EP0223064A1 - Process for the aftertreatment of reactive dyeings on cellulosic fibres - Google Patents

Abstract

• a) Methylamin und Epichlorhydrin oder
• b) durch Erhitzen von Triethanolamin und/oder Triisopropanolamin in Gegenwart von sauren Katalysatoren

erhältlich und die jeweils, bezogen auf 1 Mol Amin im Kondensationspro­dukt, mit 0,25 bis 1 Mol Benzylchlorid umgesetzt sind.Process for the aftertreatment of reactive dyeings on cellulosic fibers containing textile materials by the action of aqueous solutions of benzylated resins by condensation of

• a) methylamine and epichlorohydrin or
• b) by heating triethanolamine and / or triisopropanolamine in the presence of acidic catalysts

available and which, based on 1 mol of amine in the condensation product, are reacted with 0.25 to 1 mol of benzyl chloride.

The dyed textile materials treated in this way are characterized by high wet fastness properties.

Description

In practice, fiber materials containing cellulose fibers which are dyed with reactive dyes are usually subjected to a boiling alkaline wash in the presence of surfactants in order to remove the dye which is not fixed on the fabric. With the aid of this procedure, colored cellulose fiber materials are obtained which, although they have sufficient wash fastnesses, are in need of improvement with regard to water fastness, ironing fastness and also sweat fastness.

DE-OS 27 47 358 discloses a process for the aftertreatment of cellulose fiber materials which are dyed with reactive dyes, in which the fiber materials are treated with an aqueous solution of polyamines, polyamides, polyurethanes and / or polyureas containing secondary and / or tertiary amino groups . With the help of such an aftertreatment, the wet fastness properties of reactive dyeings on cellulose are improved, but a further increase in the fastness level of the aftertreated dyeings is desirable, in particular the light fastness and the dry rubbing fastness.

The object of the present invention is to provide a process for the aftertreatment of reactive dyeings on textile materials containing cellulose fibers, in which dyed textile materials with high wet fastness properties are obtained, the light fastness and fastness to rubbing of which practically do not deteriorate compared to a dyed material washed in the usual way are.

• a) Methylamin und Epichlorhydrin oder
• b) durch Erhitzen von Triethanolamin und/oder Triisopropanolamin in Gegenwart von sauren Katalysatoren

erhältlich und die jeweils, bezogen auf 1 Mol Amin im Kondensationspro­dukt, mit 0,25 bis 1 Mol Benzylchlorid umgesetzt sind.The object is achieved according to the invention with a process for the aftertreatment of reactive dyeings on textile materials containing cellulose fibers, in which the dyed textile materials are rinsed with water, aftertreated with aqueous solutions of cationic condensation products at temperatures from 5 to 100 ° C. and then rinsed again with water, thereby solved that water-soluble, quaternized resins are used as cationic condensation products, which by condensation of

• a) methylamine and epichlorohydrin or
• b) by heating triethanolamine and / or triisopropanolamine in the presence of acidic catalysts

available and which, based on 1 mol of amine in the condensation product, are reacted with 0.25 to 1 mol of benzyl chloride.

The textile materials containing cellulose fibers can be in the form of fibers, yarns, fabrics or other piece goods. The cellulose fibers are, for example, cotton, linen or cellulose. The textile materials which are post-treated according to the invention may consist solely of cellulose fibers or may contain cellulose fibers, optionally in a mixture with synthetic fibers, such as polyamide, polyacrylonitrile or polyester fibers.

The cellulose fibers are dyed in a known manner with the commercially available reactive dyes, e.g. at 20 to 100 ° C after the exhaust process or at room temperature after the cold dwell process. After dyeing, the textile material is first rinsed with cold water, then cleaned once or twice with hot water (70 to 100 ° C) and, if necessary, once more with water at a temperature of 60 to 80 ° C. Only then is the textile material containing the cellulose fibers dyed with the reactive dyes treated with the cationic benzylated resins to be used as aftertreatment agent in aqueous solution.

The cationic condensation products to be used according to the invention are produced by condensation of methylamine and epichlorohydrin in a molar ratio of 1: 0.8 to 1. The condensation of methylamine and epichlorohydrin is known and takes place in the temperature range from 30 to 90 ° C., preferably 40 to 80 ° C. The condensation is carried out in aqueous or alcoholic solution with a solids content of the solution of usually 20 to 60% by weight. The alcoholic solvent used is, for example, ethylene glycol, propylene glycol, diglycol and / or neopentyl glycol. The condensation takes place in the pH range from 8 to 12, preferably 8 to 9. Bases, such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, calcium oxide, calcium hydroxide, barium oxide or balium hydroxide, are optionally used to adjust the pH. If an excess of methylamine is used in the condensation, a pH in the alkaline range is established due to the basicity of the methylamine. The condensation is carried out so far that water-soluble products are formed which have a viscosity of at least 300 mPa.s in 20% aqueous solution at a temperature of 20 ° C.

The cationic condensation products according to b) to be used according to the invention, which are obtainable by heating triethanolamine and / or triisopropanolamine in the presence of acidic catalysts at temperatures from 120 to 280 ° C., are also known compounds, cf. DE-AS 11 27 084 and DE-AS 12 43 874. Examples of acidic catalysts used are formic acid, oxalic acid and the salts and esters water acids, phosphorous acid or their ammonium and amine salts, halides, di- and triesters of phosphorous acid, amides of phosphorous acid, ester amides or phosphonic acid or their halides, esters, amides or ester amides. The condensation of triethanolamine, triisopropanolamine or mixtures of the compounds mentioned is preferably carried out in the presence of phosphorous acid or hypophosphorous acid. The acidic catalysts are used in an amount of 0.1 to 1.0% by weight, based on the hydroxyalkylamine to be condensed. In this way, the condensation products b) are obtained which have a viscosity of at least 40,000 mPa.s, preferably 40,000 to 60,000 mPa.s, at 100% at a temperature of 20 ° C.

The water-soluble cationic condensation products a) and b) described above are quaternized in a second reaction step, 0.25 to 1 mol, preferably 0.5 to 1 mol, based in each case on 1 mol of amine in the condensation product a) and b) Benzyl chloride used. The quaternization takes place in an aqueous, preferably in an aqueous-alcoholic medium at temperatures from 60 to 100 ° C., but can also be carried out at higher temperatures, but then pressure must be used. The reaction of the condensation products a) and b) can be carried out in the presence of alcohols as solubilizers. The aqueous or alcoholic solutions of the benzylated condensation products a) and b) can be used directly for the aftertreatment of reactive dyeings on textile materials containing cellulose fibers. The viscosity of the condensation products a) and b) reacted with benzyl chloride in 20% aqueous solution at 20 ° C. is at least 6 mPa.s and is preferably in the range from 8 to 200 mPa.s.

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 with an aqueous liquor of the benzylated condensation products a) or b), or continuously for Kandenband in lisseuses, or flat material on foulards or wide-washing machines. The discontinuous aftertreatment of the dyed materials with the aqueous liquors generally takes 5 to 30 minutes. The concentration of the water-soluble quaternary resins in the aftertreatment liquor is 0.1 to 5, preferably 0.25 to 2 g / l. The liquor ratio is in the range from 1: 5 to 50, preferably 1:10 to 20. The aftertreatment liquor has a pH in the range from 4 to 11, preferably 5 to 8. However, the quaternized resins can also be applied to the goods, which is to be treated, is padded.

When padding, aqueous solutions of the benzylated resin are generally used in a concentration of 1 to 50 g / l, preferably 2.5 to 15 g / l.

Before the cellulose fiber materials dyed with reactive dyes are aftertreated with the benzylated cationic resins, they are rinsed well with water, advantageously first at least once with cold water and then at least once with water at a temperature of 70 to 100.degree. The hydrolyzed reactive dyes washed out of the textile material do not give any precipitates in the presence of the products to be used according to the invention. If, on the other hand, condensation products of dimethylamine and epichlorohydrin are used, then there are disruptive precipitations in the aftertreatment liquor.

The aftertreatment according to the invention can be carried out in the temperature range from 5 to 100.degree. C. and is carried out in a procedure analogous to an exhaust process, preferably at temperatures from 40 to 70.degree. The procedure can also be such that the cellulose material colored with the reactive dyes is first rinsed out with cold and hot water, then treated with the aqueous solution of the benzylated resin at near boiling temperature and then rinsed with water. The textile material containing post-treated cellulose fibers according to the invention shows no color brightening, so that even with combination dyeings there are no color shifts. In this way, dyeings are obtained which meet the strict requirements placed on dyeings in practice in terms of water fastness. The light fastness and fastness to rubbing of the dyeings is practically not deteriorated by the aftertreatment according to the invention. Following the aftertreatment according to the invention, the textile material containing cellulose fibers can be rinsed. Then it is dried.

The parts given in the examples are parts by weight, the percentages relate to the weight. The viscosities were measured in a rotary viscometer (Haake, Rotavisco). The following products were used as the benzylated cationic resins:

Resin 1 (condensation product of methylamine and epichlorohydrin)

606 g of a 40.9% aqueous methylamine solution (8 mol) are diluted with 636 g water and at 20 to 40 ° C with cooling within 30 minutes with 333 g epichlorohydrin (3.6 mol) and 288 g 50% aqueous Sodium hydroxide solution added. As soon as the exothermic reaction has subsided, a further 348 g of epichlorohydrin (3.76 mol) are added within 30 minutes drips and the temperature is raised from 40 to 90 ° C. After the end of the epichlorohydrin addition, the mixture is kept at 90 ° C. for 1 hour, 144 g of 50% sodium hydroxide solution are added and the mixture is condensed at 90 ° C. for a further 2 hours. The mixture is then cooled to 40 ° C. and 810 g of water and 144 g of sodium hydroxide solution are added.

The resin has a viscosity of 350 mPas (20 ° C, D _k : 74 s⁻¹), a chloride content of 2.22 mmol / g and a refractive index of n _D 20: 1,393.

3300 g of this methylamine-epichlorohydrin condensation product are mixed with 1620 diglycol and 65 g of 50% sodium hydroxide solution, heated to 60 to 70 ° C., 1008 g of benzyl chloride are added dropwise at this temperature in the course of 0.5 hours and then stirred at 80 ° C. for 3 hours. It is adjusted to pH 4.0 with 53 g (99% strength) formic acid, diluted with 2459 g diglycol and cooled to room temperature. The cationic resin shows a chloride content of 1.83 mmol / g, an acid number (alcoholic KOH) of 0.30 mmol / g, a viscosity (Haake Rotavisco) of 150 mPas (measured at 20 ° C.) (D _k : 26, 4 s⁻¹), a refractive index of 1.4546 and a pH of 4.0.

Resin 2 (condensed triethanolamine)

1790 g of triethanolamine (12 mol) and 12 g of hypophosphorous acid (H₃PO₂, 50% aqueous) are heated to 230 ° C. in a reaction vessel with a stirrer and distillation device under nitrogen. Within 4 to 5 hours the viscosity of the reaction solution increases to 42,000 to 44,000 mPas with elimination of water (measured at 20 ° C, D _k 12 s⁻¹ in a cone-plate rotary viscometer). 1610 g of polyaminopolyether are obtained. Amine number: 7.44 mmol / g.

1480 g of this triethanolamine polyether are mixed with 2880 g of water, heated to 60 to 70 ° C and then quaternized at 80 ° C with 1386 g of benzyl chloride within one hour. The mixture is left to react for 3 hours at 80 ° C. and then cooled to room temperature. Chloride content of the solution: 1.92 mmol / g. Viscosity (Rotavisco v. Haake): 140 mPas (20 ° C; D _k 76.8 s⁻¹).

example 1

Knitwear made of cotton is, based on the goods, dyed with 5% of the orange reactive dye of Color Index No. 18260 in a liquor ratio of 1:20 with a liquor which, in addition to dye, contains 60 g / l sodium chloride, 9 g / l sodium carbonate and 1 g / l Contains sodium bicarbonate. To After a dyeing time of 30 min, the liquor is drained, the material is then rinsed with cold water in a liquor ratio of 1:20, the rinsing liquor is drained off and the material is then treated with water at 95 ° C. for 10 min. The water is drained off again and the dyed textile material is treated with an aqueous solution containing 2 g / l of resin 1. The aftertreatment with the aqueous solution of resin 1 is 10 minutes at the boiling point. The pH of the liquor is adjusted to 5 to 6. After the 10-minute treatment, the originally colorless liquor is clearly stained. It is drained off and the material treated with it is rinsed with cold water and then dried.

A dyeing is obtained which is difficult to achieve in water fastness (according to DIN 54 006, staining of the cotton accompanying fabric) with a rating of 4 to 5 and is thus 1.5 marks better than a dyeing which is treated with a conventional anionic or nonionic detergent becomes. For this it is difficult to determine the grade 3 for water justice.

The dry rub fastness properties (according to DIN 54 021) and the light fastness properties according to Xenotest lighting (DIN 54 004) are practically unchanged for the material aftertreated according to the invention. Similar improvements as with water fastness are also obtained if the wet dyeing between two pieces of cotton fabric is ironed in a standardized manner according to the ironing test described below.

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 are subjected to this ironing test. The "sandwiches" are pressed twice in the ironing machine at 180 ° C for 30 s each (Siemens Heimbügler Spezial) and then dried while the machine is running.

Similar results are achieved as with water justice. The same result is obtained if a cotton fabric is used instead of the knitted fabric.

Example 2

A cotton knitwear is dyed as described in Example 1 and then rinsed with cold and hot water. The goods are then treated with an aqueous solution which contains 2 g / l of the resin 2 dissolved. The aftertreatment is carried out at 100 ° C. within 10 minutes. The goods are then rinsed once with cold water and dried.

When testing the water fastness difficult (according to DIN 54 006, staining of the cotton fabric), the grade 4 to 5 is achieved.

Example 3

wird eine 3 %ige Färbung auf Baumwoll-Wirkware hergestellt, indem man im Flottenverhältnis 1:20 mit einer Flotte färbt, die außer dem genannten Farbstoff noch 60 g/l Natriumchlorid und 20 g/l Natriumcarbonat enthält. Die Ware wird in dieser Flotte innerhalb von 40 min auf 80°C erhitzt, dann 60 min bei 80°C gehalten und danach, wie im Beispiel 1 beschrieben, je einmal kalt und heiß gespült. Sie wird dann anschließend 5 min bei einer Temperatur von 100°C mit einer wäßrigen Lösung von 1 g/l des Harzes 1 nachbehandelt. Die dabei entstehende gefärbte Flotte wird ab­gelassen und das Material anschließend mit kaltem Wasser gespült und ge­trocknet. Man erhält eine Färbung, deren Reibechtheit und Lichtechtheit gegenüber einer Färbung, die auf übliche Weise geseift wurde, nicht ver­schlechtert ist. Die Wasserechtheit schwer (Anbluten von Baumwollgewebe nach DIN 54 006) liegt bei 4 bis 5.Using the red dye of the formula

a 3% dyeing on knitted cotton fabric is produced by dyeing in a 1:20 liquor ratio with a liquor which, in addition to the dye mentioned, also contains 60 g / l sodium chloride and 20 g / l sodium carbonate. The goods in this liquor are heated to 80 ° C. in the course of 40 minutes, then kept at 80 ° C. for 60 minutes and then, as described in Example 1, rinsed once cold and hot. It is then aftertreated for 5 min at a temperature of 100 ° C. with an aqueous solution of 1 g / l of resin 1. The resulting colored liquor is drained off and the material is then rinsed with cold water and dried. A dyeing is obtained whose fastness to rubbing and lightfastness is not impaired by a dyeing which has been soaped in the customary manner. The water fastness difficult (bleeding of cotton fabric according to DIN 54 006) is 4 to 5.

If the goods aftertreated according to the invention are stored for 3 days at 80 ° C. in saturated moisture (tropical test), then no deterioration in water fastness occurs with difficulty.

Example 4

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 %, bezogen auf das Garngewicht, des Harzes 1 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 10 Min. bei Kochtemperatur mit einer wäßrigen Lösung nachbehandelt, die 2 %, bezogen auf das Garngewicht, 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%, based on the weight of the yarn, of resin 1 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 for 10 minutes at boiling temperature with an aqueous solution which contains 2%, based on the weight of the yarn, of the condensation product of 1 mol of methyldipropylenetriamine and 0.87 mol of epichlorohydrin ( Contains 21.9%) and has a pH of about 7.

The ironing test shows that the accompanying fabric heavily stains the untreated yarn (sample a). Treatment c) can reduce bleeding, but it cannot be prevented. Bleeding of the accompanying tissue is prevented only by treatment b).

Example 5

0,99 kg des roten Reaktivfarbstoffes der Formel

und 0,04 kg des blauen Reaktivfarbstoffes der Formel

jeweils in handelsüblicher Einstellung sowie 20 g/l Soda und 80 g/l Natriumchlorid enthielt, wie folgt gefärbt.In an overflow dyeing machine, 75 kg of bleached cotton jersey in 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 contained in a commercially available setting and 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 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 cold for 10 minutes, then 2 × 10 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 resin 2 and had a pH of about 7. In the subsequent ironing test, an undyed accompanying fabric made of cotton calico is not bled on.

Claims (6)

1. A process for the aftertreatment of reactive dyeings on cellulose fiber-containing textile materials, in which the dyed textile materials are rinsed with water, aftertreated with aqueous solutions of cationic condensation products at temperatures from 5 to 100 ° C. and then rinsed again with water, characterized in that uses water-soluble, quaternized resins as cationic condensation products a) methylamine and epichlorohydrin or b) by heating triethanolamine and / or triisopropanolamine in the presence of acidic catalysts available and which, based on 1 mol of amine in the condensation product, are reacted with 0.25 to 1 mol of benzyl chloride. 2. The method according to claim 1, characterized in that water-soluble, benzylated resins are used which are obtainable by reacting the condensation products a) or b) with 0.5 to 1 mol of benzyl chloride based on 1 mol of amine in the condensation products. 3. Process according to claims 1 and 2, characterized in that the concentration of the water-soluble, benzylated resins in the aqueous solution is 0.1 to 5 g / l and the liquor ratio is 1: 5 to 50. 4. Process according to claims 1 and 2, characterized in that the water-soluble, benzylated resins are applied to the cellulose fiber materials by padding an aqueous solution containing 1 to 50 g / l of the resin. 5. Process according to claims 1 to 3, characterized in that the dyed textile material is rinsed at least once with cold water, then at least once with water at a temperature of 70 to 100 ° C and then the aftertreatment at 90 to 100 ° C carries out.