodium carbonate was added, dyed at the same temperature for 1 hour, and then 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 is uniform,
It was a dark blue color. Also, chlorine resistance of the obtained dyed product,
Light fastness, sweat resistance, sweat sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance and peroxide washing resistance were all good.

Dyeing Example 2 Dyeing was carried out in exactly the same manner as in Dyeing Example 1, except that the amount of sodium sulfate was changed from 20 parts to 10 parts. The obtained dyed products each have the same quality as the dyed product obtained in Dyeing Example 1.

Dyeing Example 3 Dyeing is carried out in exactly the same manner as in Dyeing Example 1, except that the used amount of sodium sulfate is changed from 20 parts to 4 parts. The obtained dyed products each have the same quality as the dyed product obtained in Dyeing Example 1.

Dyeing Example 4 In each of Dyeing Examples 1 to 3, dyeing is performed in exactly the same manner except that the dyeing temperature is changed from 60 ° C. to 70 ° C.
The dyeings obtained have the same quality as the dyeings obtained in Dyeing Examples 1 to 3, respectively.

Dyeing Example 5 In each of Dyeing Examples 1 to 3, dyeing is performed in exactly the same manner except that the dyeing temperature is changed from 60 ° C. to 80 ° C.
The dyeings obtained have the same quality as the dyeings of Dyeing Examples 1 to 3, respectively.

Dyeing Example 6 Instead of using 0.3 part of each compound in each of Dyeing Examples 1 to 5, 0.3 part of each compound and the sodium salt of a condensate of methylnaphthalenesulfonic acid and formaldehyde (sulfone) Degree of polymerization 110%, average degree of polymerization 1.8) 0.
Dyeing is carried out in exactly the same manner except that 06 parts are used. The dyeings obtained have the same quality as the dyeings of Dyeing Examples 1 to 5, respectively.

Dyeing Example 7 Using each of the compounds obtained in Examples 1 to 10, a color paste having the following composition is prepared.

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

This color paste was printed on mercerized cotton broad, and after intermediate drying, steaming was performed at 100 ° C. for 5 minutes, and washed with hot water, soaping, hot water, and dried.
Finish. The print is uniform and dark blue. In addition, all the fastnesses of chlorine resistance, light resistance, sweat resistance, sweat sunlight resistance, acid hydrolysis resistance, alkali resistance, washing resistance and peroxide washing resistance of this printed matter are good. .

Dyeing Example 8 In Dyeing Examples 1 to 7, the compounds of Example 1 were used in place of the compound of Example 1.
Dyeing is performed with 10 compounds or formulations. The obtained dyed products have the same quality as the dyed products obtained in Dyeing Examples 1 to 7, respectively.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshiyuki Araki 3-1-198 Kasuganaka, Konohana-ku, Osaka-shi F-term in Sumitomo Chemical Co., Ltd. 4H056 JA06 JB02 JB03 JB04 JE04 4H057 AA02 BA07 BA24 DA01 DA24 DA33 DA34 GA04 GA07

Claims (10)

[Claims] 1. A bisazo compound represented by the following general formula (1) or a salt thereof. Embedded image [In the formula, X ¹ and X ² are each one hydroxy and the other amino, R ¹ and R ² are the same or different and represent hydrogen or an optionally substituted alkyl, R ³ and R ⁴ Is
Same or different, represents hydrogen, sulfo, methyl, methoxy or chloro, m and n are the same or different and represent 0 or 1, and U represents the following formula (2a), (2b) or
represents a group represented by c), <Wherein, R ⁵ represents hydrogen or an optionally substituted alkyl, R ⁶ and R ⁷ have the same meaning as R ⁵ , or represent phenyl, and A ¹ represents an optionally substituted phenylene or Represents an optionally substituted naphthylene, A ² represents an optionally substituted alkylene, Q ¹ represents —O—,
—S— or —NR ⁸ —, wherein R ⁸ represents hydrogen, optionally substituted alkyl or optionally substituted phenyl, and r and s are the same or different,
Or Z ¹ , Z ^2, and Z ³ are the same or different and are represented by the following formula (3a) or (3b): (Y ¹ and Y ² are the same or different and represent —CH ＝ CH ₂ or —CH ₂ CH ₂ L, wherein L is a group capable of leaving under the action of an alkali, and R ⁹ is hydrogen or substituted And p represents an integer of 1 to 6.) represents a fiber-reactive group represented by the formula: and T is the same or different and has the same meaning as U, or represents fluoro, chloro, Optionally substituted pyridinio or the following formulas (4a) and (4
b) or (4c). Embedded image {R ¹⁰ and R ¹¹ are the same or different, represent hydrogen, alkyl which may be substituted, the phenyl which may be also be cycloalkyl or substituted optionally be substituted, R ¹²
Have the same or different meanings as R ¹⁰ and R ¹¹ ,
² _{-CH 2 -, - O -,} - S -, - SO 2 - or -NR
¹³ - represents, here R ¹³ represents an alkyl which may be hydrogen or substituted, q is 1, 2 or 3. ｝) 2. The bisazo compound or a salt thereof according to claim 1, wherein R ¹ and R ² are hydrogen. 3. The method according to claim 1, wherein R ³ and R ⁴ are hydrogen.
Or the salt thereof. 4. The method according to claim 1, wherein T is fluoro or chloro.
4. The bisazo compound or a salt thereof according to any one of claims 1 to 3. 5. The bisazo compound or a salt thereof according to claim 1, wherein T is optionally substituted pyridinio. 6. The formula (4a), (4b) or (4c)
The bisazo compound or a salt thereof according to any one of claims 1 to 3, which is a group represented by the formula: 7. The bisazo compound or a salt thereof according to claim 1, wherein U is a group represented by the formula (2a) or (2b). 8. The method according to claim 1, wherein U is a group represented by the formula (2a) or (2b), and Z ¹ and Z ² are groups represented by the formula (3a). Or a salt thereof. 9. A compound represented by the following general formula (1a): [Wherein R ¹ , R ² , R ³ , R ⁴ , n, U and T
Represents the meaning described in claim 1. The bisazo compound according to any one of claims 1 to 8 or a salt thereof. 10. A method for dyeing or printing a fiber material, comprising using the bisazo compound according to claim 1 or a salt thereof.