DE2322236B2 - PROCESS FOR IMPROVING THE WETFASTNESS OF COLORS PRODUCED ON CELLULOSE FIBER MATERIALS - Google Patents

Description

H ₂ N- (CH ₂ L-NH- (CH ₂ J ₆ -Nj _1n - (CH ₂ ^ -NH ₂ '5

post-treated in the

Xi and X ₂ independently of one another represent a hydrogen atom or a Ci - C ₆ -alkyl group and a, b and c independently of one another represent an integer from 1 to 8 and
m can assume the value from 0 to 6.

2. The method according to claim 1, characterized in that the aftertreatment at elevated temperatures, preferably 40 to 10O ⁰ C, is carried out.

3. The method according to claim 1, characterized in that the aftertreatment according to the preceding Rinsing by adding the compounds to be used according to the invention to the usual ones Soap baths is carried out.

4. The method according to claim 1, characterized in that the aftertreatment is followed by the usual rinsing and soap baths are carried out as a separate aftertreatment process.

40

The invention relates to a process for improving the wet fastness properties of water-soluble ones Dyes produced by reactive dyes on cellulose fiber materials; the procedure is characterized by that dyeings that have been produced with reactive dyes, the one as a reactive group Have 2,3-dichloroquinoxalinoyl-amino radical, with aqueous solutions of compounds of the formula

50

X,

H ₂ N (CH ₂ I ₀ -N -f (CH,) _fc -N

X, ¹

_m - (CH ₂ ), - NH ₂ (D

55

post-treated in the

Xi and X ₂ independently of one another represent a hydrogen atom or a Ci - Cb -alkyl group, a, b and c independently of one another represent an integer f> o from 1 to 8 and
m can assume the value from 0 to 6.

Examples of representatives of the polyalkylenepolyamines of the formula I to be used according to the invention are called: i> s

Diethylenetriamine, triethylenetetramine, pentaethylenehexamine, dipropylenetriamine, Dibutylentriamine, dihexylenetriamine,

Dioctylenetriamine and in particular
N-methyl-bis (3-mino-propyl) amine

The polyalkylenepolyamines of the formula I to be used according to the invention are used in an amount of 0.1 up to 5 g, preferably 0.2 to 1.5 g, per liter of wash bath or tile treatment bath used

The aftertreatment according to the invention with the aqueous solutions containing the polyalkylenepolyamines Formula I can contain, either simultaneously with the usual washout processes or in a separate Operation can be carried out following the usual soap and rinsing baths.

The addition of the polyalkylenepolyamines of the formula I to be used according to the invention to the customary soap and rinse baths has the advantage that the washing out process is significantly accelerated and its effect is intensified. If the aftertreatment is carried out as a separate operation, it is carried out in such a way that the fiber materials are in the aqueous solutions of the compounds of the form! I immersed for about 1 to 30 minutes, preferably at an elevated temperature, for example at 40 to 100 ^{° C.}

The wet fastness-improving effect of the aftertreatment according to the invention is independent of the method by which the cellulose fiber materials with the 2,3-dichloroquinoxalinoyl-amino group having reactive dyes were dyed. These dyes can be obtained by the exhaust dyeing method or by various impregnation processes, such as Cold dwell, one-bath block steaming, block thermofixing, Two-bath Kknz steam or alkaline shock Vc drive, aufrauu on the cellulose fiber materials have been.

When using the exhaust method, the reactive dye from the dye bath, which may also contain salts such as sodium sulfate or sodium chloride, is allowed to be absorbed onto the fiber and fixed there by adding acid-binding agents at temperatures between 20 and 100 ^° C .

When used according to the various impregnation processes, the dye can be applied to the textile material at the same time as the acid-binding agent and then reacted with the fiber by steaming or dry heat treatment, if necessary after intermediate drying. The steaming takes place for 0.5 to 10 minutes, preferably 0.5 to 2 minutes, at temperatures between 95 and 140 ^° C .; the dry heat-treatment is for 0.5 to 5 minutes, preferably 0.5 to 2 minutes at temperatures from 100 to 220 ⁰ C made. The fixation of the dyes can also be carried out in such a way that one aufklotzt the dye together with an acid binding agent to the textile material at temperatures from 20 to 8O ⁰ C, then rolled up and stored for 1 to 48 hours at 20 to 8O ⁰ C. The dye solutions used for this procedure can contain other customary additives, such as urea, wetting agents, thickeners and the like, in addition to the dye and the acid-binding agents.

Furthermore, the dye can initially without an acid-binding agent, but optionally with other additives, e.g. B. urea, wetting agents, thickeners, and the like. Be padded onto the textile material. It is then fixed by padding an aqueous solution containing acid-binding agents and 50 to 300 g per liter of a salt, e.g. B. sodium sulfate or sodium chloride, and subsequent steaming at 95 to 14O ⁰ C for 0.5 to 5 minutes. Is preferred at

this procedure before pumping the chemical solution intermediate dried The dye can also be fixed with a pass through a hot Alkali salt solution at temperatures between 80 and 100 ° C. for 3 to 20 seconds, preferably 5 to 10 seconds Seconds, whereby the alkali-salt solution 2 to 50g per liter of an alkaline agent, e.g. soda, Sodium hydroxide solution, and 50 to 300 g per liter of a salt, e.g. B. Sodium chloride or sodium sulfate

The dye can also be fixed by dyeing with one of these Alkali-salt solution puffs up at room temperature, then rolls up and stores for 1 to 48 hours

Following the dyeing described above, the dye components that are not chemically bound to the Fibers that have been bound should be removed as completely as possible. This can be done either by en- or multiple times Rinsing at 20 to 80 "C and / or rinsing one or more times at boiling temperature, if necessary using soap or synthetic detergents.

The water soluble, a 2,3-dichloroquinoxalinoylamino group having reactive dyes can belong to a wide variety of dye classes; z. B. the class of monoazo, polyazo, anthraquinone, nitro or phthalocyanine dyes. These dyes preferably contain sulfonic acid groups as water-solubilizing groups. The dyes can also Contain metal atoms bonded in a coordinated manner. Such dyes are for example in the French Patent 13 18 843 (or British Patent Nos. 9 95 79t, 9 95 792, 9 95 793, 9 95 794, 9 95 795 and 9 95 796).

As cellulose fiber materials that can be used in the process according to the invention, come those made from natural cellulose, such as cotton, linen and hemp, and from regenerated cellulose, such as Viscose wool, rayon or polynosic fibers.

With the help of the method according to the invention, an excellent improvement in the wet fastness properties, such as water, sweat, wet ironing and wash fastness, and also the acid resistance achieved Improvement is also retained if the staining is used for a longer period of time, possibly in damp and / or I was stored in an acidic atmosphere. In the case of colored bobbins, the inventive Post-treatment prevents the dye hydrolyzate remaining in the thread windings from getting to the The surface migrates and there the fastness properties are reduced or unevenness is caused.

From the DT-AS 17 19 011 it is known certain Polyalkylenepolyamines, especially ethylenediamine, to improve the wet fastness properties of cellulose with To use such reactive dyes generated dyeings that produce a 2,4-dihalo-13,5-triazinyl- {6) - «Mino group included. Because the individual types of reactive dyes are different because of their different reactivity Reactive groups differ greatly in their hydrolysis properties and the preferred one Polyalkylenepolyamine, ethylene diamine, is ineffective in improving the wet fastness properties of Dyeings that have been produced with reactive dyes that have a 2,3-dichloroquinoxylinoylamino group as the reactive group have, it was surprising that with this type of reactive dye with the in the publication only incidentally mentioned polyalkylene polyamines provide an excellent improvement in wet fastness properties is achieved.

example 1

100 g knitted cotton fabric are in FlottenverhäJtnis 1: Dyed 20 30 minutes at 4O ⁰ C in an aqueous bath which, per liter, 2.5 of Example 22 of the French patent 13 18 843 (in the table Example 2 g to Example 2 of British Patent Specification 9 95 794) of the dye described and contains 50 g of sodium sulfate. After adding 20 g of sodium carbonate

ίο is 90 minutes at 40 ⁰ C further colored is then taken the knitted fabric from the dyebath and rinsed for 5 minutes Wa "ser of 25 ° C Subsequently, the knitted fabric is washed for 20 minutes at the boil in an aqueous bath g per liter, 1 N Methylbis- {3-ariinopropyl) amine and 1 g of a 1: 1 mixture of Ci; - Ci: - Paraffin sulfonic acid (sodium salt) and the reaction product of 1 mole of nonylphenol with 10 moles of Ätr ylenoxid contains. After separating off the wash liquor, the fabric is rinsed in warm water and 50 ⁰ C Connections hließend dried

It wildly obtained a bright red colored knitted fabric, which is characterized by excellent fastness to water, perspiration, washing, wet ironing and acidic dyeing excellent Even when the dye is stored for a longer period of time, the good wet and Preserve acidity.

One sample each of a post-treated and a non-post-treated dye is taken for 1 hour at the boiling temperature with an aqueous sodium bisulfate solution, which has a pH of 1, treated. In this The acid-boiling-fastness test shows that with N-methyl-bis-i 3-aminopropyl) -amine aftertreated coloring shows a considerably lower lightening than not post-treated coloring.

To determine the resistance to acid storage, a 40 cm ² section of an aftertreated and an untreated dye with white cotton and white wool is sewn, placed in dilute acetic acid adjusted to a pH of 2.65 for 30 minutes, then squeezed off and Stored for 6 hours at 37 ° C under a weight of 5 kg and then Getrotl.net. In this acid storage test, the accompanying fabrics of the dye aftertreated with N-methyl-bis (3-aminopropyl) -amine show practically no soiling, while the accompanying fabrics of the untreated dye, in particular the woolen fabric, are heavily tinted.

An equivalent improvement in the wet and acid fastness properties was also achieved if instead of Ie of the N-methyl-bis (3-aminopropv I) amines used dl ·: the same amount of one of the following Polyalkylenpolya-nine was used: Peniaäthylenhexamin, Dipropy entramin, Triäthylenetetramine, Dibutylenetriamine, Diliexylenetriamine or dioctylenetriamine.

Was used instead of the reactive dye used in Example 207 of the French patent 13 18 84: ·! (= Table example 1 of example 3 of the british! Paientschrift 9 95 794) described reactive dye used, an equally good improvement in the wet and acid fastness properties was achieved.

Instead of the knitted cotton, rayon fiber yarn was used dyed in this way dyeings with equivalent wet fastness and acid fastness properties were also obtained.

Example 2

100 g heat-treated and bleached cotton fabric are padded with an aqueous liquor / t. the in Liter 50 jf de:> reactive color used in example 1

Substance, 150 g urea and 20 g sodium carbonate contains. The fabric is then first ^{dried at 80 °} C. and then subjected to hot air treatment at 150 ^° C. for 2 minutes. The fabric is then rinsed with cold water for 5 minutes and then with boiling water for 10 minutes. -amine and 1 g of a 1: 1 mixture of C12-Cis-paraffinsulfonic acid ^ sodium salt) and the reaction product of one mole of nonylpiienol with 10 moles of ethylene oxide

The dyeing obtained is distinguished by excellent wet and acid fastness properties. These were as described in Beispie ', 1 determined.

An equivalent improvement in the wet fastness properties was also obtained in dyeings in which the reactive dye was not fixed by drying and subsequent hot air treatment, but either by drying and steaming for 2 minutes at 10 ° C. or by holding it cold (24 hours at room temperature) or holding it warm (4 hours at 8O ⁰ C) was fixed.

Example 3

100 g of mercerized, bleached cotton fabric are padded in an aqueous solution which contains 50 g of the dye used in Example 1 per liter. The fabric is then first dried at 80 ° C., then padded at room temperature with a solution which contains 250 g of sodium chloride, 20 g of sodium carbonate and 10 g of sodium hydroxide per liter. and finally ^{steamed at 102 °} C. for 1 minute. Then, the fabric is initially cold 5 minutes, then rinsed hot for 10 minutes then soaped for 30 minutes at the boil and rinsed finally 5 minutes at 6O ⁰ C. This rinsing is followed by a 20-minute aftertreatment at boiling temperature with an aqueous solution containing 1 g of N-methyl-bis- (3-aminopropyl) -amine and 1 g of a 1: 1 mixture of Cu-Cn- Contains paraffin sulfonic acid (sodium salt) and the Umselzungsprodukt of one mole of nonylphenol with 10 moles of ethylene oxide.

An excellent improvement in the wet and acid fastness properties is achieved. The fastnesses were determined as described in Example 1.

An equivalent improvement in the fastness properties was also obtained in the case of dyeings The reactive dye is not fixed by treating it with an alkali salt solution and Subsequent steaming, but by immersion for 10 seconds in an alkali-salt solution heated to 95 ° C was made.

Example 4

1 kg of cotton yarn is dyed in a package dying machine dyed and aftertreated in the manner described in Example 1. After drying it shows on the Cross-bobbin aftertreated yarn has no dye deposits on the bobbin surface and none locally different wet fastness properties, while dye migrations in an untreated package and dye deposits occur on the surface.

Claims (1)

Patent claims: i. Process for improving the wet fastness properties of dyeings produced with water-soluble reactive dyes on cellulose fiber materials, characterized in that dyeings which have been produced with reactive dyes which have a 23-dichloroquinoxalinoylamino radical as a reactive group, with aqueous solutions of compounds of the formula