DE1619328B1 - Use of a quaternized benzothiazole azo dye for dyeing textile materials made of polyacrylonitrile - Google Patents

Description

The invention relates to the use of the dye of the formula in which X ° means a colorless anion for dyeing textile material made from an acrylonitrile polymer containing at least 50 percent by weight of acrylonitrile.

It is known that textile materials made of polyacrylonitrile can be used in luminous Colors lightfast violet to blue, if - one as. Basic dyes Benzthiazole azo dyes used. These dyes are extremely strong in color and are pretty easy to make. However, they usually have the disadvantage that they provide dyeings which only have medium thermal fastness properties. High thermal However, fastness properties of the polyacrylonitrile dyes are desirable because the colored ones Textile materials in many cases pleated or hot ironed, d. H. intense heat get abandoned. If the thermal fastness properties are inadequate, the Change the hue of the dyeings in an undesirable manner, reversibly or irreversibly. There were therefore very real dyes of the anthraquinone series even against the action of heat suggested, which also deliver beautiful, but less luminous, shades of blue. However, these dyes have a much lower color strength than the blue basic ones Azo dyes. In order to obtain colorations of the same color strength, one therefore needs significantly larger amounts of anthraquinone dyes than basic azo dyes. The aim of the present invention are therefore blue-colored textile materials Polyacrylonitrile fibers, the coloring of which is obtained with basic azo dyes and which nevertheless have good thermal fastness properties.

This aim would be achieved using 0.02 to 2 percent by weight, preferably 0.05 to 0.6 percent by weight, based on the textile materials, of the dye. formula In this formula, X'- 'means any colorless anion of a simple or complex inorganic or organic acid. For example, the following anions come into consideration: CIF "BrQ, CH3SO40, CIH7SO2, ZnC4oo, .BF4, HS04 @ S040 or P0400.

Of these, CH3SO4 and Cl "are preferred as anions for technical reasons, however, the type of anion has practically no influence on the properties of the dye.

Textile materials made of polyacrylonitrile are, for example, fibers, Threads, flakes, fabrics, or knitted fabrics made from polymers that - predominantly polymerized Acrylonitrile; z. B. more than 85%. Such polymers contain z. B. 95% acrylonitrile and approximately 5% methyl acrylate or 89% acrylonitrile, 6% methyl vinyl pyridine and 5% vinyl acetate or 94% / a acrylonitrile, 5% methylvinylpyridine and 1% vinyl acetate.

The textile materials dyed with the dye of formula I. are; are either by dyeing from a long liquor, e.g. B. with a liquor ratio from 1:40, blocks with a short fleet, z. B. with a liquor ratio of I: 3 to 1: 5, or printing with a printing paste. The dye pulls from weakly acidic medium, preferably acetic acid medium, onto the fiber.

In detail, the dyeing of the textile material goes like this: Man doughs the dye in a little water with the addition of the acid in question, for example Acetic acid, formic acid, tartaric acid, boric acid, naphthalenesulfonic acid or sulfuric acid, and dissolves it by pouring hot water over it. You can also add the dye bath later Add substances that generate acid during dyeing. As such come z. B. Salts; volatile bases with strong, non-volatile acids such as ammonium sulfate or water-soluble esters of organic acids which are saponified during dyeing. Using . Mineral acid solutions can be used during the dyeing process dull weaker acids by gradually adding alkali salts, for example with sodium acetate. One can dye while boiling in an open vessel or in a closed one Vessels under pressure at temperatures above 100 ° C.

The dye of the formula I is obtained in a manner known per se. For example, you can use 6-methoxy-. Diazotize 2-amino-benzothiazole with N-butyl-N-cyanoethylaniline couple and methylate the coupling product, -or you can 6-methoxy-benzothiazolonhydrazone Coupling oxidatively with N-butyl-N-cyanäthyjanilin. In the dyes thus obtained the anion can be exchanged for another if desired. You get'-for example in the methylation with dimethyl sulfate the dye as methosulfate, so you can easily produce the corresponding hydrochloride from it.

The dyed textile materials obtained with the dye of the formula have a brilliant blue hue; are highly lightfast, very washfast and draw Surprisingly, it is characterized by very good ironing fastness. They also have one unchanged evening color. Compared to next comparable, partially from the USA.-Patent 3,148,935 known dyes, which on the amino nitrogen carry other customary residues, the dye to be used according to the invention is distinguished due to better overfirbe fastness. It was surprising and unpredictable that from the group of very similar dyes just the new dye is this advantageous one Property shows. Other similar dyes are from the German patents 1 044 023 and 1 050 940 as well as from Belgian patent specification 655 493 are known.

The parts mentioned in the examples are parts by weight.

Example 1 0.1 part of the dye of the formula I is mixed in 3 parts Acetic acid (80o () ig) and dissolves by pouring 4000 parts of hot water over it. 6 parts of sodium acetate and 4 parts of a condensation product of 1 mol are used Adding oleic alcohol with 15 moles of ethylene oxide at 40.degree. C. brings 100 parts of polyacrylonitrile fibers into the dyebath, heated to 98 "C within 30 minutes and dyed 2 Hours of boiling bath. After this time, the dye bath is almost completely exhausted. The material dyed in this way is soaped for 15 minutes in 5000 parts of water at 80.degree. C. with addition of 5 parts of a sulfonated fatty acid condensation product, rinses and dries. The fiber shows a deep blue color, which is excellent washing, light and very has good thermal fastness properties.

The dye of the formula I is prepared as follows: Dissolve 180 Parts of 2-amino-6-methoxybenzthiazole in a mixture of 140 parts of sulfuric acid (96%) and 125 parts of ice and pour the resulting solution into a mixture of 1900 parts of ice and 2900 parts of sulfuric acid (96%). For this purpose, 290 is left at -10.degree Parts of nitrosylsulfuric acid (about 54%) run in over the course of 2 hours. The so obtained diazo solution is gradually mixed with a mixture of 212 parts of N-cyanoethyl-N-butylaniline, 5000 parts of water, 5000 parts of ice and 98 parts of sulfuric acid (96%) are combined. After the coupling has ended, a solution of 2500 parts of sodium hydroxide in Run in 50,000 parts of water, suction off and dry at 60 ° C. Yield 370 parts Coupling product.

For quaternization, 370 parts of the dried and powdered coupling product are stirred in 1500 parts of chloroform and 141 parts of dimethyl sulfate are allowed to run in at 50.degree. C. in the course of 3 hours. The mixture is refluxed for 3 to 4 hours and the chloroform is distilled off with the simultaneous addition of 3000 parts of hot water. The dye which precipitates out on cooling is filtered off with suction and dried at 50.degree. Yield 470 parts. 'Example 2 0.02 parts of the dye of the formula I are dissolved in 4000 parts of hot water. 2 parts of acetic acid (80o oig), 5 parts of Glauber's salt and 3 parts of benzyltrimethylammonium chloride are added and 100 parts of polyacrylonitrile fabric are placed in the dyebath at 40 ° C., heated to 90 ° C. over 30 minutes and dyed at this temperature for 15 minutes. It is then heated to the boil and colored from a boiling bath for another hour. The material dyed in this way is soaped for 15 minutes in 5000 parts of water at 80 ° C. with the addition of 5 parts of a sulfonated fatty acid condensation product, rinsed and dried. A light blue dyeing of excellent washfastness and lightfastness is obtained in this way.

EXAMPLE 3 0.3 part of the dye of the formula I is dissolved in 4000 parts of hot water and 10 parts of Glauber's salt, 2 parts of sulfuric acid (98%) and 3 parts of a condensation product of 1 mol of oleic alcohol and 15 mol of ethylene oxide are added C brings mixing 100 parts of polyacrylonitrile in the dyebath, heated within 30 minutes to 98 C., and dyeing continued for 2 hours in boiling bath. one soaped the thus colored over 15 minutes in 5000 parts of water at 80 'C with the addition of 5 parts of sulfonated fatty acid condensation product, rinsed and dried, giving a deep blue dyeing of excellent fastness to washing, light and ironing.

Example 4 Polyacrylonitrile fabric is printed with a color paste, to 1000 g of 10 g of the dye of formula 1, 50 g of thiodiethylene glycol, 50 g Acetic acid (30%), 35 g tartaric acid, 35 g sodium chlorate (1: 2), 160 g water, 220 g crystal rubber thickening (1: 2) and 440 g carboxymethyl cellulose thickening (18%) contains, dries and steams at 0.5 atm. It is then rinsed and with a Liquor containing 1 g / 1 of the adduct of 12 mol of ethylene oxide with oleylamine, soaped at 50%. Brilliant blue prints with very good light and wetness properties are obtained.

Claims (2)

Claims: 1. Use of a quaternized benzothiazole azo dye of the formula in which XI3 denotes a colorless anion, for dyeing textile material made from an acrylonitrile polymer; which contains at least 50 percent by weight of acrylonitrile. 2. Use according to Claim 1, characterized in that the aim is textile material an acrylonitrile polymer containing at least 89 percent by weight acrylonitrile, 0.02 to 2 percent by weight of the dye of the formula given in claim 1 brings up.