JPH03250055A - Bisazo compound, and method for dyeing or printing fibrous material therewith - Google Patents

Abstract

NEW MATERIAL:A bisazo compd. shown, in the form of a free acid, by formula I (wherein X is formula II, NR2R3, OR4, etc.; Y is pyridinio, etc.; Z1 and Z2 are each SO2CH=CH2 or SO2CH2CH2Z' wherein Z' is a group to be eliminated by the action of an alkali; A is phenylene, naphthylene, alkylene, etc.; B is formula III or IV; D is naphthylene, sulfo-substd. phenylene, etc.; R1 R7 are each H or alkyl; R2 to R4 are each H, alkyl, phenyl, etc.; R6 is H, methyl, etc.; and X1 and X2 are each NH2 or OH). USE:A dye which is fiber-reactive and capable of dyeing or printing cotton, hemp, wool, silk, leather, polyamide fiber, etc., with excellent resistances to light, wetting, alkali, acid hydrolysis, friction, etc. PREPARATION:A 2,4,6-trihalogeno-s-triazine is condensed with a compd. of formula V and then with a compd. of formula VI and the resulting compd. is condensed with a pyridine compd. to give a compd. of formula I.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is directed to materials containing hydroxyl groups and/or amide groups, particularly cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, etc., and blends thereof. The present invention relates to an improved compound suitable for dyeing and printing fibers, which enables one-light-fast and wet-fast dark blue dyeing, and its application.

<Prior art> As a compound having a vinyl sulfone reactive group and a pyridinium triazine reactive group in the same molecule,
Although it is known in Japanese Patent No. 173060, it is insufficient in terms of dyeing performance, such as build-up property, and further improvement is desired.

<Problems to be Solved by the Invention> Conventionally, various reactive dyes have been widely used in the fields of dyeing and printing textile materials. However, the current state of the art still does not fully satisfy the high requirements regarding suitability for specific dyeing methods and the increasing sophistication of requirements regarding the fastness of dyed products.

The above-mentioned known reactive dyes are insufficient in solubility, dyeing performance (for example, build-up properties, etc.), and fastness, and there is a strong desire to provide further improved dyes.

The importance of having excellent build-up properties is an extremely important factor in today's world, where demands for economic efficiency of dyeing methods are becoming higher and higher.

The present inventors completed the present invention as a result of intensive studies aimed at improving the drawbacks of the above-mentioned known dyes and finding a new compound that can broadly satisfy the requirements required for dyes.

Means for Solving the Problems> The present invention provides the following - large quantity (1) [wherein, , Y is a substituted or unsubstituted pyridinio group, Z and Z independently represent -3O2CH=CH, or SO, CH, CH2Z', and Z' is a group that is eliminated by the action of Flukaline. represent. A represents a phenylene, naphthylene or alkylene group which may have a substituent.

B represents a group represented by the following formula) (* represents a bond connected to an azo group), and D represents a naphthylene group optionally substituted with sulfo or a phenylene group substituted with sulfo. R,l
hydrogen or an optionally substituted alkyl group, R2,
R*, R4 and R1 independently represent hydrogen or an alkyl, phenyl, naphthyl or benzyl group which may be substituted with W.

R1 is hydrogen, a methyl group, a methoxy group, or a sulfo group;
1 represents hydrogen or an optionally substituted alkyl group.

One of xl and X represents an NH2 group and the other represents a 0■ group. ] The present invention provides a bisazo compound represented by the following and a method for dyeing or printing a fiber material using the bisazo compound.

In general formula (1), phenylene and naphthylene represented by 8 are preferably substituted with 1 or 2 substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo. Examples include phenylene which may be substituted with sulfo, or naphthylene which may be substituted with sulfo, such as (In the formula, the bond shown with an asterisk means a bond that connects to the -N- group). I can give it to you. In addition, the alkylene represented by 8 has the following formula, Ro (CH2) -0 (CH2)@* -(alk')-N-(alk' )-*
(c) 2 R+ (In the formula, the bond shown with an asterisk means a bond that leads to the -N- group. alk is a polymethylene group having 1 to 6 carbon atoms or a different isomer thereof, Ro is hydrogen,
chlorine, bromine, fluorine, hydroxy, sulfato, acyloxy with 1 to 4 carbon atoms, cyanide, carboxy, alkoxycarbonyl with 1 to 5 carbon atoms or carbamoyl, Ro is hydrogen or 01-G alkyl, alk ' independently represents a polymethylene group having 2 to 6 carbon atoms or a branched isomer thereof, and ark' and Ro may form a ring through a methylene group. n is 1 to 5. m is an integer from 1 to 6. ) can be mentioned.

The polymethylene group represented by alk in the above formulas (a), ra) and (C) is preferably methylene, ethylene,
In methylmethylene, propylene, and butylene, R" is hydrogen, methyl, ethyl, propyl, inpropinoheptyl, isobutyl, 5eC-butyl, tert-butylene,
Examples include L/, pentyl, hexyl, etc., and hydrogen is preferred. The polymethylene group represented by alk' is preferably ethylene, propylene or butylene.

The numbers represented by n and m are preferably 2.3 or 4 independently of each other.

Examples of the group represented by B include H3 υ(H5 CFli-CL (in the formula, the bond shown with ** means a bond that leads to the -N=N- group), and preferably , for example, (in the formula, the bond indicated by ** has the above meaning).

D is preferably a naphthylene group optionally substituted with 1 or 2 sulfo groups or a phenylene group substituted with 1 sulfo group, such as (in the formula, the bond indicated by ** is N=means a bond leading to an N- group.

Among these, those having a sulfo group at the ortho position of the azo group are preferred, such as (in the formula, the bond indicated by ** has the above meaning).

Groups that are eliminated by the action of alkali, represented by Zo, are:
For example, sulfuric esters, thiosulfuric esters, phosphoric esters, acetic esters, halogens, etc. fall under this category, and among them, sulfuric esters are preferred.

The optionally substituted alkyl represented by R1 and R1 is preferably a C1 to C4 alkyl, and the optionally substituted group includes hydroquine, cyano,
Preferred are alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl.

Particularly preferable examples of R1 and R7 include hydrogen,
Methyl, ethyl, η-propyl, js.

Propyl, n-butyl, 1so-butinope5ec-butyl, 2-hydroxyethyl, 2-hydroxypropyl,
3-hydroxypropyl, 2-hydroxybutyl, 3-
Hydroxybutyl, 4-hydroxybutinope 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-siaraburvir,
Methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-
Ethoxybrobyl, 2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxy Ethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonyl Ethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3
-ethylcarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, ethyl carbonyloxymethyl,
2-Methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfomethyl Propyl, 4-sulfobutinopesulfamoylmethyl, 2
-sulfamoylethyl, 3-sulfamoylpropyl, and 4-sulfamoylbutyl.

Particularly preferred among these are hydrogen, methyl, and ethyl.

The optionally substituted alkyl represented by R3 and R3 is, for example, 1 or 2 selected from the group of alkoxy, sulfo, carboxy, hydroxy, chloro, phenyl, and sulfate having 1 to 4 carbon atoms. Preference is given to alkyl having 1 to 4 carbon atoms, which may be substituted with 1 to 4 substituents.

Among them, particularly preferred are methyl, ethyl, n-propyl, 1so-propyl, n-butyl, 1so-butyl, 5
Examples include ec-butyl, β-hydroxyethyl, β-sulfatoethyl, β-sulfoethyl, β-methoxyethyl, and β-carboxyethyl.

In addition, the optionally substituted phenyl represented by R2 and R3 includes, for example, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, chloro, and propylene. selected from that group,
Phenyl optionally substituted with one or two substituents is preferred.

Among them, phenyl, 2-13- or 4-
Sulfophenyl, 2,4- or 2,5-disulfophenyl, 2-13- or 4-carboxyphenyl, 2-13
Examples of -4 include 4-chlorophenyl, 2-13- or 4-methylphenyl, and 2-13- or 4-methoxyphenyl.

Further, the optionally substituted naphthyl represented by R3 and R3 includes, for example, hydroxy, carboxy/, sulfo, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, and Naphthyl optionally substituted with 1, 2 or 3 substituents selected from the group of chloro is preferred.

Among them, particularly preferred is 2-13-14-25.6-1
7- or 8-sulfo-1-naphthyl, 1-15-16-
17- or 8-sulfo-2-naphthyl, 1.5-15,
7-16, 8-14, 8.4.7-13.8-14.6
-13,7- or 3,6-disulfo-2-naphthyl, 4
, 6,8.2.4.7- or 3,6.8-)disulfo-
1-naphthyl, 1.5.7-54,6,8- or 3,
6. 8-) Disulfo-2-naphthyl and the like.

Furthermore, the optionally substituted benzyl represented by R2 and R5 is selected from the group of, for example, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, and chloro. Benzyl optionally substituted with one or two substituents is preferred.

Among these, benzyl, 2-13- or 4-
Examples include sulfobenzyl.

In the present invention, either one of R2 and R5 is hydrogen, methyl or ethyl, and the other is 01-4 alkyl,
From the viewpoint of dye properties, phenyl which may be substituted with C4 alkoxy, sulfo, carboxy or halogeno is particularly preferred.

In the above-mentioned large amount (1), when X is -NR2Rs, HN used to form such a group
Examples of the compound represented by R2R3 include ammonia, 1-aminobenzene, 1-amino-2-,
-3= or -4-methyl-benzene, 1-amino-3,
4- or -3,5-dimethylbenzene, 1-amino-2
-, -3- or 4-ethylbenzene, 1-amino-2-
-3- or -4-methoxybenzene, 1-amino-23
- or -4-ethoxybenzene, l-ami/2--3=
or -4-chlorobenzene, 3- or 4-amino-phenylmethanesulfonic acid, 2.3- or 4-aminobenzenesulfone I, 3-methylaminobenzenesulfonic acid,
3-ethylaminobenzenesulfonic acid, 4-methylaminobenzenesulfone! , 4-ethylaminobenzenesulfone L 5-aminobenzene-1,3-disulfonic acid,
6-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,4-disulfone L 4-aminobenzene-1,2-disulfonic acid, 4-amino-5-methylbenzene-1,2-dinulfonic acid , 2-13- or 4-aminobenzoic acid, 5-aminobenzene-1,3-dicarboxylic acid, 5-amino-2-hydroxybenzenesulfonic acid, 4-amino-2-hydroxybenzenesulfonic acid, 5
-Amino-2-ethyquinbenzenesulfonic acid, N-methylaminobenzene, N-ethylaminobenzene, 1-methylamino-3- or -4-methylbenzene, 1-ethylamino-4-chlorohenzene, 1-ethylamino -3
- or -4-methylbenzene, 1-(2-hydroxyethyl)-amino-3-methylbenzene, 3- or 4-methylaminobenzoic acid, 3- or 4-methylaminobenzenesulfonic acid, 2-aminonaphthalene- 1-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-ami
Nonapthacine-1-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 4-amino Naphthalene-2-sulfone L 5-aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 7-
Aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-2-sulfonic acid, 7-ethylaminonaphthalene-2-sulfonic acid, 7-butylaminonaphthalene-2-sulfonic acid, 7-isobutylaminonaphthalene-2
-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid,
4-aminonaphthalene-1,3-disulfonic acid, 5-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 8- aminonaphthalene-1
, 3-disulfonic acid, 2-aminonaphthalene-1,5-
Disulfonic acid, 3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,6-disulfonic acid, 8-
Aminonaphthalene-1,6-disulfonic acid, 4-aminonaphthalene-1,7-disulfonic acid, 3-aminonaphthalene-2,6-disulfonic acid, 4-aminonaphthalene-1,7-disulfonic acid
2,6-disulfonic acid, 3-aminonaphthalene-2,7
-disulfonic acid, 4-aminonaphthalene-2,7-disulfonic acid, 6-aminonaphthalene-1,3,5-)disulfonic acid, 7-aminonaphthalene-1,3,5-)disulfonic acid, 4-aminonaphthalene-1,3,5-)disulfonic acid -1,3,6-trisulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, 8-aminonaphthalene-1,3゜6-trisulfonic acid and 4-aminonaphthalene-1,3, Aromatic amines such as 7-trisulfonic acid, or methylamine,
Ethylamine, n-propylamine, inpropylamine, n-butylamine, isobutylamine, 5ec-butylamine, dimethylamine, diethylamine, methylethylamine, allylamine, 2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol,
2-methylaminoethanol, bis-(2-hydroxyethyl)amine, 2-acetylamine ethylamine, 1
-amino-2-propatol, 3-methoxypropylamine, 1-amino-3-dimethylaminepropane, 2-
Aminoethanesulfonic acid, aminomethanesulfonic acid, 2
-Methylaminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, ε-aminocaproic acid, benzylamine, 2-13- or 4-chlorobenzylamine, 4 - Aliphatic amines such as methylbenzylamine, N-methylbenzylamine, 2-13- or 4-sulfobenzylamine, 2-phenylethylamine, 1-phenylethylamine, 1-phenyl-2-propylamine may be mentioned. can.

Particularly preferred compounds include, for example, aniline, N-methylaniline, N-ethylaniline, 2-
13--1. f is 4-chloroaniline, N-methyl-2-34 or -4-chloroaniline, N-ethyl-
2--3- or -4-chloroaniline, 2-13- or 4-methylaniline, aniline-2,4- or -2,
5-disulfonic acid, 3- or 4-methylaminobenzenesulfonic acid, 3- or 4-ethylaminobenzenesulfonic acid, 2-. Examples include 3- or 4-carboxyaniline, taurine, N-methyltaurine, mono- or di-ethanolamine, and the like.

The optionally substituted alkyl represented by R4 and Rs is, for example, one or 1 to carbon atoms optionally substituted with 2 substituents
Alkyl having 4 is preferred.

Among them, methyl, ethyl, n-propyl, 1
so-brobinopene n-butyl, 1so-butyl, 5eC
-butyl, β-hydroxyethyl, β-sulfatoethyl, β-sulfoethyl, β-methoxyethyl, β-ethoxyethyl, β-chloroethyl, β-carboxyethyl, and the like.

Furthermore, the optionally substituted phenyl represented by R2 and R3 includes, for example, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, chloro, and Preferred is phenyl optionally substituted with one or two substituents selected from the group of bromo.

Among them, Feninobe 2-13- or 4-
Sulfophenyl, 2. 4-4c2. 5 disulfophenyl, 2-13- or 4-chlorophenyl, 2-13-
or 4-methylphenyl, and 2-13- or 4-methoxyphenyl.

Further, the optionally substituted naphthyl represented by R1 and R3 includes, for example, hydroxy, carboxy, sulfo, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, and chloro. selected from the group of 1. Naphthyl optionally substituted with 2 or 3 substituents is preferred.

Among them, particularly preferred is 2-13-14-15.6-1
7- or 8-sulfo-1-naphthyl, 1-15-16-
17- or 8-sulfo-2-naphthyl, 1,5-15.
7-16.8-14,8.4. 7-13.8-14.
6-13,7- or 3,6-disulfo-2-naftinope 4.6. ．． 8.2, 4.7- or 3.6.8-) Ho 1-naphthyl for squirrels, 1.5.7-14, 6.8- or 3
．． 6.8-) disulfo-2-naphthyl and the like.

Furthermore, the optionally substituted benzyl represented by R1 and R3 is selected from the group of, for example, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, and chloro. Benzyl optionally substituted with one or two substituents is preferred.

Among these, benzyl, 2-13- or 4-
Examples include sulfobenzyl.

In the above-large quantity (1), when X is 10R4,
Compounds represented by R and OH used to form such groups include, for example, 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-, -34 is 4-ethoxybenzene, l-hydroxy-2-- 3- or -4-chlorobenzene, 3-
or 4-hydroxy-phenylmethanesulfone R13-
Hydroxybenzenesulfonic acid, 4-hydroxybenzenesulfone L 5-hydroxybenzene-13-disulfonic acid, 6-hydroxybenzene-1°4-disulfonic acid, 4-hydroxybenzene-1°2-disulfone M,
4-Hydroxy-5-methylbenzene-1,2-disulfone L 3-41;! 4-hydroxybenzoic acid, 5-hydroxybenzene-1°3-dicarboxylic acid, 5-hydroxy-2-ethoxybenzenesulfonic acid, 2-hydroxynaphthalene-1-sulfonic acid, 4-hydroxynaphthalene-1-sulfonic acid, 5 -Hydroxynaphthalene-1
-sulfonic acid, 6-hydroxinaphthalene-1-sulfonic acid, 7-hydroxinaphthalene-1-sulfonic acid, 8
- Hydroquinaphthalene-1-sulfonic acid, 1-hydroxynaphthalene-2-sulfonic acid, 4-hydroxynaphthalene-2-sulfonic acid, 5-hydroxynaphthalene-2
-sulfonic acid, 6-hydroxynaphthalene-2-sulfone [7-hydroxynaphthalene-2-sulfonic acid, 8-
Hydroxynaphthalene-2-sulfonic acid, 4-hydroxynaphthalene-1,3-disulfonic acid, 5-hydroxynaphthalene-1,3-disulfonic acid, 6-hydroxynaphthalene-1,3-disulfonic acid, 7-hydroxynaphthalene-1,3-disulfonic acid -1,3-disulfonic acid, 8-hydroxynaphthalene-1°3-disulfonic acid, 2-hydroxynaphthalene-1,5-disulfonic acid, 3-hydroxynaphthalene-1,5-disulfonic acid, 4-hydroxynaphthalene-
1,5-disulfonic acid, 4-hydroxynaphthalene-1
,6-disulfone 18-hydroxynaphthalene-1,6
-disulfonic acid, 4-hydroxynaphthalene-1,7-
Disulfonic acid, 3-hydroxynaphthalene-2,6-disulfonic acid, 4-hydroquinnaphthalene-2,6-disulfone 13-hydroquinnaphthalene-2,7-disulfonic acid, 4-hydroquinnaphthalene-2,7-disulfone acid, 6-hydroxynaphthalene-1.3゜5-trisulfonic acid, 7-hydroxynaphthalene-1.3.5-)disulfonic acid, 4-hydroxinaphthalene-1,3,6-
) disulfonic acid, 7-aminonaphthalene-1,3,6-
Trisulfonic acid, 8-aminonaphthalene-1,3,6-
) disulfonic acid and 4-aminonaphthalene-1,3,7
- aromatic compounds such as trisulfonic acid, or methanol, ethanol, n-propanol, isopropanol, n-butanol, imbutanol, 5ec-butanol, 2-chloroethanol, 2-methoxyethanol,
2-ethoxyethanol, 3-methoxypropertool,
3-ethoxybrono(nol, 2-hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2
-Cyanoethanol, 2-sulfatoethanol, glycolic acid, 3-hydroxypropionic acid, benzyl alcohol, 2-. 3-Also L<1t4-10 lobenzyl alcohol, 4-methylbenzyl alcohol, 2-. 3-
or aliphatic compounds such as 4-sulfobenzyl alcohol, 2-phenylethanol, and 1-phenyl-2-propanol; Examples of R55H used to form a group include the above-mentioned compounds in which hydroxy is mercapto.

When Y is a pyridinio group having a substituent, examples of the substituent include carboxy, cal/imoyl, sulfo, halogeno, and substituted or unsubstituted alkyl having 1 to 4 carbon atoms.

Examples of substituted alkyl groups include β-hydroxyethyl and β-sulfoethyl. The pyridinio group represented by Y is preferably a carboxy- or carbamoyl-substituted pyridinio group, and a carboxypyridinio group is especially preferred from the viewpoint of dye properties.

Preferably, pyridine which may have a substituent is
Pyridine, 2-23- or 4-carboxypyridine, 2
−． Examples include 3- or 4-carbamoylpyridine, 3-sulfopyridine, 4-β-sulfoethylpyridine, 3-β-hydroxyethylpyridine, 4-chloropyridine, 3-methylpyridine, 3,5-dicarboxypyridine, etc. .

Among these, particularly preferred are 3-1 or 4-carboxypyridine, cotinic acid, and isonicotinic acid.

The compounds of the invention are present in the form of the free acid or in the form of its salts, in particular the alkali metal and alkaline earth metal salts, especially the soda, potassium and lithium salts.

The compound of the present invention can be produced, for example, in the following manner. A compound represented by the following general formula (II> [wherein B, D, Rt,
R1 (III) HNA Z2 HNR, R3 (IV) HOR, (V) HS R, (Vl) (wherein A, R1, R2, Rs, R4, Rs and Z
2 has the meaning given above. ) by condensing any of the compounds represented by 2,4.6-dolyhalogenoS-)riazine with the following general formula (■) [where T represents a halogen, B%D ,X,X,.

Xz, Rt and Zl have the meanings given above. ], and then condensing a pyridine compound to obtain a compound of general formula (1).

2.4.6-)Rehalogeno-5-)In the condensation reaction with riazine, the order is not particularly limited,
Also, the reaction conditions are not particularly limited, but - secondly, temperature -
Condensation is carried out while adjusting the pH to 2 to 9 at a temperature of 10 to 40 degrees Celsius, pH 2 to 9 at a temperature of 0 to 70 degrees Celsius in the second stage, and pH 2 to 7 at a temperature of 10 to 100 degrees Celsius in the case of a tertiary step. A compound represented by (1) or a salt thereof can be obtained.

As the raw material 2.4.6-)rehalogeno-S-)riazine, cyanuric chloride and cyanuric fluoride are particularly preferred.

As the dye matrix in the present invention [a compound in which the vinyl sulfone reactive group in the general formula (n) is a hydrogen atom], for example, 1-hydroxy-2-(1'-sulfonaphtho-2'-
ylazo)-L-(5'-amino-2'sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7 -(5'-amino-2'sulfophenylazo)-8-aminonaphthalene3.5-disulfonic acid, 1-hydroxy-2-(5'-amino-2'sulfophenylazo) -7-(1 '-sulfonaphtho-21-ylazo)-8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-(5'-amino-2'sulfophenylazo)-7-(1'-sulfonaphtho-21 -ylazo)-8-aminonaphthalene-3,5-disulfonic acid, l-hydroxy-2-(1'-sulfonaphtho2'-ylazo)-7-(5'-amino-2'4'-disulfophenylazo )-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(1'-sulfonaphtho2'-ylazo)-7-(5'-amino-2'4'-disulfophenylazo)- 8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2-(5'-amino-2'4'-disulfophenylazo)-7-(1'-sulfonaphtho-2'
-ylazo)-8-ami/naphthalene-3,6-disulfonic acid, 1-hydroxy-2-(5'-amino-2'4'-disulfophenylazo)-7-(1'-sulfonaphtho-2'
-ylazo)-8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2-(1',?'-disulfonaphtho~2'-ylazo)-7-(5'-amino-21-sulfophenylazo )-8-aminonaphthalene-3,6-
Disulfonic acid, l-hydroxy-2-(5'-amino-2'sulfophenylazo)-7-(]]', 7'-disulfophenylnaphtho-21-ylazo)-8-aminonaphthalene-3,
6-disulfonic acid, ■-Hydroxy-2-(5'-amino-2'sulfophenylazo)-7-(6'-sulfonaphth-21-ylazo)-8-aminonaphthalene-3
,6-disulfonic acid, 1-hydrocyto2-(5'-amino-2'sulfophenylazo>-7-(8'-sulfonaphtho-2'-ylazo)-8-aminonaphthalene-3,6-disulfone Acid, 1-hydroxy-2-(5'-amino-2'sulfophenylazo)-7-(6'-sulfonaphth-21-ylazo)-8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2 -(1' ~ sulfonaphthol 2'-
ylazo)-7-<4'-ami/-2'sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(1'-sulfonaphth-2'-ylazo)- 7-(4'-amino-2'5'-disulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(1'-sulfonaphtho-2'-
ylazo)-7-(4'-amino-2'5'-disulfophenylazo)-8-aminonaphthalene-3,5-disulfonic acid, ■-Hydroxy-2-(1'-sulfo-5'aminomethylnaphtho) -2'-ylazo)-7-(2,'-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-(2'-sulfophenylazo)-
7-(1'-sulfo-51-aminomethylnaphtho-21
-ylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(1'-sulfo-5'aminomethylnaphtho-2'-ylazo)-7-(1'-sulfonaphtho-2' -ylazo)-8-aminonaphthalene-3,
6-disulfonic acid, 1-hydroxy-2-(1'-sulfonaphtho-2'-ylazo)-7-(1'-sulfo-
5'Aminomethylnaphtho-21-ylazo)-8-aminonaphthalene-3,6-disulfonic acid, nihydroxy-2-(1',7'-disulfo5'-aminomethylnaphtho-2'-ylazo)-7 -(2'-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(2'-sulfophenylazo)
-7-(1',7'-disulfo-5'-aminomethylnaphtho-2'-ylazo)-8-aminonaphthalene-3,
6-Disulfonic acid, 1-hydroxy-2-(5'-aminomethyl-4'-methyl-2'-sulfophenylazo)-7-(1'-sulfonaphth-2'-ylazo)-8
-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(1'-sulfonaphtho-2'-ylazo)-7-(5'-aminomethyl-4'-methyl-2'-
sulfophenylazo)-87minonaphthalene-3,6-
Disulfonic acid, l-hydroxy-2-(2'-sulfophenylazo)-7-(5'-amino-2'-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy- 2-(5'-ami7-2'sulfophenylazo)-7-(2'-sulfophenylazo)-8-
Aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(2'-sulfophenylazo")
-7-(5'-amino-2',4'-disulfophenylazo)-8-aminonaphthalene-36-disulfonic acid, )-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7 -(1'7'-disulfo-51-aminomethylnaphtho-21-ylazo) = 8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-
(1'-sulfonaphtho-2'-ylazo)-7-<51
-amino-4'methyl-21-sulfophenylazo)-
8-aminonaphthalene-3,6-disulfonic acid, l-hydroquine-2-(1'-sulfonaphtho-2'-ylazo)-7-(4'-amino-5'methoxy-2'-sulfophenylazo)- 8-aminonaphthalene-3,6-disulfonic acid, l-and droxy-2-(1'-sulfonaphtho-2'-ylazo)-7-(5'-amino-4'methoxy-2'-sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-
(2'-sulfophenylazo)-7-(4'-amino-
5'-methoxy-2'-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(4'-amino-5'methquin-
2'-sulfophenylazo)-7-(1'-sulfonaphtho-2'-ylazo)-8-aminonaphthalene-3,6
-disulfonic acid, 1-hydroxy-2-(5'-amino-4'methoxy-2'-sulfophenylazo)-7-
(1'-sulfonaphth-21-ylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-
2-(4'-amino-5'methoxy-2'-sulfophenylazo)-7-(2'-sulfophenylazo)-8
-aminonaphthalene-3,6-disulfonic acid and the like.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing hydroxyl group-containing or carbonamide group-containing materials. Preferably, the material is used in the form of a fibrous material or a blend thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or their regenerated products and polyvinyl alcohol.

Cellulose fiber material is cotton, as well as other vegetable fibers,
For example, linen, hemp, jute and ramie fibers are preferred. Regenerated cellulose fibers are, for example, viscose stable and filament viscose.

Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-4.

The compounds of the present invention can be dyed or printed on the above-mentioned materials, in particular on the above-mentioned fiber materials, in a manner depending on their physical and chemical properties.

For example, in the case of exhaust dyeing on cellulose fibers, in the presence of an acid binder such as soda carbonate, sodium phosphate or caustic soda, a neutral salt such as mirabilite or common salt is optionally added, and if desired, a solubilizer is added. , use a penetrant or leveling agent together,
It is carried out at relatively low temperatures. The neutral salts which accelerate the exhaustion of the dyestuff can be added only after the actual dyeing temperature has been reached, or even before then, optionally in portions.

When dyeing cellulose fibers according to the padding method, it can be padded at room temperature or at an elevated temperature and, after drying, fixed by steaming or dry heat.

When printing is carried out on cellulose fibers, it can be printed in one phase, e.g. with a printing paste containing baking soda or other acid condensing agents, and then steamed at 100-160°C, or in two phases, e.g. This can be carried out by printing with an acidic or weakly acidic printing paste, passing it through a hot alkaline bath containing an electrolyte, or overpadding with a padding liquid containing an alkaline electrolyte and steaming or dry heat treatment.

Thickening agents or emulsifiers, such as, for example, sodium alginate or starch ethers, are used in the printing pastes, if desired in combination with customary printing auxiliaries and/or dispersants, such as, for example, urea.

Acid binders suitable for immobilizing the compounds of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali upon heating. Particular mention may be made of alkali metal hydroxides and alkali metal salts of weak to medium strength inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Examples of such acid binders include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary, or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate, and the like.

The dyeing of synthetic and natural polyamide and polyurethane fibers can be carried out by first exhausting under pH control from an acidic or slightly acidic dye bath and then changing to a neutral or even alkaline OpH value for fixation. . Dyeing can usually be carried out at a temperature of 60 to 120°C, but in order to achieve level dyeing properties, conventional leveling agents such as a condensation product of cyanuric chloride and 3 times the mole of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, addition products of stearylamine and ethylene oxide can also be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing textile materials.

Especially suitable for dyeing cellulose fiber materials, good light fastness and sweat resistance, good moisture resistance, such as washing resistance, peroxidation washing resistance, chlorine resistance, sweat resistance, acid hydrolysis resistance and alkali resistance, as well as good abrasion resistance and ironing resistance.

In addition, it has excellent build-up properties, level dyeing properties, and wash-off properties, as well as good solubility, exhaustion and fixation properties, and is less susceptible to fluctuations in dyeing temperature and dye bath ratio, resulting in dyed products of stable quality. It has characteristics in certain points.

Another characteristic of the dyed product is that there is little discoloration during fix treatment or resin processing, and there is little change due to contact with basic substances during storage.

Hereinafter, the present invention will be explained in detail with reference to Examples.

In the examples, parts and % represent parts by weight and % by weight, respectively.

(Left below) Example 1 2.4-diaminobenzenesulfonic acid 4.
70 parts of cyanuric chloride are condensed together, followed by condensation with 2.33 parts of aniline, which is diazotized, and then with 7.73 parts of 1-amine-8-hydroxynaphthalene-3,5-disulfonic acid. Coupling under strong acidity, and further coupling with 2-naphthylamine-6-β-sulfatoethylsulfone-
Coupling was carried out with a diazo compound containing 1 to 10.25 parts of sulfonic acid. Finally, 3.1 parts of 3=pyridinecarboxylic acid is added and a substitution reaction is carried out at 70 to 80°C to convert into chloride) IJ
A bisazo compound represented by the following formula was obtained in the form of a free acid.

Example 2 2-naphthylamine-6-β used in Example 1
-sulfatoethylsulfone-1-sulfonic acid, 2.
4-diaminobenzenesulfonic acid, 1-amino-8-hydroxynaphthalene-3,6 disulfonic acid, aniline,
Instead of 3-pyridinecarboxylic acid, the compounds in the second column, third column, 41st (lil, fifth column, and sixth column) of the table below were used in order to synthesize in the same manner as in Example 1, and the corresponding A bisazo compound was obtained and dyed to obtain a dyed product having the color tone shown in column 7 of the table below.

(Leaving space below) Example 3 The procedure was carried out in the same manner as in Example 1, except that the coupling order of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and two types of diazo compounds was reversed, and the coupling order of the free acid was A bisazo compound represented by the following formula was obtained.

Example 4 Using each compound described in each column of Example 2, a corresponding bisazo compound was synthesized in the same manner as in Example 3.

Example 5 In place of the compounds described in the fifth column of Nα1 to Nα32 in the table of Example 20, the compounds shown below were used,
Synthesis was carried out in the same manner as in Example 2 or 4 to obtain the corresponding disazo compound.

Phenol, phenol-2-, -3- or -4-sulfonic acid, phenol-2,4- or -2°5-disulfonic acid, benzylamine, benzylamine-2-, -3-
, or -4-sulfonic acid, taurine, N-methyltaurine, β-alanine, mono- or di-ethanolamine.

Example 6 Each bisazo compound described in Examples 1 to 5 0.1,0
．． Dissolve 3, 0, and 6 parts in 200 parts of water, and add 10 parts of mirabilite.
The mixture was heated to 60°C, 4 parts of soda carbonate was added, and dyed for 1 hour. After washing with water, soaping, rinsing with water and drying, a navy dyed product with excellent fastness and good build-up properties was obtained.

Example 7 A colored paste having the following composition was made using each of the bisazo compounds described in Examples 1 to 5.

Bisazo compound 5 parts urine
Base: 5 parts Sodium alginate (5%) Base paste: 50 parts Heat
Hot water 25 parts weight
Cao 2nd part balance
Part 13 This color paste is printed on mercerized cotton broadcloth, and after intermediate drying, it is steamed at 100℃ for 5 minutes, washed with hot water, soaped, washed with hot water, and dried to produce a navy-colored textile with excellent fastness. I got something.

(Margin below)

Claims (8)

[Claims] (1) In the form of free acid, the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -
NR_2R_3, -OR_4 or -SR_5, Y is a substituted or unsubstituted pyridinio group, Z_1 and Z
_2 independently represents -SO_2CH=CH_2 or -SO_2CH_2CH_2Z', and Z' represents a group that is eliminated by the action of an alkali. A represents a phenylene, naphthylene or alkylene group which may have a substituent. B is a group represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (The * mark represents a bond connected to an azo group.) D is a sulfo group Represents an optionally substituted naphthylene or sulfo-substituted phenylene group. R_1
represents hydrogen or an optionally substituted alkyl group, R_2
, R_3, R_4 and R_5 each independently represent hydrogen or an optionally substituted alkyl, phenyl, naphthyl or benzyl group. R_6 is hydrogen, methyl group, methoxy group or sulfo group,
R_7 represents hydrogen or an optionally substituted alkyl group. One of X_1 and X_2 represents an NH_2 group and the other represents an OH group. ] A bisazo compound represented by (2) The compound according to claim 1, wherein D is a phenylene or naphthylene group having a sulfo group at the ortho position of the azo group. (3) The compound according to claim 1 or 2, wherein Y is a pyridinio group substituted with a carboxyl group or a carbamoyl group. (4) The compound according to any one of claims 1 to 3, wherein R_1 and R_7 are independently hydrogen, methyl, or ethyl. (5) Z_1 and Z_2 independently of each other -SO_2CH
=CH_2 or -SO_2CH_2CH_2OSO_3
The compound according to any one of claims 1 to 4, which is H. (6) X is −NR_2R_3, and R_2 and R_3
6. The compound according to claim 1, wherein are each independently hydrogen, an optionally substituted alkyl group, or a phenyl group. (7) The compound according to any one of claims 1 to 5, wherein X is -NR_2R_3, R_2 is hydrogen, methyl or ethyl, and R_3 is an optionally substituted phenyl group. (8) A method for dyeing or printing a fiber material, which comprises using the bisazo compound according to claim 1.