JPH03250056A - Bisazo compound, and method for dyeing or printing fibrous material therewith - Google Patents

Abstract

NEW MATERIAL:A bisazo compd. shown by formula I (wherein X is NR2R3, OR4, or SR5; 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 II or II; D is phenylene, naphthylene, etc.; R1 and R7 are each H or alkyl; R2 to R5 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 IV, a compd. of formula V, and a comp. selected from the group consisting of compds of formulas VI, VII, and VIII, in an arbitrary order, to give a compd. of formula I.

Description

Detailed Description of the Invention <Industrial Application Fields> 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> A bisazo compound having a triazinyl group and a plurality of novinylsulfone reactive groups in the same molecule is known from JP-A-63-118376; is sufficient;
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 is based on the following formula (I) [wherein, X is NR2R3, OR4 or SRs,
Z and Z are independently S Oz CH= CH
2 or -3O2CH2CH2Z', and Zo represents a group that is eliminated by the action of an alkali. Δ represents a phenylene, naphthylene or alkylene group which may have a substituent.

B represents a group represented by the following formula (the mark * represents a bond connected to an azo group), and D represents a phenylene or naphthylene group which may have a substituent. R represents hydrogen or an optionally substituted alkyl group, and R2, R3, R- and R9 each independently represent hydrogen or an optionally substituted alkyl, phenyl, naphthyl or benzyl group. However, R1
represents a group other than hydrogen. R6 represents hydrogen, a methyl group, a methoxy group, or a sulfo group, and R1 represents hydrogen or an optionally substituted alkyl group. One of Xl and x2 is Nl2
group, and the other one represents an OH 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 (I), phenylene and naphthylene represented by 8 are preferably substituted with one or two substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo. Examples include phenylene which may be substituted with sulfo, and naphthylene which may be substituted with sulfo. In addition, as lekylene, a Ro (CH2), -0-(CH2), -* (b
) (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 branched isomer thereof, Ro is hydrogen, chlorine, bromine, fluorine, hydroxy, sulfato, acyloxy with 1 to 4 carbon atoms, cyano, carboxy, alkoxycarbonyl with 1 to 5 carbon atoms or carbamoyl, R'' is hydrogen or 01-6
Alkynope alk' independently means a polymethylene group having 2 to 6 carbon atoms or a branched isomer thereof, and alk' and R'' may mutually form a ring through a methylene group. n is 1 to 6.m is an integer from 1 to 6.〉 Examples include the groups shown below.

The polymethylene group represented by alk in the above formulas (a), et al.) and (C) is preferably methylene, ethylene,
These are methylmethylene, propylene, and butylene.

R″ is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 5eC-butyl, ter
Examples include t-butyl and pentinopehexyl, with hydrogen being 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.

The group represented by B is nz- CH2 (In the formula, The bonds indicated with ** are -N=N- means a bond that is the same as the

) For example, preferably, (In the formula, Bonds marked with ** have the above meanings. ) etc. can be mentioned.

D is preferably selected from the group of methinopeethyl, methquine, ethoxy, chloro, bromo and sulfo.
Examples include phenylene which may be substituted with one or two substituents or naphthylene which may be substituted with sulfo. (means a bond that connects to the N-group).

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

The group 2″ that is eliminated by the action of an alkali is:
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-C4 alkyl, and the optionally substituted group includes hydroxy, cyano,
Preferred are alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl.

Preferred examples of R and R7 include hydrogen, methyl, ethyl, n-propyl, 1so-propyl, n-butyl, 1so-butyl, 5ec-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl. 2-Hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxyptynopecyanomethino
2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethquinpropyl, 2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl JL=,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-methoxycarbonylprobinope 3-ethoxycarbonylprobyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyl oxymethyl, ethylcarbonyloxymethyl, 2-
Methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl,
3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfobrobinope 4-sulfobutyl, sulfamoylmethyl, 2-
Sulfamoylethyl, 3-sulfamoylpropyl,
4-sulfamoylbutyl can be mentioned. Particularly preferred among these are hydrogen, methyl, and ethyl.

The optionally substituted alkyl represented by R7 and R5 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, methyl, ethyl, n-propyl, 1so-propyl, n-butyl, 15O-butyl, 5
Examples include ec-butyl, β-hydroxyethinohe, β-sulfatoethyl, β-sulfoethyl, β-methoxyethyl, and β-carboxyethyl.

Furthermore, the optionally substituted phenyl represented by R7 and R5 includes, for example, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, chloro, and hybromo. selected from the group of
Phenyl optionally substituted with one or two substituents is preferred.

Among them, Feninobe 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 R7 and R1 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 f 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-naphthyl, 4
．． 6. 8.2, 4.7~ or 3. 6. Examples include 8-) disulfo-1-naphthyl, 1,5.7-14,6.8- or 3.6.8-) disulfo-2-naphthyl, and the like.

Furthermore, the optionally substituted benzyl represented by R2 and R3 is selected from the group of, for example, alkyl having 1 to 4 carbon atoms, alcoquine 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, one of R2 and R1 is hydrogen, methyl or ethyl, and the other is 01-.

From the viewpoint of dye properties, phenyl which may be immodified with alkyl, 01-4 alkoxy, sulfo, carboxy or halogeno is particularly preferred.

- In formula (1) above, when X is =N Rt R-, H used to form such a group
Examples of the compound represented by N Rz Rs include ammonia, 1-aminobenzene, ■-amino-2
-, -3- or -4-methyl-benzene, I-amino-
3,4- or -3,5-dimethylbenzene, l-amino-2-, -3- or -4-ethylbenzene, l-amino-2-3- or -4-methoxybenzene, 1-amino-2- -3- or -4-ethoxybenzene I-ami/
-2--3- or -4-chlorobenzene 3- or 4-
Amino-phenylmethanesulfonic acid, 2,3- or 4-
Aminobenzenesulfonic acid, 3-methylaminobenzenesulfone B, 3-ethylaminobenzenesulfonic acid, 4
-Methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid, 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-disulfonic 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-ethoxybenzenesulfonic acid, N-methylaminobenzene, N-ethylaminobenzene, 1-methylamino-3- or -4-methylbenzene, l-ethylamino-4-chlorobenzene, 1-ethylamino-3- or -4-methylbenzene, 1- (2
-hydroxyethyl)-amino-3-methylbenzene,
3- or 4-methylaminobenzoic acid, 3- or 4-methylaminobenzenesulfone M, 2-aminonaphthalene-
1-Sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid 1-sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 7-aminonaphthalene-2-sulfonic acid 2-sulfonic acid, 7-
Methylaminonaphthalene-2-sulfonic acid, 7-nitylaminonaphthalene-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
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-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic acid, 4-aminonaphthalene-2,7-disulfonic acid, 6-amino Naphthalene-1,
3,5-trisulfonic acid, 7-aminonaphthalene-1,
3,5-)disulfonic acid, 4-aminonaphthalene-1,
3,6-trisulfonic acid, 7-aminonaphthalene-1,
3,6-trisulfonic acid, 8-aminonaphthalene-1,
3,6-trisulfonic acid and 4-aminonaphthalene-1
゜3, 7-) Aromatic amines such as disulfonic acid, or methylamine, ethylamine, n-propylamine,
Isopropylamine, n-butylamine, isobutylamine, 5ec-butylamine, dimethylamine, diethylamine, methylethylamine, allylamine, 2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol, 2-methylamineethanol, bis-
(2-Hydroxyethyl)amine, 2-acetylaminoethylamine, l-amino-2-propatol, 3-methoxyprobylamine, 1-amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid, aminomethanesulfone acid, 2-methylaminoethanesulfone II,
3-Amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, ε-aminocaproic acid, benzylamine, 2-. 3- or 4-chlorobenzylamine, 4-methylbenzylamine, N-methylbenzylamine, 2-13-4) or 4
-sulfobenzylamine, 2-phenylethylamine,
Mention may be made of aliphatic amines such as 1-phenylethylamine, 1-7enyl-2-propylamine.

Particularly preferred compounds include, for example, aniline, N-methylaniline, N-ethylaniline, 2-1
3-7 or 4-chloroaniline, N-methyl-2-, -
34f: -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, 2-13- or 4-carboxyaniline, Examples include taurine, N-methyltaurine, mono-modified or di-ethanolamine, and the like.

The optionally substituted alkyl represented by R1 and R3 is selected from the group consisting of alkoxy, sulfo, carboxy, hydroxy, chloro, phenyl, cyano and sulfate having 1 to 4 carbon atoms, for example. 1 to carbon atoms optionally substituted with 2 substituents
Alkyl having 4 is preferred.

Among them, methyl, ethyl, n-propyl, 1
so-propyl, n-butyl, 1so-butyl, 5eC
-butyl, β-hydroxyethyl, β-sulfatoethyl, β-sulfoethinoheβ-methoxyethyl, β-ethquinethyl, β-chloroethyl, β-carboquinethyl, and the like.

In addition, the optionally substituted phenyl represented by R2 and R6 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, 2-13-4 includes 4-chlorophenyl, 2-13- or 4-methylphenyl, and 2-13- or 4-methoxyphenyl. .

Further, the optionally substituted naphthyl represented by R4 and R2 includes, for example, hydroxy, carboxy, sulfo, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, and chloro. Naphthyl optionally substituted with 1,2 or 3 substituents is preferred.

Among them, particularly preferred is 2-13-14-15.6-1
7- or 8-sulfo-1-naphthyl, 1-15-56-
17- or 8-sulfo-2-naftinope 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, 1.5.7-14 ．． 6. 8- or 3, 6. 8-) Disulfo-2-naphthyl and the like.

Furthermore, the optionally substituted benzyl represented by R4 and R6 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 formula (1) above, when X is -OR,
Compounds represented by R and OH used to form such groups include, for example, phenol, l-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, l -hydroxy-2--3- or -4-
Chlorbenzene, 3- or 4-hydroxy-phenylmethanesulfonic acid, 3-hydroxybenzenesulfonic acid,
4-hydroxybenzenesulfonic acid, 5-hydroxybenzene-1゜3-disulfonic acid, 6-hydroxybenzene-1゜4-disulfonic acid, 4-hydroxybenzene-
1゜2-disulfonic acid, 4-hydroxy-5-methylbenzene-1,2-disulfonel, 3-4 is 4-hydroxybenzoic acid, 5-hydroxybenzene-1,3-dicarboxylic acid, 5-hydroxy-2 -ethoxybenzenesulfonic acid, 2-hydroquinaphthalene-1-sulfonic acid, 4
-Hydroxynaphthalene-1-sulfonic acid, 5-hydroxynaphthalene-1-sulfone M, 6-hydroxynaphthalene-1-sulfonic acid, 7-hydroxynaphthalene-1-sulfonic acid, 8-hydroxynaphthalene-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, 8-hydroxynaphthalene-1°3-disulfonic acid,
2-hydroxynaphthalene 1,5-disulfonic acid, 3-
Hydroxynaphthalene-1,5-disulfonic acid, 4-hydroxynaphthalene-1,5-; Sulfonic acid, 4-hydroxynaphthalene-1,6-disulfonic acid, 8-hydroquinaphthalene-1,6-disulfone M, 4 -Hydroxynaphthalene-1,7-disulfone [3-hydroxynaphthalene-2,6-disulfonic acid, 4-hydroxynaphthalene-2,6-disulfonic acid, 3-hydroxynaphthalene-2,7-disulfonic acid, 4-hydroxynaphthalene -2,7-disulfonic acid, 6-hydroxynaphthalene-1,3゜5-trisulfonic acid, 7-hydroxynaphthalene-1,3,5-trisulfonic acid, 4-hydroxynaphthalene-1,3,6 -) disulfonic acid, 7-aminonaphthalene-1,3,6-)disulfonic acid, 8-aminonaphthalene-1,3,6-)disulfonic acid and 4-aminonaphthalene-1,3,7-)disulfonic acid. aromatic compounds such as methanol, ethanol, n-propanol, impropanol, n-butanol, imbutanol, 5ec-butanol, 2-chloroethanol,
2-methoxyethanol, 2-ethoxyethanol, 3
-methoxypropanol, 3-ethoxypropanol,
2-hydroxyethanesulfonic acid, 3-hydroxy-1-
Propanesulfonic acid, 2-cyanoethanol, 2-sulfatoethanol, glycolic acid, 3-hydroxypropionic acid, benzyl alcohol, 2-. 3-1: or 4-chlorobenzyl alcohol, 4-methylbenzyl alcohol, 2-. 3-MoL< is 4-sulfobenzyl alcohol, 2-phenylethanone 1-phenyl-
Examples include aliphatic compounds such as 2-propatol, and when X is -SR6 in the above general formula (1), R35H used to form such a group includes the above compounds. Compounds in which hydroxy is mercapto can be mentioned.

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. It has the meaning of the following general formula (formerly XI x2 [wherein, BSD, Rt, XI, X2 and Z, c above]). ] A compound represented by the following general formula (III) 1
(■) H-N-A-22 [wherein R,, A and Z2 have the above-mentioned meanings. ], and further the following general formulas (IV) to (Vlf>
HN R2R3 (IV ) HOR, (V) HS R, (Vl) (wherein R2, R3, R-, and R3 have the above-mentioned meanings) with any of the compounds represented by 2. 4. A compound of general formula (1) can be obtained by condensation with 6 trihalogeno S-) lyazine in any order.

In the condensation reaction with 2,4.6-)rehalogeno-5-)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-5-)riazine, cyanuric chloride and cyanuric fluoride are particularly preferred.

As the dye matrix in the present invention [a compound in which the vinyl sulfone-based reactive group in formula (II) above is a hydrogen atom], for example, l-hydroquine-2-(1'-sulfonaphtho-2'-
ylazo)-7-(5'-amino-2'sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-(1'-sulfonaphtho-2'-
ylazo)-L-(5'-amino-2'sulfophenylazo)-8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2-(5'-amino-2'sulfophenylazo) -7-(1'-sulfonaphth-2'-ylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(5'-amino-2'-sulfonaphthyl-2'-ylazo)-7- (1'-sulfonaphth-22-ylazo)-8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7-(5'-amino-2 '4'-disulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-(1'-sulfonaphtho-2'-
ylazo) -7-(5'-amino-2'4'-disulfophenylazo)-8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2-(5'-amino-2'4'-disulfophenylazo)-7-(1'-sulfonaphtho-21
-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',7'-disulfonaphtho-2'-ylazo)-7-(5'-amino2'-sulfophenylazo )-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(5'-amino-2'sulfophenylazo)-7-(1'7'-disulfophenylnaphtho-2'- Ylazo)-8-aminonaphthalene-3,6
-Disulfonic acid, I-hydroxy-2-(5'-amino-2'sulfophenylazo)-7-(6'-sulfonaphth-21-ylazo)-8-aminonaphthalene-3,6
-Disulfonic acid 1. 1-Hydroxy-2-(5'-amino-2'sulfophenylazo>-7-(8'-sulfonaphth-21-ylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2 -(5'-amino-2'sulfophenyla7')-7-(6'-sulfonaphth-21-ylazo)-8-aminonaphthalene3.5-disulfonic acid, 1-hydroxy-2-(1'-sulfonaphtho- 2'-
ylazo)-7-(4'-amino-2'sulfophenylazo)-8-aminonaphthalene = 3.6-disulfonic acid, 1-hydroxy-2-(1'-sulfonaphtho2'-ylazo')-7 -(4'-amino-2'5'-disulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, ■-Hydroxy-2- (1'-sulfonaphtho-2'-
ylazo)-7-(4'-amino-2'5'-disulfophenylazo)-8-aminonaphthalene-3,5-disulfonic acid, 1-hydroxy-2-(1'-sulfo-5'aminomethyl naphtho-2'-ylazo)-7-(2'-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(2'-sulfophenylazo)-
7-(1'-sulfo-51-aminemethylnaphtho-21
-ylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(1'-sulfo-5'aminomethylnaphtho-2'-ylazo)-7-(1'-sulfonaphtho-21- 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, l-hydroxy-2-(1',7'-disulfo-5'-aminomethylnaphtho-2'-ylazo) -7-(2'-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroquine-2-(2'-sulfophenylazo)-L-(1',7'-disulfo- 5'-aminomethylnaphtho-2'-ylazo)-8-aminonaphthalene-3
, 6-disulfonic acid, 1-hydroxy-2-(5'-
Aminomethyl-4'-methyl-2'-sulfophenylazo)-7=(1'-sulfonaphtho-2'-ylazo)-
8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-(1'-sulfonaphtho-2'-ylazo)-7-(5'-aminomethyl 4'-methyl-2'-
sulfophenylazo)-8=aminonaphthalene-3,6
-disulfonic acid, 1-hydroxy-2-(2'-sulfophenylazo)-7-(5'-amino-2'-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy -2-(5'-amino-2'sulfophenylazo>-7-(2'-sulfophenylazo)-
8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-(2'-sulfophenylazo)-
7-(5'-amino-2',4'-disulfophenylazo)-8-aminonaphthalene-36-disulfonic acid, l-hydroxy-2-(1'-sulfonaphth-2'-ylazo)-7- (1',?'-disulfo-5'-aminomethylnaphtho-21-ylazo)-8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-(
1'-sulfonaphtho-2'-ylazo)-7-(5'-
Amino-4'methyl-2'-sulfophenylazo)-8
-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(5'-amino-2'sulfophenylazo)-7-phenylazo-8-aminonaphthalene-3,6
-disulfonic acid, 1-hydroxy-2-(5'-amino-2'4'-disulfophenylazo)-7-phenylazo-8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-( 1'-Sulfonaphtho-2'-ylazo)-7-(4'-amino-5'methoxy-2'-
Sulfophenylazo)-8-aminonaphthalene-3,6
-disulfonic acid, 1-hydroxy-2-(1'-sulfonaphtho2'-ylazo)-7-(5'-amino-4'methoxy-21-sulfophenylazo)-8-aminonaphthalene-3,6-disulfone acid, 1-hydroxy-2-
(2'-sulfophenylazo)-7-(4'-amino-
5'-methquin-2'-sulfophenylazo)-8-aminonaphthalene-3,6-disulfonic acid, l-hydroxy-2-(4'-amino-5'methoxy-2'-sulfophenyla7') -7-(1'-sulfonaphth-21-ylazo)-8-aminonaphthalene-3
, 6-disulfonic acid, 1-hydroxy-2-(5'-
Amino-4'methoxy-21-sulfophenylazo)-
7-(1'-Sulfonaphth-2'-ylazo)-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-(4'-amino-5'methquin-27-sulfophenyl-7')-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 materials containing hydroxyl groups or carbonamide groups. 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 is carried out first by exhaustion under pH control from an acidic or slightly acidic dye bath, and then by changing to a neutral or even alkaline pH value for fixation. I can do it. 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.

(The following is a blank space) Example 1 2.4-diaminobenzenesulfonic acid 4.
70 parts and 4.61 parts of cyanuric chloride are condensed, and then 1-
Aminobenzene was condensed with 6.95 parts of 3-β-sulfatoethyl sulfone, and after diazotization, 1-amino-
8-Hydroxynaphthalene 3.6-disulfonic acid 7.7
This was coupled with 3 parts of 2-naphthylamine-6-βsulfatoethylsulfone-1-sulfonic acid under strong acidity, and further coupled with 10.25 parts of a diazo compound of 2-naphthylamine-6-βsulfatoethylsulfonic acid.

Finally, 2.33 parts of aniline was added to carry out a condensation reaction at 70 to 80°C, followed by salting out with sodium chloride to obtain a bisazo compound represented by the following formula 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, 1-aminobenzene-3-βsulfatoethylsulfone, aniline (7) Substituent: 1, in order Synthesize in the same manner as in Example 1 using the compounds in the second column, third column, fourth column, fifth column, and sixth column to obtain the respective corresponding bisazo compounds,
After dyeing, a dyed product having the color tone shown in column 7 of the table below was obtained.

(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 the compounds represented by Nα in each first column in the table of Example 2, the corresponding bisazo compounds were synthesized in the same manner as in Example 3.

Example 5 Synthesis was carried out in the same manner as in Example 2.4, using the compounds shown below in place of the compounds listed in column 5 of N(,1-Nα36) in the table of Example 2, and the corresponding bisazo The compound was obtained.

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
．． 3 and 0.6 parts each in 200 parts of water, and 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 division
Lance
Part 13 This color paste is printed on mercerized cotton broadcloth, and after intermediate drying, steaming at 100℃ for 5 minutes, washing with hot water, buffing, washing with hot water, and drying produces a navy-colored paste with excellent fastness. A printed product was obtained.

(Margin below)

Claims (7)

[Claims] (1) In the form of free acid, there are the following general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is -NR_2R_3, -OR_4 or -
SR_5, Z_1 and Z_2 independently of each other -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 substituent represents a phenylene or naphthylene group which may have R_1 is hydrogen or an optionally substituted alkyl group, R_2, R_3, R_4 and R_
5 independently represents hydrogen or an optionally substituted alkyl, phenyl, naphthyl or benzyl group. However, R_4 represents a group other than hydrogen. R_6 represents hydrogen, a methyl group, a methoxy group, or a sulfo group, and R_7 represents hydrogen or an optionally substituted alkyl group. X_1 and X
One of _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 has a sulfo group at the ortho position of the azo group and is an optionally substituted phenylene or naphthylene group. (3) X is -NR_2R_3, R_2 and R_3
3. The compound according to claim 1, wherein are each independently hydrogen, an optionally substituted alkyl group, or a phenyl group. (4) The compound according to claim 1 or 2, wherein X is -NR_2R_3, R_2 is hydrogen, methyl or ethyl, and R_3 is an optionally substituted phenyl group. (5) The compound according to any one of claims 1 to 4, wherein R_1 and R_7 are independently hydrogen, methyl or ethyl. (6) 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 5, which is H. (7) A method for dyeing or printing a fiber material, which comprises using the bisazo compound according to claim 1.