EP0209787A2 - 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 27 47 358 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 aid 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.

The object of the present invention is to provide 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 : O,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 : O,5 bis 1,1 und Benzylierung der Kondensationsprodukte erhältlich ist, wobei man bei der Benzylierung pro Äquivalent Stickstoff in der Komponente (c) O,15 - 1,O 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: O, 5 to 1.1 or by reacting
• (c) piperazine, bis-1,4- (aminopropyl) piperazine, 1-aminoethylpiperazine, 2-hydroxyethylpiperazine, 1-methylpiperazine or mixtures thereof

is obtainable with the compounds according to (b) in a molar ratio of 1: 0.5 to 1.1 and benzylation of the condensation products, O, 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 in the usual way with the commercially available reactive dyes, e.g. at 2O - 100 ° C using the pull-out method or at room temperature using the cold dwell method. 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 Lich by reacting (a) bis-benzylpiperazine with (b) ethylene chloride, epihalohydrin, propylene chloride, 1,3-dichloro-2-hydroxypropane, bis-epoxy-butane, 1,4-dichlorobutane or mixtures thereof in a molar ratio a : b from 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 given 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 sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, calcium oxide, calcium hydroxide, barium oxide or barium hydroxide are optionally used to adjust the pH during the condensation. 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 to 60% by weight and temperatures of 60 to 100 ° C. The alcoholic solvent used is e.g. Ethylene glycol, propylene glycol, diglycol and / or neopentyl glycol. The water-soluble, not yet quaternized condensation products have a viscosity of at least 5OO mPas in 45% aqueous solution at a temperature of 20 ° C. Effective cationic aftertreatment agents are obtained if the cationic condensation products - in particular those from piperazine and epichlorohydrin or ethylene chloride - are subsequently quaternized with benzyl chloride.

For the benzylation of the condensation products from components (c) and (b), 0.15 to 1.0 O is used per N equivalent of component (c). preferably 0.4 to 0.75 mol of benzyl chloride. 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 150-040 mPas.

The aftertreatment of the cellulose fiber materials dyed with reactive dyes, which may optionally be present in a mixture with other fibers, is carried out discontinuously in dyeing apparatus or continuously for combing 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 thoroughly washed out 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 44OO mPas (2O ° 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 27O mPas (2O ° C).

175O parts of this solution were mixed with 3O5O 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 14O 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

173O parts of the piperazine-epichlorohydrin condensation product, the preparation of which is described under condensation product 1, were mixed with 256O parts of ethylene glycol and 44O parts of 50% 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 22O 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 30 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 × 3O s at 18O ° C in the ironing machine (Siemens Heimbügler special) and then dried with the machine running.

example 1

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

in handelsüblicher Einstellung enthält, wie folgt gefärbt:In a strand yarn dyeing machine, 8O kg of crosslinked mercerized cotton yarn are put into 1OOO l of dye liquor, the 10 4 kg of the yellow reactive dye of the formula

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 residence time of 10 minutes at 95 ° C., 30 kg 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 10 minutes cold with 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 2O Min. bei 4O°C mit einer wäßrigen Lösung nachbehandelt, die 2 % des Kondensationspro­duktes 1 (21,9%rig) enthält und einen pH-Wert von etwa 7 hat.
• c. Der dritte Teil des gefärbten Garns wird gemäß der Lehre der DE-OS 27 47 358 1O Min. bei Kochtemperatur mit einer wäßrigen Lösung nachbehandelt, die 2 % des Kondensationsproduktes aus 1 Mol Methyl­dipropylentriamin und O,87 Mol Epichlorhydrin (21,9%rig) 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% rig) and has a pH of about 7.
• c. The third part of the dyed yarn is aftertreated according to the teaching of DE-OS 27 47 358 10 min. At boiling temperature with an aqueous solution which comprises 2% of the condensation product of 1 mol of methyldipropylenetriamine and 0.87 mol of epichlorohydrin (21.9% rig) 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,
18O kg Natriumchlorid und
45 kg Natriumcarbonat
enthält, 3O Min. bei 8O°C gefärbt.On a JET dyeing machine, 300 kg of knitted cotton fabric 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,
18O kg sodium chloride and
45 kg sodium carbonate
contains, 3O min. at 8O ° C.

Rinsing is carried out cold for 10 minutes, then 2 × 10 minutes at cooking 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 / l of a C₁₈ fatty alcohol oxyethylate with 80 mol ethylene oxide

The liquor 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.The dyeing and aftertreatment was carried out as described in Example 2, with the exception that the 30,000 liter dye liquor contained 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

O,99 kg des roten Reaktiv-Farbstoffes der Formel

und O,O4 kg des blauen Reaktiv-Farbstoffes der Formel

jeweils in handelsüblicher Einstellung sowie 2O g/l Soda und 8O g/l Natriumchlorid enthielt, wie folgt gefärbt:
Zunächst wird 15 Min. bei 25°C gefärbt, dann in 3O Min. auf 5O°C erwärmt, und anschließend das Färbebad 2O Min. bei dieser Temperatur gehalten. Anschließend wird in 3O Min. auf 8O°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

0.19 kg of the red reactive dye of the formula

and 0.14 kg of the blue reactive dye of the formula

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

Rinsing is carried out cold for 10 minutes, then 2 × 10 minutes at the 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 dyed 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 the cooking 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 7O g/l Natriumsulfat, 5 g/l Soda und 2 g/l 44,8%rige wäßrige Natronlauge enthält, zugegeben. Das Material wird 6O Min. bei 8O°C gefärbt, danach 1O Min. kalt, dann 2×1O Min. bei Koch­temperatur und anschließend 1O Min. bei 6O°C im Überlauf gespült.In an overflow dyeing machine, 100 kg of cotton jersey are put into 20000 l of dyeing liquor, the 5 kg of the red reactive dye of the formula

contains in a commercial setting as well as 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 2 × 10 minutes at the 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 1O Min. bei Kochtemperatur mit einer wäßrigen Lösung nachbehandelt, die 2 % des Kondensationsproduktes 2 (27,8%rig) enthielt und einen pH-Wert von etwa 7 hatte.
• c) Der dritte Teil des gefärbten Baumwoll-Trikots wurde gemäß der Lehre der DE-OS 27 47 358 1O Minuten bei Kochtemperatur mit einer Lösung nachbehandelt, die 2 % des Kondensationsproduktes aus 1 Mol Methyldi­propylentriamin und O,87 Mol Epichlorhydrin (27,%rig) 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 condensation product 2 (27.8% rig) 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 27 47 358 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% rig ) 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).

Example 8

in handelsüblicher Einstellung enthält, wie folgt gefärbt:
Das Färbebad wird innerhalb von 2O Min. auf 95°C aufgeheizt. Nach einer Verweilzeit von 1O Min. bei 95°C setzt man 3O kg Natriumchlorid zu und hält anschließend die Temperatur weitere 5 Min. bei 95°C. Innerhalb von 1O Min. wird auf 8O°C abgekühlt. Dann gibt man 4 kg Soda und 2 l 44,8%rige wäßrige Natronlauge zu.In a fully flooded jet dyeing machine, 100 kg of cotton fabric in 1500 l of dyeing liquor, the 5 kg of the orange-colored 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 residence time of 10 minutes at 95 ° C., 30 kg 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.

• a) Ein Teil des Gewebes wird getrocknet und dem Bügeltest unterworfen.
• b) Der zweite Teil des gefärbten Baumwollgewebes wird auf dem Foulard mit einer wäßrigen Lösung behandelt, die folgende Zusätze enthält:
  8O g/l Dimethylolglyoxalmonourein (45%ig)
  12 g/l MgCl₂ . 6 H₂O
  Die Flottenaufnahme beträgt 78 %. Das Gewebe wird anschließend bei 11O°C getrocknet und danach 4 Min. bei 155°C kondensiert.
• c) Der dritte Teil des gefärbten Baumwollgewebes wird auf dem Foulard mit einer wäßrigen Lösung folgender Zusammensetzung behandelt:
  8O g/l Dimethylolglyoxalmonourein (45%ig)
  12 g/l MgCl₂ . 6 H₂O
  4O g/l des Kondensationsproduktes 3 (24%ig)
  Flottenaufnahme, Trocknungs- und Kondensationsbedingungen werden, wie unter b) beschrieben, eingehalten.

Then the tissue is divided into 3 parts:

• a) Part of the fabric is dried and subjected to the ironing test.
• b) The second part of the dyed cotton fabric is treated on the padder with an aqueous solution which contains the following additives:
  80 g / l dimethylolglyoxal monourein (45%)
  12 g / l MgCl₂. 6 H₂O
  The fleet intake is 78%. The fabric is then dried at 110 ° C. and then condensed at 155 ° C. for 4 minutes.
• c) The third part of the dyed cotton fabric is treated on the foulard with an aqueous solution of the following composition:
  80 g / l dimethylolglyoxal monourein (45%)
  12 g / l MgCl₂. 6 H₂O
  40 g / l of the condensation product 3 (24%)
  The liquor intake, drying and condensation conditions are observed as described under 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).

The effectiveness of the wrinkle-free, shrink-free finish was not adversely affected by the addition of the condensation product 3 in treatment c). The equipment according to b) and c) gave the same shrinkage values for household washing (20 minutes at 60%). There were also no differences when assessing the smoothness according to Monsanto.

With the additional use of a hydrophobizing agent in baths b) and c), it was found that the hydrophobicity of the finished fabric was also not influenced by the use of the condensation product 3.

Claims (5)

1. A process for the aftertreatment of dyeings with reactive dyes on cellulose fiber materials with aqueous solutions of condensation products from polyamines and epichlorohydrin, characterized in that a cationic condensation product is used as the aftertreatment agent, which by reaction of (a) Bis-benzylpiperazine with (b) ethylene chloride, epihalohydrin, propylene chloride, 1,3-dichloro-2-hydroxypropane, bis-epoxybutane, 1,4-dichlorobutane or their mixtures in a molar ratio of 1: O, 5 to 1.1 or by reacting (c) piperazine, bis-1,4- (aminopropyl) piperazine, 1-aminoethylpiperazine, 2-hydroxyethylpiperazine, 1-methylpiperazine or mixtures thereof with the compounds according to (b) in a molar ratio of 1: O, 5 to 1.1 and benzylation of the condensation products, wherein in the benzylation per equivalent of nitrogen in component (c) O, 15-1, O mol of benzyl chloride starts. 2. The method according to claim 1, characterized in that one uses the post-treatment agent (100%) in an amount of 0.1 to 5 wt.%, Based on the cellulose fiber materials. 3. Process according to claims 1 and 2, characterized in that the aftertreatment is carried out at a temperature of the aqueous solution of 5 to 120 ° C and a pH of 4 to 11. 4. Process according to claims 1 to 3, characterized in that a benzylated piperazine-epichlorohydrin condensation product is used as the cationic condensation product.