EP0209787B1 - Process for the after-treatment of dyeings with reactive dyes on cellulosic fibrous materials - Google Patents

Abstract

Dyeings with reactive dyes on cellulose fiber materials are after-treated with an aqueous solution of a condensate which is obtainable by reacting (a) bisbenzylpiperzine with (b) ethylene chloride, an epihalohydrin, propylene chloride, 1,3-dichloro-2-hydroxypropane, bisepoxybutane or 1,4-dichlorobutane or a mixture of these, in a molar ratio of from 1:0.5 to 1:1.1, or by reacting (c) piperazine, bis-1,4-aminopropylpiperazine, 1-aminoethylpiperazine, 2-hydroxyethylpiperazine or 1-methylpiperazine, or a mixture of these, with a compound according to (b) in a molar ratio of from 1:0.5 to 1:1.1 and benzylating the condensate, the benzylation being carried out using 0.15-1.0 mole of benzyl chloride per equivalent of nitrogen in component (c). The cellulose fiber materials after-treated in this manner possess very good wetfastness.

Description

From DE-OS 2 747 358 it is known to dye with reactive dyes on cellulose fiber materials with aqueous solutions of condensation products from polyamines and epichlorohydrin at a pH of the aqueous solutions between 3.5 and 11 and at temperatures of preferably 65 to 100 _° C to treat. The amounts of cationic condensation products used are between 0.5 and 4% by weight, based on the dry weight of the dyed textile goods. With the help of such a treatment, the wet fastness properties of reactive dyeings on cellulose are improved, but a further increase in the fastness level of the aftertreated dyeings is desired.

DE-A 3 217 835 discloses a method for improving the fastness properties of a dye or an optical brightener on textile materials made from cellulose fibers, in which, among other things, a textile material dyed or printed with reactive dyes is brought into contact with a post-treatment agent which (a ) a linear or branched polymer which contains, as repeating units, at least two quaternary ammonium groups which are bonded to one another by alkylene or arylene groups as bridge members, (b) optionally an N-methylol derivative of a urea, melamine, guanamine, triacinone, urone, carbamate or acid amide and contains as essential component (c) a catalyst for the crosslinking of N-methylol compounds according to (b) and then carries out a heat treatment in which the dyes are fixed and the cellulose fibers are simultaneously crosslinked (finishing).

The present invention is based on the object of providing a process for the aftertreatment of dyeings with reactive dyes on cellulose fiber materials, in which textile materials dyed in deep tones are obtained which do not stain an untreated white cotton accompanying fabric when tested in the ironing test.

• (a) Bis-benzylpiperazin mit
• (b) Ethylenchlorid, Epihalogen-hydrin, Propylenchlorid, 1,3-Dichlor-2-hydroxy-propan, Bis-epoxibutan, 1,4-Dichlorbutan oder deren Gemische im Molverhältnis 1:0,5 bis 1,1 oder durch Umsetzung von
• (c) Piperazin, Bis-1,4-(aminopropyl)-piperazin, 1-Aminoethylpiperazin, 2-Hydroxyethylpiperazin, 1-Methylpiperazin oder deren Gemische
  • mit den Verbindungen gemäß (b) im Molverhältnis 1:0,5 bis 1,1 und Benzylierung der Kondensationsprodukte erhältlich ist, wobei man bei der Benzylierung pro Äquivalent Stickstoff in der Komponente (c) 0,15-1,0 Mol Benzylchlorid einsetzt.

The object is achieved in that a cationic condensation product is used as the aftertreatment agent, which by reacting

• (a) Bis-benzylpiperazine with
• (b) ethylene chloride, epihalohydrin, propylene chloride, 1,3-dichloro-2-hydroxypropane, bis-epoxybutane, 1,4-dichlorobutane or mixtures thereof in a molar ratio of 1: 0.5 to 1.1 or by reacting
• (c) piperazine, bis-1,4- (aminopropyl) piperazine, 1-aminoethylpiperazine, 2-hydroxyethylpiperazine, 1-methylpiperazine or mixtures thereof
  • is available with the compounds according to (b) in a molar ratio of 1: 0.5 to 1.1 and benzylation of the condensation products, 0.15-1.0 mol of benzyl chloride being used in the component (c) for the equivalent of nitrogen in the benzylation.

The cellulose fiber materials can be in the form of fibers, yarns, fabrics or other piece goods. The fiber materials consist of cotton, linen or rayon. The cellulose fiber materials can optionally be in a mixture with synthetic fibers, such as polyamide, polyacrylonitrile or polyester fibers.

The cellulose fibers are dyed with the commercially available reactive dyestuffs in the customary manner, for example at 20-100 _° C. using the exhaust process or at room temperature using the cold residence process. Following dyeing, the textile material is first rinsed with cold water, then washed twice with hot water (95-100 _° C) and, if necessary, once more with water at a temperature of 60-80 ° C. Only then is the cellulose material dyed with reactive dyes treated with the cationic condensation product to be used as aftertreatment agent in aqueous solution.

The cationic condensation products to be used according to the invention can be obtained by reacting (a) bis-benzylpiperazine with (b) ethylene chloride, epihalohydrin, propylene chloride, 1,3-dichloro-2-hydroxypropane, bis-epoxy-butane, 1,4-dichlorobutane or their Mixtures in a: b molar ratio of 1: 0.5 to 1.1.

They are also obtainable by reacting (c) piperazine, bis-1,4- (aminopropyl) piperazine, 1-aminoethylpiperazine, 2-hydroxyethylpiperazine, 1-methylpiperazine or mixtures thereof with the bifunctional crosslinking agents specified in (b) above and benzylation of these condensation products, 0.15 to 1.0 mol of benzyl chloride being used in the benzylation per equivalent of nitrogen in component (c).

The condensation of components (a) or (c) with (b) takes place in the pH range from 6.5 to 12, preferably 7 to 10. Bases such as. Are used for the adjustment of the pH during the condensation Sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, calcium oxide, calcium hydroxide, barium oxide or barium hydroxide. If the compounds of group (a) or (c) are used in excess in the condensation, a pH in the alkaline range is established due to the basicity of these compounds. The condensation is carried out in aqueous or alcoholic solution at a solids content of the solution of usually 20-60% by weight and temperatures of 60-100 _° C. The alcoholic solvents used are, for example, ethylene glycol, propylene glycol, diglycol and / or neopentyl glycol. The water-soluble, not yet quaternized condensation products have a viscosity of at least 500 mPas in 45% aqueous solution at a temperature of 20 _° C. Effective cationic aftertreatment agents can be obtained by using the cationic condensation pro products - especially those from piperazine and epichlorohydrin or ethylene chloride - then quaternized with benzyl chloride.

For the benzylation of the condensation products from components (c) and (b), 0.15 to 1.0, preferably 0.4 to 0.75 mol of benzyl chloride is used per N equivalent of component (c). This achieves a benzylation of 15-90% of the tertiary and - if present in the condensation product - the secondary nitrogen atoms in the condensation product. Condensation products with secondary and tertiary nitrogen atoms are formed when 1-aminoethylpiperazine or bis-1,4- (aminopropyl) piperazine is used as component (c). The benzylation is preferably carried out in an aqueous medium at temperatures of 60-100 _° C. Both the condensation reaction and the benzylation of the condensation products can be carried out at temperatures above 100 _° C. under pressure. This results in shorter response times. The aqueous or alcoholic solutions of the benzylated condensation products can be used directly as a cationic condensation product for the aftertreatment. The viscosity of the cationic condensation products containing benzyl groups (measured in 24% aqueous solution at a temperature of 20 _° C.) is at least 75 mPas and is preferably in the range of 150-400 mPas.

The aftertreatment of the cellulose fiber materials dyed with reactive dyes, which may optionally be in a mixture with other fibers, is carried out discontinuously in dyeing apparatus or continuously for roving in lissuses, or area material on foulards or wide-wash systems. The discontinuous aftertreatment of the colored materials with the aqueous liquors generally takes 5 to 30 minutes. The cationic aftertreatment agents are used in an amount of 0.1 to 5, preferably 0.2 to 3% by weight, based on the dry cellulose fiber material. The aftertreatment of the dyeing, which had previously been washed well with water, using reactive dyes on cellulose fiber materials is carried out at a temperature of the aqueous solution of 5 to 120 _° C., preferably 30 to 100 _° C. and a pH of 4 to 11, preferably 5 to 8 . The reactive dye removed from the dyed material, which is in hydrolyzed form, remains in the aftertreatment liquor and does not deposit on the dyed and aftertreated material. The cellulose fiber materials aftertreated with reactive dyes according to the invention show no color brightening after the treatment according to the invention, so that there are no color shifts even in combination dyeings. In this way, dyeings are obtained which meet the strict requirements placed on dyeings in practice in terms of water fastness. After the treatment according to the invention, the cellulose fiber material is rinsed and then dried. The drying temperature has no significant influence on the improvement in wet fastness.

The parts given in the examples are parts by weight, the percentages relate to the weight of the substances. The viscosities were measured with a rotary viscometer. The following resin solutions were used as cationic condensation products:

Condensation product 1

516 parts of piperazine (6 mol) in 644 parts of water were mixed with 496.7 parts of epichlorohydrin within 50 minutes. The reaction temperature was allowed to rise from 50 to 88 _° C. The reaction mixture was then kept at 90 to 95 _° C. for a further 4 hours. The reaction product then had a viscosity of 4400 mPas (20 _° C) and a chloride content of 3.25 mmol / g. 414 parts of water were added and the mixture was cooled to room temperature (viscosity 270 mPas (20 _° C.)).

1750 parts of this solution were mixed with 3050 parts of 1,2-propanediol and 1050 parts of water, 400 parts of 50% sodium hydroxide solution were added and then 882 parts of benzyl chloride were slowly introduced at 60 to 70 _° C. After a reaction time of 5 hours at 80 _° C., the clear solution had a chloride content of 1.59 mmol / g, a pH of 3.9 and a viscosity of 90 mPas (20 _° C.). The active substance content of the solution of the condensation product 1 was 21.9%. The viscosity of a 24% solution of the condensation product was 140 mPas at 20 _° C. 70% of the nitrogen atoms were quaternized with benzyl chloride, corresponding to 0.7 mol of benzyl chloride per equivalent of nitrogen in the piperazine.

Condensation product 2

1730 parts of the piperazine-epichlorohydrin condensation product, the preparation of which is described under condensation product 1, were mixed with 2560 parts of ethylene glycol and 440 parts of 50% strength aqueous sodium hydroxide solution. At 60 to 80 _° C, 882 parts of benzyl chloride were added within 0.5 hours and then kept at 80 _° C for 5 hours. After cooling to room temperature, the clear solution had a pH of 4.3, a chloride content of 2.05 mmol / g and a viscosity of 285 mPas (20 _° C.). The active ingredient content was 27.8% of condensation product 2. The viscosity of a 24% solution of the condensation product was 220 mPas at 20 _° C. 70% of the nitrogen atoms were quaternized with benzyl chloride, corresponding to 0.7 mol of benzyl chloride per equivalent of nitrogen in the piperazine.

Condensation product 3

The procedure was as indicated under condensation product 2, but the benzylation was carried out not in ethylene glycol but after adding the same amount of diethylene glycol to the piperazine-epichlorohydrin condensation product. A clear solution of the condensation product 3 was obtained. The viscosity of a 24% solution was 300 mPas at 20 _° C. As with the condensation product 2, 70% of the nitrogen atoms were quaternized.

In order to test the wet fastness of the dyeing, the ironing test was carried out.

Ironing test

In practice, the end point of a post-washing process in reactive dyeing is often checked in such a way that a piece of the dyed, not yet dried material is placed between two damp white cotton fabrics and these "sandwiches" ironed to dryness.

As a result of this treatment, the unfixed dyes migrate from the colored to the white material. The test method is very sensitive, since the smallest amounts of unfixed dyes stain the white material.

The dyeings were subjected to this ironing test. The "sandwiches" were pressed 2 x 30 s each at 180 _° C in the ironing machine (Siemens Heimbügler special) and then dried while the machine was running.

example 1

und 1,6 kg des roten Reaktiv-Farbstoffes der Formel

in handelsüblicher Einstellung enthält, wie folgt gefärbt:80 kg of crosslinked mercerized cotton yarn in 1000 l of dye liquor, the 1.04 kg of the yellow reactive dye of the formula, are placed in a strand yarn dyeing apparatus

and 1.6 kg of the red reactive dye of the formula

contains in the commercial setting, colored as follows:

The dyebath is heated to 95 _° C. within 20 minutes. After a dwell time of 10 minutes at 95 _° C., 30 kg of sodium chloride are added and the temperature is then kept at 95 _° C. for a further 5 minutes. The mixture is cooled to 80 _° C. within 10 minutes. Then 4 kg of soda and 2 l of 44.8% aqueous sodium hydroxide solution are added.

The dyebath is then kept at 80 _° C. for a further 30 minutes and then drained off. It is rinsed cold for 10 minutes with an overflow.

Then it is cleaned twice for 10 minutes at 98 _° C. and once for 10 minutes at 70 _° C.

• a. Ein Teil des gefärbten Garns wird getrocknet und dem Bügeltest unterworfen.
• b. Der zweite Teil des gefärbten Garns wird 20 Min. bei 40_°C mit einer wäßrigen Lösung nachbehandelt, die 2% des Kondensationsproduktes 1 (21,9%ig) enthält und einen pH-Wert von etwa 7 hat.
• c. Der dritte Teil des gefärbten Garns wird gemäß der Lehre der DE-OS 2 747 358 10 Min. bei Kochtemperatur mit einer wäßrigen Lösung nachbehandelt, die 2% des Kondensationsproduktes aus 1 Mol Methyldipropylentriamin und 0,87 Mol Epichlorhydrin (21,9%ig) enthält und einen pH-Wert von etwa 7 hat.

The yarn is then divided into 3 parts:

• a. Part of the dyed yarn is dried and subjected to the ironing test.
• b. The second part of the dyed yarn is aftertreated for 20 minutes at 40 _° C. with an aqueous solution which contains 2% of the condensation product 1 (21.9%) and has a pH of about 7.
• c. The third part of the dyed yarn is after-treated according to the teaching of DE-OS 2 747 358 for 10 minutes at boiling temperature with an aqueous solution which comprises 2% of the condensation product from 1 mol of methyldipropylenetriamine and 0.87 mol of epichlorohydrin (21.9%) contains and has a pH of about 7.

The ironing test showed that the accompanying fabric on the untreated yarn (sample a) is heavily stained. Treatment c) reduced bleeding, but could not be prevented. Bleeding of the accompanying tissue was prevented only by treatment b).

Example 2

in handelsüblicher Einstellung

• 4,5 kg m-Nitrobenzolsulfonsaures Natrium,
• 180 kg Natriumchlorid und
• 45 kg Natriumcarbonat
• enthält, 30 Min. bei 80_°C gefärbt.

On a JET dyeing machine, 300 kg of cotton knitwear in 3000 l of dye liquor, the 4.5 kg of the red reactive dye of the formula

in a commercial setting

• 4.5 kg of sodium m-nitrobenzenesulfonate,
• 180 kg sodium chloride and
• 45 kg sodium carbonate
• contains, colored at 80 _° C for 30 min.

• 10 g/I des Kondensationsproduktes 2 (27,8%ig),
• 4 g/I eines kationischen Weichmachers (Kondensationsprodukt aus Stearinsäure und Aminoethylethanolamin) und
• 10 g/1 eines G₁₈-Fettalkoholoxethylates mit 80 Mol Ethylenoxid

It is rinsed cold for 10 minutes, then 2x10 minutes at the boiling temperature and then spun and dried. The cotton fabric was then treated on the padder with an aqueous solution which contained the following additives:

• 10 g / l of the condensation product 2 (27.8%),
• 4 g / l of a cationic plasticizer (condensation product of stearic acid and aminoethylethanolamine) and
• 10 g / 1 of a G ₁₈ fatty alcohol oxyethylate with 80 moles of ethylene oxide

The fleet uptake was 80%. The knitted fabric was then dried at 120 ° C.

The ironing test showed that, in contrast to the untreated fabric, the knitted fabric treated in this way did not show any bleeding on the accompanying fabric.

Example 3

in handelsüblicher Einstellung enthielt. Der Bügeltest ergab, daß ein Begleitgewebe aus Baumwoll-Kaliko nicht anblutete.Dyeing and aftertreatment were carried out as described in Example 2, but with the exception that the 3000 l dye liquor was 4.8 kg of the turquoise dye of the following formula

contained in a commercial setting. The ironing test showed that a cotton calico accompanying fabric did not stain.

Example 4

0,99 kg des roten Reaktiv-Farbstoffes der Formel

und 0,04 kg des blauen Reaktiv-Farbstoffes der Formel

jeweils in handelsüblicher Einstellung sowie 20 g/I Soda und 80 g/I Natriumchlorid enthielt, wie folgt gefärbt: Zunächst wird 15 Min. bei 25_°C gefärbt, dann in 30 Min. auf 50_°C erwärmt, und anschließend das Färbebad 20 Min. bei dieser Temperatur gehalten. Anschließend wird in 30 Min. auf 80_°C aufgeheizt und in 45 Min. zu Ende gefärbt.In an overflow dyeing machine, 75 kg of bleached cotton jersey are put into 1200 l of dyeing liquor, the 2.475 kg of the scarlet-colored reactive dye of the formula

0.99 kg of the red reactive dye of the formula

and 0.04 kg of the blue reactive dye of the formula

each in a commercially available setting and containing 20 g / l of soda and 80 g / l of sodium chloride, dyed as follows: first dyeing at 25 _° C. for 15 minutes, then heating to 50 _° C. in 30 minutes, and then the dye bath for 20 minutes kept at this temperature. The mixture is then heated to 80 _° C. in 30 minutes and finished in 45 minutes.

Rinsing is cold for 10 minutes, then 2x10 minutes at cooking temperature and then once for 10 minutes at 50 ° C.

The goods are then aftertreated for 10 minutes at 60 _° C. with an aqueous solution which contained 1.5% of the condensation product 3 (24%) and had a pH of about 7. In the subsequent ironing test, an undyed accompanying fabric made of cotton calico was not bled on.

Example 5

Staining and rinsing was carried out as described in Example 4. Aftertreatment was carried out for 10 minutes at boiling temperature with an aqueous solution containing 1.5% of the condensation product 3 (24%) and 1.6% (= 1 g / l) soda calc. contained and had a pH of about 10.5.

During the subsequent ironing test, an undyed accompanying fabric made of cotton calico was not bled on.

Example 6

Staining was carried out as described in Example 4. The colored material was then rinsed three times for 10 minutes at 25 ° C., then once for 10 minutes at the boiling temperature and then with an aqueous solution containing 1.5% of the condensation product 3 and 1.6% soda calc. contained and had a pH of about 10.5, aftertreated. The aftertreatment bath was entered at 40 _° C. and then heated to boiling temperature within 20 minutes. The ironing test showed that the cotton jersey treated in this way showed no bleeding of the accompanying fabric.

Example 7

in handelsüblicher Einstellung sowie 70 g/I Natriumsulfat, 5 g/I Soda und 2 g/I 44,8%ige wäßrige Natronlauge enthält, zugegeben. Das Material wird 60 Min. bei 80_°C gefärbt, danach 10 Min. kalt, dann 2x10 Min. bei Kochtemperatur und anschließend 10 Min. bei 60_°C im Überlauf gespült.In an overflow dyeing machine 100 kg of cotton jersey in 2000 l dyeing liquor, the 5 kg of the red reactive dye of the formula

contains in a commercial setting and 70 g / l sodium sulfate, 5 g / l soda and 2 g / l 44.8% aqueous sodium hydroxide solution. The material is dyed for 60 minutes at 80 _° C, then cold for 10 minutes, then 2x10 minutes at boiling temperature and then rinsed in the overflow for 10 minutes at 60 _° C.

• a) Ein Teil des gefärbten Baumwoll-Trikots wurde getrocknet und dem Bügeltest unterworfen.
• b) Der zweite Teil des gefärbten Baumwoll-Trikots wurde 10 Min. bei Kochtemperatur mit einer wäßrigen Lösung nachbehandelt, die 2% des Kondensationsproduktes 2 (27,8%ig) enthielt und einen pH-Wert von etwa 7 hatte.
• c) Der dritte Teil des gefärbten Baumwoll-Trikots wurde gemäß der Lehre der DE-OS 2 747 358 10 Minuten bei Kochtemperatur mit einer Lösung nachbehandelt, die 2% des Kondensationsproduktes aus 1 Mol Methyldipropylentriamin und 0,87 Mol Epichlorhydrin (27%ig) enthielt und einen pH-Wert von etwa 7 hatte.

The cotton jersey was then divided into 3 parts:

• a) Part of the dyed cotton jersey was dried and subjected to the ironing test.
• b) The second part of the dyed cotton jersey was aftertreated for 10 minutes at boiling temperature with an aqueous solution which contained 2% of the condensation product 2 (27.8%) and had a pH of about 7.
• c) The third part of the dyed cotton jersey was after-treated according to the teaching of DE-OS 2 747 358 for 10 minutes at boiling temperature with a solution containing 2% of the condensation product from 1 mol of methyldipropylenetriamine and 0.87 mol of epichlorohydrin (27%) contained and had a pH of about 7.

The ironing test showed that the accompanying fabric on the untreated cotton jersey (sample a) was heavily stained. Treatment c) reduced bleeding, but could not be prevented. Bleeding of the accompanying tissue was prevented only by treatment b).

The ironing test shows that the accompanying material stains heavily on the untreated tissue (sample a) and the tissue which has been subjected to treatment b). Bleeding of the accompanying tissue could only be prevented by treatment c).

Claims (4)

1. A process for the after-treatment of dyeings with reactive dyes on cellulose fiber materials, using an aqueous solution of a condensate of polyamines and epichlorohydrin, wherein the sole after-treatment agent used is a cationic condensate which is obtainable by reacting

a) bisbenzylpiperazine with

b) ethylene chloride, an epihalohydrin, propylene chloride, 1.3-dichloro-2-hydroxypropane, bisepoxyb- utane or 1.4-dichlorobutane or a mixture of these, in a molar ratio of from 1:0.5 to 1:1.1,

or by reacting

c) piperazine, bis-1.4-aminopropylpiperazine, 1-aminoethylpiperazine, 2-hydroxyethylpiperazine or 1-methylpiperazine, or a mixture of these,

with a compound according to (b) in a molar ratio of from 1:0.5 to 1:1.1 and benzylating the condensate, 0.15-1.0 mole of benzyl chloride being used per equivalent of nitrogen in component (c) for the benzylation.

2. A process as claimed in claim 1, wherein the after-treatment agent (100% strength) is used in an amount of from 0.1 to 5% by weight, based on the cellulose fiber materials.

3. A process as claimed in either of claims 1 and 2, wherein the after-treatment is carried out using an aqueous solution at from 5 to 120_°C and a pH of from 4 to 11.

4. A process as claimed in any of claims 1 to 3, wherein the cationic condensate used is a benzylated piperazine/epichlorohydrin condensate.