DE1619391A1 - Process for improving the wet fastness properties of dyeings and prints produced with sulfur dyes on cellulose textile fibers - Google Patents

Description

Process for improving the wetness properties from Färhun ^ enunct soaked with sulfur dyes Printing on Geilulosetextilfaseyn

The German patent no. 1 151 241 and the addition? No. 1 ggl 607 relates to a method for improving wetness *. Properties of dyeings made with sulfur dyes and bruises on cellulose textile fibers by freshly prepared dyeings, splendor and rinsing before the oxidation with polyfunctional dyeing products which are supplied with the freshly dyed materials that are supplied with the dye materials Qde, y. b Textiles after brief spitting with 0.1 to 5, Q # accented to aliphatic, aromatic or heterocyclic polyoxy compounds or their immediate. Precursors »corresponding PaIy- ^ Ma lagenhf in it s _s along with their iialagengehalt at least ä ^ iTaleRten Me ^ pregnated ge alkali in" and then completes "

Ea has now been found that. one can achieve more favorable colorings and bridges on G © lluloaete ^ tilfaae; rii, if one uses the colorations and; Print here ^ ar or near the oxidation after a short spilling with Ü, 1 to 5 _t Q ^. theirs;

importance of aliphatic or heteroeyolic y

containing at least one basic nitrogen atom. _% Bis- or poly-ijü-halo hydrins, preferably in the presence of alkali

impregnated and then finished.

ι oa ß f ι j% 4 m

- 2 - Ref. 2749

For the method according to the invention, for example, are suitable. such water-soluble, nitrogenous bis- or poly-oC, ß-halohydrins, in a known manner by reacting an epihalohydrin with ammonia or amines of the general formula

are accessible.

In this formula feedeutet

A «hydrogen, alkyl with 1 to 5 carbon atoms, Oxyalkyl with 1 to 5 G «atoms,

R »alkyl with 1 to B carbon atoms, oxyalkyl with 1 to 5 carbon atoms

- (aikylen.N) - »alkylen.N-A, (n-O5), AH

■ m (alkylen.5C.alkylen, N), alkylen, X, alkylen, NA

AH

(X s oxygen © the sulfur) (n ** - q - S)

or R and A together

JM

Amines which correspond to the formula given above include, for example, mono-methyl-ethyl-, -propyl, "isopropyl-", ^ foutyi ^ "■ i.so.bu.tylamine, monoojcäthyl-, Monooxypropyl amine, ethylenediamine, biaminopropanei ßiaminobutane _t diaminohexane, 3,3 * -diamino-diprQpyläther, piperazine, mono-oxethyl- and di-oxethyl-ethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine and others

108827/1486 BADORtGTN ^ L "

The water-soluble, nitrogen-containing bis- or poly-i> - _f ß-halohydrins used according to the invention not only improve the wet fastness properties of dyeings and prints produced with sulfur dyes to a greater extent than the poly- c ^ ßhalogenhydrins, but at the same time they also cause a considerable reduction in the decrease in tear strength of dyeings and prints produced with sulfur dyes, especially with sulfur black. In addition, in contrast to the known products mentioned, the aftertreatment agents to be used according to the invention also allow their use after the dyeings and prints have been oxidized.

In the following examples, the percentages are provided nothing else is noted,% by weight based on the weight of the to coloring goods.

example 1

A 5 percent Coloring of Immediallichtgelb GWL (Color Index Sulfur Yellow 5) on cotton, produced in the usual way with 3.75 g / l crystalline sodium sulphide, 4 g / l soda calc. and 10 g / l Glauber's salt calc. in a liquor ratio of 1:20, is introduced into a bath after rinsing which contains 3% of a reaction product of ammonia and epichlorohydrin, the preparation of which is described below. The bath is adjusted to pH = 10 by adding soda solution and heated in the course of 20 minutes to 90-95 ° and 10 minutes at 90-95 °; then it is rinsed well. The perborate wash fastness carried out in accordance with DIN 5 ^ 015 and the soda boiling test carried out in accordance with DIN 5 ^ 031 show a significantly better result than with a dyeing that was not aftertreated.

'© AD ORIGINAL

1 0 9 8 2 7 / U 8 6

- 4 - Ref. 2 749

Also the wash fastness in the presence of reducing substances, such as dextrin, is significantly improved in the aftertreated coloration.

The product used as an aftertreatment agent is prepared as follows: In a solution of 185 g of epichlorohydrin in 200 ml

Methanol is left. a solution of IT g of ammonia in 2.00 ml of methanol is added dropwise at 25-30 ° C. in the course of three hours. It is then stirred for 2 hours at 25-3O ° C and then heated in the course of three hours at 70 C and then for two hours at 70 ⁰ C. After Abdes ti liieren of methane oil in vacuo at 5O-6Q ° C is obtained 2O2 g Reaction product in the form of a thick, viscous oil that is easily soluble in water. To make it pure, the product is repeatedly dissolved in methanol and precipitated with ether.

A product of similar effect is made by analogous implementation obtained from 277 g of epichlorohydrin dissolved in 300 ml of methanol with a solution of 17 g of ammonia in 200 ml of methanol.

* ψ

Example 2 :

A 4 percent Dyeing of hydron blue R for sol (color index 53630 = Vat Blue 43) on cotton is produced in the usual way with 9 ml / 1 sodium hydroxide solution 33 ° Be and 4 g / l hydrosulfite in a liquor ratio of 1:20. After rinsing, the aqueous solution, adjusted to pH 10 with soda, of a reaction product of n-butylamine and epichlorohydrin, the preparation of which is given below, is padded onto the dyeing in such a way that 2% of the product is on the goods .

109827/1486 ⁵

- 5 - Ref. 2 749

Then it is steamed for 2 minutes, then rinsed well and finished. The coloration obtained in this way does not show any opposite to one After-treated dyeing of Hydron Blue R significantly improved wet fastness, especially good fastness to soda and peroxide on.

The product used as the post-treatment agent is as follows prepared: a solution of 73 g of butylamine in 100 ml of ethanol is slowly dripped into 185 g of epichlorohydrin at 25 ° C permit. The mixture is then heated to 60-65 ° C. in the course of two hours and an additional 2 hours at 60-65 ° C. Then the solution becomes that Ethanol is distilled off, the reaction product being obtained in the form of a clear, yellowish, easily water-soluble oil,

A product with a similar effect is obtained if 61 g of monoethanolamine are mixed with 185 g of epichlorohydrin in an analogous manner implements,

Example 3 :

An 8 percent Coloring of Indocarbon CL for Sol (Color Index 53290 Sulfur Black 11), prepared in the usual way with 8 g / l sulfur sodium crystalline, 8 g / l soda calc and 20 g / l Glauber's salt calc. in a liquor ratio of 1:10, after rinsing, it is treated in a bath which contains 2% of a reaction product of a diamine and epichlorohydrin indicated below. After the treatment liquor has been adjusted to pH = 10 with soda solution, it is heated to 90-95 ° C. in the course of 30 minutes and kept at 90-95 ° C. for 10 minutes. After a good rinse, it is finished as usual.

109827 / U 86

- 6 - Ref. 2749

A dyeing is obtained whose wet fastness properties, but especially its Washfastness in the presence of dextrin is significantly improved compared to dyeing that has not been aftertreated.

The following reaction products can be used for the aftertreatment: epichlorohydrin and ethylenediamine in a molar ratio of 2: 1, 3: 1 and 4: 1, as well as corresponding products from 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 3 , 3 ¹ -Diaminodipropyläther, also the reaction product of 3 moles of epichlorohydrin and 1 mole of mono-hydroxyethyl-ethylenediamine, and N, N'-bis- (3-chloro-2-oxy-propyl) -piperazine.

The manufacture of these products can be carried out, for example, as follows; In the appropriate amount of epichlorohydrin a solution of 1 mol of amine in 150 ml of water is slowly added dropwise at room temperature. Then one warms up in the course from 2-3 hours to 60-70 ° C. and the reaction is ended by heating for 2 hours at this temperature. After removing the Water, the reaction products are obtained in pure form by distillation under reduced pressure.

Example 4 :

A dyeing of hydrosol black B (Color Index 53186 Solubilized Sulfur Black) on cotton yarn * made with 10% of the dye, 2.5 g / l soda calc, 2.5 g / l sodium sulfhydrate and 10 g / l Glauber's salt caIc * in a liquor ratio of 1 : 20 at 90 ° C after rinsing for 10 minutes treated at 30 ⁰ C in a bath containing 4% of a reaction product of 4 moles of epichlorohydrin with 1 mole of

10S8.27 / U86 - ⁷ -

- 7 - Ref. 2749

3, S'-Dlamino-Dipropyläther and 2% soda contains. Afterward the temperature of the bath is increased to 90 ° C. in the course of 20 minutes and held at this temperature for a further 10 minutes. Then the dye is rinsed, with 2 ml / 1 acetic acid 60 percent. acidified and dried.

To test the shelf life, strands of a non-treated and one post-treated as described above. Staining for six hours at 135 ° C in a humid atmosphere the AATCC method B / 93 (AATCC yearbook 1963) and the Tear strength determined before and after this treatment.

With 10% hydrosol black B tear strength in g remaining tear-colored Cotton strand before after strength after

artificial Artificial aging Aging

in %

a) untreated . 594 122 21st b) Post-treatment according to
the information in
Example 4 633 53O 84 Example 5:

A coloring of Indocarbon CL conc. (Color Index 53290 Sulfur Black 11) on cotton cheeses, made with 10% of the dye, 30 g / l crystalline sodium sulphide, 4 g / l soda calc. and 20 g / l Glauber's salt calc. in the liquor ratio 1:10 at 90 ⁰ C is rinsed cold, suctioned off and then in the liquor ratio 1:10 with 3%, based on the dry weight of the goods, of a reaction product of 5 moles of epichlorohydrin with 1 mole of diethylenetriamine and 1 percent. Soda calc. increasing from 30 ° C to 90 ° C in 20 minutes and 10 minutes at 90 ° C

10 9 827 / U86

- 8 - Ref. 2749

treated; then it is rinsed. The dye made in this way has very good wet fastness properties, in particular very good peroxide and dextrin wash fastness, as well as good storage stability, the latter even if the coloration has been aftertreated or enriched with acid.

Instead of the above-mentioned conversion product, the following products can be used with equal success: Reaction products of 5 moles of epichlorohydrin with 1 mole of dipropylenetriamine, Furthermore, those from 6 moles of epichlorohydrin with 1 mole of triethylenetetramine, 7 moles of epichlorohydrin with 1 mole of tetraethylene pentamine, 8 moles of epichlorohydrin with 1 mole of pentaethylene hexamine.

The manufacture of these products is carried out in accordance with those described in the preceding Methods described in the examples.

Example 6 :

A 5 percent Dyeing of hydrosol yellow RR (Color Index 53121 Solubilized Sulfur Yellow 2) on cotton, produced in the usual way with 3.75 g / l crystalline sodium sulphide, 4 g / l soda calc. and 10 g / l Glauber's salt calc. in a liquor ratio of 1:20, is introduced into a bath after rinsing, which contains 3% of one of the reaction products mentioned in Example 3, paragraph 2, and 1.5% soda calc. contains. The mixture is heated from 30 to 90 ° C. in the course of 10 minutes and then treated at 90 ° C. for a further 5 minutes. Then it is rinsed well. The dyeing produced in this way shows a flawless wash No. 3 according to AATCC and a significantly improved dyeing compared to the untreated dye

109 827 / U86

- 9 - Ref. 2749

Fastness to washing and peroxide washing (according to DIN 54011 and 54015). The non-post-treated, oxidized with bichromate-acetic acid in the usual manner coloring bleeds during washing no. 3 in accordance with AATCC the accompanying tissue sharply. AATCC wash no. 3 in perfect condition is also obtained if the aftertreatment with the reaction product is carried out after a bichromate-acetic acid oxidation carried out in the usual way.

Example 7 ;

A 4 percent Dyeing of hydrosol light blue B (Color Index 53441 Solubilized Sulfur Blue 7) on cotton is carried out in the usual way with 3 g / l crystalline sodium sulphide, 4 g / l soda calc. and 10 g / l Glauber's salt calc. produced in a liquor ratio of 1:20. After rinsing and squeezing off, the dyeing is treated in a bath containing 3% of the reaction product mentioned in Example 4, Paragraph 1 and 1.5% soda calc. contains. It is heated from 30 to 60 ° C. in the course of 10 minutes and treated for 10 minutes at 60 ° C. It is then rinsed thoroughly. The dyeing shows a flawless wash no. 3 according to AATCC and compared to an untreated dyeing or dyeing oxidized with bichromate-acetic acid in the usual manner, washing and peroxydwashfastness is significantly improved (according to DIN 54011 and 54015).

1098 111 14 86

Claims (2)

16 '! 9391 - 10 - Ref. 27 ^ 9 Claims .1. Process for improving the wet fastness properties of dyeings and prints on cellulose textile fibers produced with sulfur dyes by aftertreatment, dyeings or prints with polyfunctional substances which provide stable reaction products with the dyes, characterized in that the dyed or printed textiles are here before or after the oxidation after brief rinsing with 0.1 to 5% of their dry weight of aliphatic or heterocyclic, water-soluble, containing at least one basic nitrogen atom, bis- or poly- ^ C, ßhalohydrinen impregnated and then finished. 2. The method according to claim i, characterized in that the impregnation with the bis- or poly-X, ßhalogenhydrinen in the presence of alkali. 109827 / U8 8