CS250569B3 - Method of afterdyeing by means of sulphur dye stuffs - Google Patents

Description

The invention relates to a method for finishing the dyeing of cellulosic fibrous materials and mixtures with synthetic sulfur dye fibers by means of water-soluble cationic polyelectrolytes and is dependent on the author's certificate No. 245 170.

The invention is applicable in the dyeing of textile processing operations.

Sulfur dyes are hitherto widely used groups of dyes in dyeing of natural and regenerated cellulose fibers. They are mainly used for dyeing deep shades on permanently less demanding items such as work twill and technical fabrics. It is still the cheapest group of cellulose fiber dyes.

The wet fastnesses of sulphurous dyes can be labeled as maximum average. By treating the previously unoxidized dyes in metal salt solutions, in particular Cu ²⁺ and Cr ³⁺ , the stability level can be increased. It is particularly advantageous to stabilize and at the same time oxidize the sulfur dyes in the acidic solutions of potassium dichromate.

However, under current environmental conditions, it is necessary to foresee a prohibition of the presence of chromium and copper salts in wastewater and thus a withdrawal from the technology providing improved stability of sulfur discharges. It has been shown that in the waste water of some coloring plants the value of 0.7 mg.l ^-1 Cr ³⁺ is exceeded by a factor of 10, which is referred to as the hazard limit for toxicity.

This has caused a considerable technological problem, since the dyes completed by oxidation with active oxygen releasing chemicals have considerably lower washing stability, which would not meet the values prescribed by ČSN 80 0080.

This drawback is solved by the method of finishing the sulfur dyes according to the invention, which comprises the use of cationic polyelectrolytes which, together with the production, are protected as substances by the author's certificate No. 245 170.

The process according to the invention is characterized in that the hitherto reduced sulfur dye on the cellulose fiber is treated at a temperature of 10 to 20 g. I ^-1 water-soluble cationicactiv up to 20 g: l ^-1 water-soluble cationic polyelectrolytes containing a structural group of the general formula r

(1) —CH2 — CH — CH2 — M ^{k +} —CH2 — CH—

I I

OH OH

CH Η —CH2 — Ν- [(CH2) n ~ N] _S - where r is an integer of 1, 2 or 3 k an integer of 1 or 2 n an integer of 2 to 10

X an anionic radical of a strong inorganic or organic acid with an integer of 1, 2, 3 or 4 M heterocyclic radical selected from the group consisting of:

where

R is a hydrogen atom or an alkyl having a carbon number of 1 to 4 obtainable by the reaction of compounds of the formula RY-M-Y] ^k + X ^r -r

(2) where

Y is a group

CH2-CH-CH2 or

I I

OH Cl

CH 2 - CH - CH 2 -

r is an integer of 1, 2 or 3 to an integer of 1 or 2

X an anionic residue of a strong inorganic or organic acid

M is a heterocyclic radical derived from a heterocycle having two nitrogen atoms and multifunctional amines of the general formula

H

R — N— · [(CH2) _n —N] _s - (3) where n is an integer from 2 to 10 with an integer of 1, 2, 3 or 4

R is hydrogen or alkyl having 1 to 4 carbons.

Table 1 lists the basic structural units of these compounds.

The starting materials for the production of cationic polyelectrolytes are contained in Table 2.

The process according to the invention is characterized by a marked increase in the wet fastness of the dyeing compared to the oxidation finishing processes with active oxygen releasing chemicals, and in wash fastness, results exceeding the dye fastness values fixed by the chromium salts are achieved.

The process according to the invention is applicable to all dyeing machines in which it is dyeed in practice with sulfur dyes or water-soluble derivatives of sulfur dyes. It is therefore a discontinuous and a continuous device.

By utilizing the invention in textile refinement plants, the toxic substances in the waste water are significantly reduced.

The technological advantages of the invention are illustrated in the following examples:

Example 1

Cotton yarn 14,5 tex in the form of winding on cross spools is dyed by conventional technology Sulfur black CI number 1 in saturation 6%. After dyeing, the dyed yarn is rinsed for 5 minutes with cold water and treated at 30 ° C with a bath containing 1 g / ^{l of} cationic polyelectrolyte # 1 according to Table 1.

In this bath, the yarn is treated with water at 60 ° C for 10 minutes and finally rinsed briefly with cold water. The yarn possesses very good wash fastness at 60 ^Q C and 95 ° C, in water and perspiration.

Example 2

Pad-Steam is dyeed with a cotton fabric of 66 ° / o, a viscose staple of 34 ° / o, as usual, to a blue shade of Sulfur Blue No. I. I. 5.

After steaming, the fabric is washed in the first three baths with cold water. In the fourth and fifth baths, a bath fabric containing 2 g.l ^{-1 of} compound number 2 of Table 1 is passed. The other two baths contain 0.5 ml of acetic acid. I ' ¹ . The spa has a temperature of 50 degrees Celsius. In the eighth and ninth tubs, the fabric passes through hot water at 60 ° C and in the last tub through cold water.

The fabric exhibits wash stability at 60 ° C

4/4 / 4-5, while the dyeing finished by H2O2 oxidation has a wash stability at 60 ^° C of only 3-4 / 2-4-3 / 4.

Example 3

A 100% cotton dye cord is dyed on a dye jug according to standard procedures

Soluble sulfur green C. C. 2 at saturation 2%.

After dyeing, the fabric is washed with cold water overflow for two passages.

This is followed by a bath treatment containing 3 g. . 1 ^{* 1 of} Compound No. 3 of Table 1, at a temperature of 50 ° C and a bath ratio of 1: 3. Two passages were followed by a 50 ° C hot water wash, two passages and a final cold water wash. An equal amount of compound 1, 2, 4, 5 or 6 may be used in place of compound number 3 of Table 1.

Claims (2)

SUBJECT OF THE INVENTION A method of finishing dyeing of sulfur dyes on textile materials containing cellulosic fibers by means of water-soluble cationic polyelectrolytes, characterized in that the previously reduced sulfur dyeing is treated at temperatures of 10 to 70 ° C with aqueous solutions containing 0.1 to 20 g. Even ^one water-soluble cationic polyelectrolyte containing a structural group of formula (lj r (1) —CH2 — CH — CH2 — M ^{k +} - CH2 — CH— I I OH OH —CH2 — N - [(CH2) _n —N] _s - where r is an integer of 1, 2 or 3 k an integer of 1 or 2 n an integer of 2 to 10 with an integer of 1, 2, 3 or 4 X an anionic radical of a strong inorganic or organic acid M a heterocyclic radical selected from the group consisting of R, ‘J i anywhere R is hydrogen or alkyl having 1 to 4 carbons. Table 1 Compound number Basic structural unit CH 2 Cl ² -CH 3 CH 2 N ² '- 1.2OH OH CH 2 CH-CH 2 -CH 2 -CH-CH 2 -CH 2 CH 2 CH-N-CH 2 CH; OH 2CÍ oh Whose HZC Μ C K-C-N-CH? -C H ₅ CH-N-CH = CH 2 and _d ^{4 2} I ² | 2 2 OH OH N ~ CHA ~ Hx-H-Ci-CCHA · ´ | /. 2.7 7, / l λ X SO / *. -CH ^ CH-CH-H ^ Jy ² *, ij} H ' ^{c H} 2 ^ ^{H CH} 2 ^N - ( ^{CH 2} ) {, ^N OH ch ₃ coo-CH 2 CH-C-CH ₃ c -H-CH 2 - (CH 2 -t OH c H, OH CH. ^CH 3 C _Z H £ AzA CH = CH-ENV ^ - C ^ CH-N-CH _£ cm _from C ^ OH SO, 2 “OH Table 2 Compound number Starting materials [Y — M — Y] ^{k +} - - X ^r r R H H- [N - (CH ² ) _n ] _{with -} N - R 1,3-bis (3-chloro-2-hydroxypropyl) imidazolinium sulfate 1 mol 1,4-bls (3-chloro-2-hydroxypropyl) pyrazinediyl chloride 1 mol 1,3-bis (2,3-epoxypropyl) imidazolinium chloride 1 mot 1,3-bis (3-chloro-2-hydroxypropyl) pyrimidinediamine sulphate 1 mol 1,4-di (3-chloro-2-hydroxypropyl) -1-methyl- N, N‘-dimethylhexamethylenediamine 1 piperazinium acetate 1 mol 1,4-di (3-chloro-2-hydroxypropyl) -1,4-diethylenediamine 0.8 mol ethylpiperazinium sulfate 1 mol ethylenediamine 1 mol diethylenetriamine 0.8 mol triethylenetetramine 0.6 mol hexamethylenediamine 1 mol mol