JPS6029749B2 - Fiber-reactive disazo dyes, their production methods and their uses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fiber represented by the formula (wherein each of A and A2 is an amine group independently bonded to an s-triazine ring via an amine nitrogen atom). Relating to reactive disazo dyes.

The groups A, and A2 may be aliphatic, cycloaliphatic, aromatic or heterocyclic amine groups. Possible A, and A2
The groups are, for example, the corresponding groups of the amines of the formulas '3} and '41 mentioned later in the description of the preparation of fiber-reactive disazo dyes of the formula '1'. A preferred fiber-reactive disazo dye is A
, and are the same dyes of the formula [1}.

In particular, each of A, and is a sulfophenylamine group. Disazo dyes of type '11 are di-reactive with fibers.

This is because these dyes contain removable fluorine atoms in each of the two s-triazine rings. By fiber-reactive compounds is meant compounds that can react with the hydroxyl groups of cellulose or the amino groups of natural or synthetic polyamides to form covalent chemical bonds.

The method for producing the fiber-reactive disazo dye of the formula {1} is to combine 2,4,6-trifluoro-striazine (cyanuric fluoride) represented by the formula A in any order.
The amine represented by (3) and (1) is condensed with the disazo compound represented by the formula to form a fiber-reactive disazo compound of the formula '1}.

Preferably '3' and ' where A and A2 are the same group
An amine of type 41 is used as starting material. Especially A,
and A2 are each a sulfophenylamino group'
Amines of formula 3' and [4} are used as starting materials.

The order in which the process steps described above are carried out can be varied and, if appropriate, some can be carried out simultaneously, so that a large number of process variations are possible.

The starting materials used for each partial reaction are clear from formula '11. Generally, the reaction continues stepwise,
The order of the single reactions of the individual reaction components of formula {21, '3', '4} and (5} can be freely chosen. An important variation of this method is (a} 2, 4, 6 -trifluoro-s-triazine 2
mol is condensed with 1 mole of disazo compound of formula '5}, and the obtained di-primary condensation product is condensed with an equimolar mixture of amines of formula '3' and '4} in a molar ratio of 1:2 to form '1. Fiber-reactive disazo dye of the formula 'b1 2
, 2 moles of 4,6-trifluoro-s-triazine
The primary condensation product obtained was condensed with 1 mole of a disazo compound of formula {51,
A fiber-reactive disazo dye of the formula (A2=A, This is a method in which the primary condensation product is condensed with 2 moles of an amine of the formula [3} to produce a fiber-reactive disazo dye of the formula '1} (A).

{The disazo compound of the formula 5' is obtained by coupling 1,8-aminonaphthol-3,6-disulfonic acid with 2 equivalents of diazotized 4-nitroaniline-2-sulfonic acid (acidic and alkaline coupling) and then converting this nitro group. or by reducing 2 equivalents of 1,8-aminonaphthol-3,6-disulfonic acid into 4
-acetylaminoaniline-2-sulfonic acid and then saponification of this acetylamino group.

Examples of amines of formula {31 and 4- which can be used as starting materials to obtain disazo dyes of formula , dibutylamine, isobutylamine, sec-butylamine, tertiary-butylamine, hexylamine, methoxyethylamine, ethoxyethylamiso, methoxypropylamine, chloroethylamine, hydroxyethylamine, dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, 8- Sulfatoethylamine, benzylamine, cyclohexylamine, aniline, o-, m- and p-toluidine, 2,3-, 2,4-, 2,5-,
2.6-, 3,4- and 3,5-dimethylaniline, o-, m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 4-acetylaminoaniline, o-, m- or p-nitro Aniline, o-, m- or p-aminophenol, 2-methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4
Nitroaniline, 2-nitro-4-methyl-aniline, 3-nitro-4-methyl-aniline, o-, m- or p-phenylenediamine, 3-amino-4-methylaniline, 4-amino-3-methylaniline , 2-amino-4-methyl-aniline, o-, m- or p-anisidine, o-, m- or p-phenetidine, naphthylamine-'11, naphthylamine-■, 1,4-diaminonaphthalene, 1,5- Diaminonaphthalene, 2-amino-1-hydroxynaphthalene, 1-amino-4-
Hydroxy-naphthalene, 1-amino-8-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, orthanilic acid, metanilic acid, sulfanilic acid, ani-2,4
-disulfonic acid, aniline-2,5-disulfonic acid, anthranilic acid, m- or p-aminobenzoic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotoluene-
5-sulfonic acid, p-aminosalicylic acid, 1-amino-4-carboxybenzene-3-sulfonic acid, 1-amino/1-2-carboxybenzene-5-sulfonic acid, 1-
Amino-5-carboxybenzene-2-sulfonic acid, 1
Naphthylamine-2-,13-,141,151,-
6-, 17- or 18-sulfonic acid, 2-naphthylamine-11, 14-, 15-1, 16-1, 17- or 18-sulfonic acid, 1-naphthylamine-2,4- , 12
,5-,12,7-,12,8-,13,51,13,
6-, one 3, 7-, one 3, 8-, one 4, 6 one, one 4, 7
1, 4,8 1 or -5,8-disulfonic acid, 2 naphthylamine-1,5 1, 1,6-, 1,7-, 3
,61,-3,71,14,71,14,81,15,
7- or -6,8-disulfonic acid, 1-naphthylamine-2,4,6-, -2,4,7-, -2,5,7-
-3,5,7-, -3,6,8- or -4,6,8-
Trisulfonic acid, 2-naphthylamine-, 3,7-,
---, 5, 7-1, 3, 5, 7--3, 6, 7-1, 3,
6,8-or-4,6,8-trisulfonic acid, 2-,
Mention may be made of 3- or 4-aminopyridine, 2-ami/penzthiazole, 5-, 6- or 8-aminoquinoline, 2-aminopyrimidine, morpholine, piverizine and piverazine.

■ 2,4,6-trifluoro-s triazine and '
The condensation reaction with the amine of formula 31 and {4) and the disazo compound of formula {5) is preferably carried out in an aqueous solution or suspension at low temperature and at a slightly acidic or neutral to slightly alkaline pH.
Done by value.

Conveniently, the hydrogen fluoride liberated during this condensation is continuously neutralized by addition of aqueous alkali hydroxide, carbonate or bicarbonate. {1' Fiber-reactive azo dyes are distinguished by pronounced reactivity, high degree of fixation and easy removal of unfixed dyes.

These dyes are suitable for dyeing and printing a very wide variety of materials, such as silk, leather, wool, polyamide or polyurethane fibers, and the like, as well as cellulosic materials of fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. These dyes are suitable both for dyeing by the exhaust method and by the pad dyeing method. In this pad dyeing process, the article is impregnated with an aqueous and, if appropriate, also salt-containing dye solution, and the dye is fixed with or without heat after treatment with alkali or in the presence of alkali. . These dyes are also particularly suitable for printing on cotton and also for printing nitrogen-containing fibers such as wool, silk or wool-containing blends.

It is advisable to wash dyeings and prints thoroughly with cold and hot water, if appropriate with the addition of agents that act as dispersants and promote the diffusion of unfixed dyestuffs.
In the following examples, parts and percentages are by weight.

Example 1 A solution of 14.8 parts of cyanuric fluoride dissolved in 1 part of toluene was mixed with 17 parts of ortanilic acid. $ parts in 400 parts of water are added to an ice-cold neutral solution over a period of 5 minutes, and the pH of this solution is maintained at 6-7 by simultaneous addition of IN sodium hydroxide solution.

After this acylation is completed, the first condensation product is mixed with 4 ml of water.
0 Disazo dye represented by the formula 35. Add $ part to the neutral solution.

The reaction mixture is warmed to 30-390°C and the feed value is kept at 7-8 by dropwise addition of IN sodium hydroxide solution. After acylation of both amides/groups with the addition of 10% by volume of sodium chloride, the dye is isolated and collected by filtration.

The resulting dye paste is mixed with a concentrated aqueous solution of 2 parts of dibasic hydrogen phosphate and dried under vacuum at 50°C. The dye thus obtained dyes cotton a blue-green color. According to the details of this example, the disazo dyes described above were prepared from the following amines:
Diacylation with an equivalent amount of difluorotolylazine compound simultaneously yields other dyes that dye cotton blue-green.

Amine: Aniline-2,5-disulfonic acid, aniline-2,4-disulfonic acid, anthranilic acid, 2-aminotoluene-5-sulfonic acid, 2-aminotoluene-4
-sulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid.

Example 2 A solution of 14.8 parts of cyanuric fluoride dissolved in 1 part of toluene was prepared by dissolving (1-amino-8-naphthol-3,
(formed by acidic and alkaline coupling of 2 equivalents of 5-nitroaniline-2-sulfonic acid to 6-disulfonic acid, followed by reduction of both nitro groups with sodium sulfide or hydrosulfite) Disazo dye 35. Nobe was dissolved in 50 parts of water and added dropwise to an ice-cold neutral solution over a period of 5 minutes, and at the same time a bottle of IN sodium hydroxide solution was added to bring the pH value of the reaction mixture to 6-7. Keep it.

After complete acylation of both amino groups, this diprimary condensation product is treated with methanic acid 17. Add a neutral solution of Moribe dissolved in 400 parts of water.

The reaction mixture is flooded to 30 DEG-35 DEG C. and the value is maintained at 7-8 with IN sodium hydroxide solution during this second condensation. The dye is buffered with 2 parts of isolated dibasic sodium phosphate and dried under vacuum at 50°C. This dye dyes cotton a blueish color. In this example, tetrafluorotriazine was replaced with 2 equivalents of the following amines in place of methanic acid: sulfanilic acid, o-toluidine, ammonia, 2-naphthylamine-4,8-disulfonic acid, aniline, N-methylaniline, N-ethylaniline, taurine, Similar dyes are obtained by reaction with 2-naphthylamine-4,6,8-trisulfonic acid, 2-naphthylamine-6-sulfonic acid, 4-aminosalicylic acid, 2-chloroaniline or 2,5-dimethylaniline.

Dyeing method 1 2 parts of the dye obtained in Example 1 were mixed with 10 parts of water while adding 0.5 part of sodium nitrobenzenesulfonate.
This dissolves.

A cotton fabric is impregnated with this solution to a level of liquid absorption of 75% and then dried. The fabric is then impregnated with a warm solution of 20 qC containing 30 parts of sodium hydroxide and 30 parts of sodium chloride and squeezed to 75% absorption.

The dyed material is steamed at 100 to 10 RO, rinsed, soaped for 15 minutes in a 0.3% boiling solution of an ionic detergent, rinsed and dried. Dyeing method 0 2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water.

Claims (1)

[Claims] 1 Formula ▲ Numerical formulas, chemical formulas, tables, etc. A fiber-reactive disazo dye represented by 2. The fiber-reactive disazo dye according to claim 1, wherein A_1 and A_2 are the same group. 3. The fiber-reactive disazo dye according to claim 1 or 2, wherein each of A_1 and A_2 is a sulfophenylamino group. 4. The fiber-reactive disazo dye according to claim 1, which is represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 5 Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the method for producing fiber-reactive disazo dyes, 2,4,6-trifluoro-s-triazine represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 4) (In the formula, A_1 and A_2 have the same meanings as above)
A method for producing fiber-reactive disazo dyes, which consists of condensing an amine represented by the following formula with a disazo compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ in any order. 6 2 moles of 2,4,6-trifluoro-s-triazine are condensed with 1 mole of the disazo compound of formula (5), and the resulting di-primary condensation product is condensed with amines of formulas (3) and (4). The method according to claim 5, wherein the fiber-reactive disazo dye of formula (1) is obtained by condensation with an equimolar mixture in a molar ratio of 1:2. 7 2 moles of 2,4,6-trifluoro-s-triazine are condensed with 2 moles of amine of formula (3), and the obtained primary condensation product is condensed with 1 mole of disazo compound of formula (5) to obtain ( 1) The method according to claim 5, wherein the fiber-reactive disazo dye of the formula (A_2=A_1) is used. 8 2 moles of 2,4,6-trifluoro-s-triazine are condensed with 1 mole of the disazo compound of the formula (5), and the resulting di-primary condensation product is condensed with 2 moles of the amine of the formula (3). (1) The method according to claim 5, wherein the fiber-reactive disazo dye of the formula (A_2=A_1) is used. 9 A_1 and A_2 are the same group as starting materials (
A method according to claim 5, in which amines of formulas 3) and (4) are used. 10. The method according to claim 5, wherein amines of formulas (3) and (4) are used as starting materials, in which each of A_1 and A_2 is a sulfophenylamino group. 11 The 2,4,6-trifluoro-s-triazine of formula (2) is condensed with 1-aminobenzene-2-sulfonic acid, and the obtained formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The condensation product is condensed with the disazo compound of formula (5) at a molar ratio of 2:1 to obtain a fiber-reactive disazo dye represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Claim 5 Method described.