JPS5821454A - Trisazo black reactive dye - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formulaI[X is -CH2=CH2 or -CH2CH2Z (Z is a group which may be eliminated with an alkali); Y is (1-4C alkyl, 1-4C alkoxy, Cl- or Br-substituted) phenylene, (sulfonic group-substituted) naphthylene]in the form of a free acid. EXAMPLE:A compound shown by the formula II. USE:Dyeing cellulose fiber material, polyamide fiber, or polyurethane fiber in black with providing improved fastness, especially fastness to base. Having high water-solubility, improved dirt pickup rate, retention ratio, and build-up. PROCESS:For example, in the form of a free acid, a monoazo dye (4-aminoazobenzene-2,4'-disulfonic acid) shown by the formula III is diazotized, and, in the form of a free acid, the resultant compound is coupled with a monoazo reactive dye[e.g., 1-amino-2-(4-beta-sulfate ethyl sulfenyl azo)-8-hydroxynaphthalene-3,6- disulfonic acid, etc.]shown by the formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel reactive dyes. More specifically, the present invention can be used in the form of a free acid represented by the following general formula (1) [wherein X bar J3
H=OH24ta4-i -CL-12-C1i2-Z(
2 means a group that can be removed with an alkali), and Y
means a phenylene group or a naphthylene group, and the phenylene group is substituted with 1 to 8 same or different substituents selected from C1-C<alkyl group, 01-04 alkoxy group, chlorine atom and bromine atom. The present invention relates to a trisazo-reactive dye in which the nuclear naphthylene group may be substituted with 1 to 8 sulfonic acid groups.

In the trisazo reactive dye of the present invention represented by the general formula (1), groups zFi that can be removed with alkali, such as halogen atoms such as chlorine and bromine atoms, ester groups of organic carboxylic acids and sulfonic acids, such as lower lower groups such as acetyloxy residues, etc. These include an alkanoyloxy residue, a pencilyloxy residue, a benzenesulfonyloxy residue, or an acidic ester group of phosphoric acid or sulfuric acid represented by the formula -0P03H2 or 10803H in the form of a free acid.

Although the trisazo-reactive dyes of the invention can also exist in the free acid form, they are preferably in the form of salts, especially alkali and alkaline earth metal salts, especially sodium, potassium and hydric salts.

More preferred forms are alkali metal salts.

Among the dyes of the present invention, representative dyes of particular interest industrially are:
a phenylene group in which the residue Y is polysubstituted with chlorine, bromine, methyl, ethyl/L/, methoxy or ethoxy;
Or it is a trisazo dye meaning a phenylene group which may be polysubstituted with two same or different substituents selected from chlorine, bromine, methyl, ethyl, methoxy and ethoxy.

As the residue Y, mention may be made in particular of the residue of the following formula: 0Ct130CHa B r l (wherein the bond marked with an asterisk is =N-N- in the coupler
is a bond that leads to the group).

Among the novel dyes according to the invention, preference is given in particular to trisazo dyes in which the residue Y is an optionally polysubstituted phenylene group and the residue X is a β-sulfatoethyl residue or a vinyl residue. .

7. Although the dye of the present invention has only one fiber-reactive group in one molecule, it has two fiber-reactive groups. C,1
, &active Black 5, cellulose fibers can be dyed in a deeper color, and the fastness of the dyed product obtained is better.

Furthermore, the dye of the present invention has a higher solubility in water than the dyes described in Japanese Patent Publication No. 4B-15299 and Japanese Patent Publication No. 45-4887, and can dye cellulose fibers with excellent exhaustion rate, fixation rate, and build-up property. Moreover, the dyed product obtained is excellent in various fastnesses such as needle base and sunlight resistance, especially in chlorine fastness.

A new dye of general formula (1) can be produced as follows.

A monoazo dye of the formula (2) in the form of a free acid is diazotized by a known method, and a monoazo dye of the general formula (3) (wherein X and Y have the meanings given above) in the form of a free acid is obtained. It can be produced by combining a monoazo reactive dye with a known method.

The monoazo reactive dye of the general formula (3) has the general formula (4)
The amine of 802-Y-Na3 (4) (wherein X and Y have the above-mentioned meanings) was diazotized by a known method, and the 1-
Toyoshi can be produced by coupling amino-8-11:l'loxinaphthalene-8,6-disulfonic acid over a period of 2 to 1.0 hours.

Depending on the reaction conditions, each of the abovementioned starting compounds is present or used in the form of acid and/or salts, especially alkali salts.

The dyes prepared according to the invention are separated by generally known methods by salting out from the reaction medium with electrolytes, such as sodium or potassium chloride, or by evaporation of the reaction solution, for example by spray drying.

The novel dyes according to the invention are fiber-reactive and have very good suitability for dyeing (including printing) materials made of cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers.

Cellulose fiber materials are preferably cotton fiber materials, such as natural or synthetic fibers such as wool and other animal hairs, silk, polyamide-6,6-, polyamide-6, polyamide-11 or polyamide-4.

The application of the dyes according to the invention is particularly excellent in cellulosic fiber materials.

In the case of the exhaust method, cellulose fiber materials are dyed at relatively low temperatures in a dyebath containing mirabilite or common salt in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate or caustic soda. Dyeing can also be done by a textile printing method. For example, a color paste containing an acid binder such as bicarbonate of soda, sodium carbonate, tribasic sodium phosphate, or caustic soda, urea, and a sizing agent, preferably sodium alginate, is printed on the fiber, and after intermediate drying, 100% ~200
It is carried out by steaming or dry heating at ℃.

Furthermore, the dyeing of the present invention may be carried out by a continuous method, or cord pad batch dyeing is also possible.

Dyeing of polyamide fibers, polyurethane fibers and leather can be carried out in an acidic medium by conventional methods.

For example, acetic acid or acetic acid and ammonium acetate can be added to the dyebath to obtain the desired pH value. In order to obtain level dyeing properties, a reaction product of a conventional leveling aid such as cyanuric chloride and 8 times the molar amount of aminobenzenesulfonic acid and/or amitunaphthalenesulfonic acid and/or a reaction product of, for example, stearylamine and ethylene oxide, is used. Preference is given to adding a leveling aid based on the reaction product of . Dyeing is 6
The novel dyestuffs according to the invention can be carried out at temperatures above 0° C. or above 60° C., for example at the boiling temperature of an aqueous bath, optionally under pressure. It is characterized by excellent physical and chemical stability in liquids and in the presence of alkalis, and has very good affinity for ordinary dyeing and printing, as well as excellent exhaustion rate, fixation rate, and build-up rate. has.

The dyed or printed products obtained using the dye of the present invention have high tinting power and excellent gloss, and are excellent in various fastnesses, especially chlorine fastness, light fastness, sweat/sunlight fastness, etc., and are extremely It has good painting and dyeing properties.

Next, the present invention will be explained by examples. Unless otherwise specified, parts are parts by weight and percentages are percentages by weight.

Example 1 4-aminoazobenzene-2,4-disulfonic acid 18.
Add 125 parts of water and 7 parts of hydrochloric acid to 95F and lower the temperature to below 5°C.
After adding 86 parts of sodium nitrite and diazotizing at 5 to 15° C. for 8 hours, excess nitrous acid is removed with sulfamine.

1-amino-2-(4-p-sulfatoethylsulfonylphenylazo)-8-hydroxynaphthalene-3,
A neutral aqueous solution containing 88.86 parts of the trisodium salt of 6-disulfonic acid is added to the diazo liquid. P by dropping 16111 sodium carbonate aqueous solution at 10-20℃
Keep at H4-7 for 8 hours. When the diazo compound is no longer detected, the pH is 4 to 6. Salting out at 80 to 40℃, filtering, and dissolving the resulting wet cake in water. By drying, a dye represented by the following formula (1) was obtained in the form of a free acid.

HOa 8 80sH<1> [Smix 628 nm (water solvent)] Above dye 0
．． Dissolve 6 parts in 200 parts of water, add 20 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 50°C. Then, after 80 minutes had elapsed, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, it is washed with water and soaped to achieve excellent fastness.
A dyed product of deep black color with high build-up properties and excellent fastness was obtained.

l-Amino-2-(8-β-sulfatoethylsulfonylphenylazo)-8-1? )'Waxinaphthalene-
0 to 10°C containing ε0.65 part of 8,6-disulfonic acid,
Suspension of PH0.5-2 (this is l-aminobenzene-
The key β-sulfatoethyl sulfone was converted into niyoridiazotized by a conventional method, and l-amino-8-hydroxynaphthalene-8,
It is obtained by dropwise coupling of a neutral solution of the 6-disulfon edge. ), 2-naphthylamine-1-
After diazotizing 11.25 parts of sulfonic acid by a conventional method, a solution in which excess nitrous acid had been removed with sulfamic acid was added, and 5 to
By adding sodium bicarbonate at 15° C. over a period of about 1 hour, fi P)l is brought to 6 and the diazo compound is no longer detected. Stir at t. The obtained dye solution was adjusted to pH 4.5 to 6.6 and then dried to obtain a dye represented by the following formula (2) in the form of a free acid.

(2) [λmax 620 nm (water solvent)] Dissolve 6 parts of Kami Kamijo dye in 200 parts of water, add 20 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 50°C. Then, after 80 minutes had elapsed, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After the dyeing was completed, washing with water and soaping were carried out to obtain a dyed product with excellent color fastness, a deep black color with high build-up property, and excellent fastness.

Examples 8 to 1O Corresponding dyes were obtained in the same manner as in Example 1 or 2 using the raw material compounds listed in the table below. Using each of the obtained dyes, cotton was dyed in the same manner as in Example 2 to obtain a black dyed product with excellent performance.

Claims (1)

[Claims] In the form of a free acid, a compound of the following formula [wherein,
OH2-Z (2 means a group that can be removed with an alkali)
in, Y means a phenylene group or naphthyleneftt, the phenylene group Fic1-Ca alkyl group,
Cl-C4aA/: may be substituted with 1 to 8 same or different substituents selected from 2xy groups, chlorine atoms, and bromine atoms, and the naphthylene group has 1 to 8 substituents selected from Trisazo-reactive dyes optionally substituted with sulfonic acid groups