EP0223064B1 - Process for the aftertreatment of reactive dyeings on cellulosic fibres - Google Patents

Process for the aftertreatment of reactive dyeings on cellulosic fibres Download PDF

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Publication number
EP0223064B1
EP0223064B1 EP86114237A EP86114237A EP0223064B1 EP 0223064 B1 EP0223064 B1 EP 0223064B1 EP 86114237 A EP86114237 A EP 86114237A EP 86114237 A EP86114237 A EP 86114237A EP 0223064 B1 EP0223064 B1 EP 0223064B1
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EP
European Patent Office
Prior art keywords
water
aftertreatment
rinsed
resin
condensate
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EP86114237A
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German (de)
French (fr)
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EP0223064A1 (en
Inventor
Ulrich Dr. Baumgarte
Rolf Dr. Fikentscher
Sigismund Dr. Heimann
Heinrich Dr. Mertens
Siegfried Schneider
Michele Dr. Vescia
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular

Definitions

  • 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.
  • surfactants in order to remove the dye which is not fixed on the fabric.
  • 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-A-2 747 358 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 treated.
  • 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 lightfastness 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 colored 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.
  • 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 known to be dyed 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.
  • the textile material is first rinsed with cold water, then cleaned once or twice with hot water (70-100 ° C) and, if necessary, once more with water at a temperature of 60 to 80 ° C.
  • the cationic condensation products according to a) to be used according to the invention are prepared by condensing 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 at 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 barium hydroxide are optionally used to adjust the pH. If methylamine is used in excess in the condensation, a pH in the alkaline range is established due to the basicity of the methylamine. The condensation is carried out to such an extent 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 triisopropanoiamine in the presence of acidic catalysts at temperatures of normally 120 to 280 ° C., are also known compounds, cf. DE-B-1 127 084 and DE-B-1 243 874.
  • acidic catalysts used are formic acid, oxalic acid and the salts and esters of these acids, phosphorous acid or its ammonium and amine salts, halides, di- and triesters phosphorous acid, amides of phosphorous acid, ester amides or phosphonous acid or their halides, esters, amides or ester amides.
  • the condensation of triethanolamine, triisopropanoiamine 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 normally 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, wherein 0.25 to 1 mol, preferably 0 to 1 mol, of benzyl chloride are used, based in each case on 1 mol of amine in the condensation product a) or b).
  • the quaternization is carried out 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 it is then necessary to work under pressure.
  • 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 is carried out discontinuously in dyeing apparatuses a) or b) in dyeing machines or continuously for card sliver in liss recipients, or area material on foulards or wide-wash systems.
  • 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.
  • the quaternized resins can also be applied to the goods, which is to be treated, is padded.
  • Blocking generally uses aqueous solutions of the benzylated resin in a concentration of 1 to 50 g / l, preferably 2.5 to 15 g / l.
  • the cellulose fiber materials dyed with reactive dyes are aftertreated with the benzylated, cationic resins, they are rinsed well with water, expediently 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 made from dimethylamine and epichlorohydrin are used, annoying failures occur in the aftertreatment liquor.
  • the aftertreatment according to the invention can be carried out in the temperature range from 5 to 100 ° C. and is carried out in a procedure analogous to an exhaust process, preferably at temperatures from 40 to 70 ° C.
  • 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. Obtained in this way dyeings which, relative to satisfy the Wasserechthei t the strict requirements which are imposed on dyes in practice. The light fastness and fastness to rubbing of the dyeings is practically not deteriorated by the aftertreatment according to the invention.
  • the textile material containing cellulose fibers can be rinsed. Then it is dried.
  • Resin 1 (condensation product of methylamine and epichlorohydrin)
  • the resin has a viscosity of 350 mPa.s (20 ° C, D k : 74s- 1 ), a chlorine content of 2.22 mmol / g and a refractive index of nD 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 mPa.s (measured at 20 ° C.). (D k : 26.4 s- 1 ), a refractive index of 1.4546 and a pH of 4.0.
  • Knitwear made of cotton is dyed, based on the goods, 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.
  • 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.
  • 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 aftertreated with a conventional anionic or nonionic detergent becomes. For this it is difficult to determine the grade 3 for water justice.
  • the non-fixed 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.
  • a cotton knitted fabric 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.
  • red dye of the formula 3% dyeing on knitted cotton fabric is produced by dyeing in a liquor ratio of 1:20 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. within 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.
  • 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 2144.8% 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.
  • the ironing test shows that the accompanying fabric on the untreated yarn (sample a) is heavily stained. Treatment c) can reduce bleeding, but it cannot be prevented. Bleeding of the accompanying tissue is prevented only by treatment b).
  • 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 x 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 the resin and had a pH of about 7.
  • an undyed accompanying fabric made from cotton calico is not bled on.

Abstract

1. A process for the aftertreatment of a reactive dyeing on a textile material containing cellulose fibres, in which the dyed textile material is rinsed with water, aftertreated with an aqueous solution of a cationic condensate at from 5 to 100 degrees C and then rinsed again with water, wherein the cationic condensate used is a water-soluble, quaternized resin which is obtainable a) by condensation of methylamine and epichlorohydrin or b) by heating triethanolamine and/or triisopropanolamine in the presence of an acidic catalyst and has been reacted with from 0.25 to 1 mole of benzyl chloride per mole of amine in the condensate.

Description

Cellulosefasern enthaltende Fasermaterialien, die mit Reaktivfarbstoffen gefärbt sind, werden in der Praxis meistens einer kochenden alkalischen Wäsche in Gegenwart von Tensiden unterworfen, um den nicht auf dem Gewebe fixierten Farbstoff zu entfernen. Mit Hilfe dieser Verfahrensweise erhält man gefärbte Cellulosefasermaterialien, die zwar ausreichende Waschechtheiten aufweisen, jedoch bezüglich der Wasserechtheit, der Bügelechtheit und auch der Schweissechtheit verbesserungsbedürftig sind.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.

Aus der DE-A-2 747 358 ist ein Verfahren zur Nachbehandlung von Cellulosefasermaterialien bekannt, die mit Reaktivfarbstoffen gefärbt sind, bei dem man die Fasermaterialien mit einer wässrigen Lösung von sekundäre und/oder tertiäre Aminogruppen enthaltenden Polyaminen, Polyamiden, Polyurethanen und/oder Polyharnstoffen behandelt. Mit Hilfe einer solchen Nachbehandlung werden die Nassechtheitseigenschaften von Reaktivfärbungen auf Cellulose verbessert, jedoch ist eine weitere Steigerung des Echtheitsniveaus der nachbehandelten Färbungen erwünscht, insbesondere der Lichtechtheit und der Trockenreibechtheit.DE-A-2 747 358 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 treated. With 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 lightfastness and the dry rubbing fastness.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Nachbehandlung von Reaktivfärbungen auf Cellulosefasern enthaltenden textilen Materialien zur Verfügung zu stellen, bei dem man gefärbte textile Materialien mit hohen Nassechtheiten erhält, deren Lichtechtheit und Reibechtheit gegenüber einem in üblicher Weise nachgewaschenen gefärbten Material praktisch nicht verschlechtert sind.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 colored 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.

Die Aufgabe wird erfindungsgemäss mit einem Verfahren zur Nachbehandlung von Reaktivfärbungen auf Cellulosefasern enthaltenden textilen Materialien, bei dem die gefärbten textilen Materialien mit Wasser gespült, mit wässrigen Lösungen kationischer Kondensationsprodukte bei Temperaturen von 5 bis 100°C nachbehandelt und danach nochmals mit Wasser gespült werden, dadurch gelöst, dass man als kationische Kondensationsprodukte wasserlösliche, quaternierte Harze einsetzt, die durch Kondensation von

  • 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 one uses water-soluble, quaternized resins 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.

Die Cellulosefasern enthaltenden textilen Materialien können in Form von Fasern, Garnen, Geweben oder anderen Stückwaren vorliegen. Bei den Cellulosefasern handelt es sich beispielsweise um Baumwolle, Leinen oder Zellwolle. Die textilen Materialien, die erfindungsgemäss nachbehandelt werden, können allein aus Cellulosefasern bestehen oder Cellulosefasern gegebenenfalls in Mischung mit synthetischen Fasern, wie Polyamid- Polyacrylnitril- oder Polyester-Fasern enthalten.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.

Die Cellulosefasern werden mit den handelsüblichen Reaktivfarbstoffen in bekannterweise gefärbt, z.B. bei 20 bis 100°C nach dem Ausziehverfahren oder bei Raumtemperatur nach dem Kaltverweilverfahren. Im Anschluss an das Färben wird das textile Material zunächst mit kaltem Wasser gespült, danach ein- bis zweimal mit heissem Wasser (70-100°C) und gegebenenfalls ein weiteres Mal mit Wasser einer Temperatur von 60 bis 80°C gereinigt.The cellulose fibers are known to be dyed 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 (70-100 ° C) and, if necessary, once more with water at a temperature of 60 to 80 ° C.

Erst danach wird das mit den Reaktionsfarbstoffen gefärbte Cellulosefasern enthaltende textile Material mit den als Nachbehandlungsmittel einzusetzenden kationischen benzylierten Harzen in wässriger Lösung behandelt.Only then is the textile material containing the cellulose fibers dyed with the reaction dyes treated with the cationic benzylated resins to be used as aftertreatment agents in aqueous solution.

Die erfindungsgemäss zu verwendenden kationischen Kondensationsprodukte gemäss a) werden durch Kondensation von Methylamin und Epichlorhydrin im Molverhältnis 1:0,8 bis 1 hergestellt. Die Kondensation von Methylamin und Epichlorhydrin ist bekannt und erfolgt in dem Temperaturbereich von 30 bis 90°C, vorzugsweise 40 bis 80°C. Die Kondensation wird in wässriger oder alkoholischer Lösung bei einem Feststoffgehalt der Lösung von üblicherweise 20 bis 60 Gew.-% durchgeführt. Als alkoholische Lösungsmittel verwendet man beispielsweise Ethylenglykol, Propylenglykol, Diglykol und/ oder Neopentylglykol. Die Kondensation erfolgt in dem pH-Bereich von 8 bis 12, vorzugsweise 8 bis 9. Für die Einstellung des pH-Werts bei der Kondensation verwendet man gegebenenfalls Basen, wie Natronlauge, Kalilauge, Natriumcarbonat, Kalziumoxid, Kalziumhydroxid, Bariumoxid oder Bariumhydroxid. Falls Methylamin bei der Kondensation im Überschuss eingesetzt wird, stellt sich aufgrund der Basizität des Methylamins ein pH-Wert im alkalischen Bereich ein. Die Kondensation wird so weit geführt, dass wasserlösliche Produkte entstehen, die in 20%iger wässriger Lösung bei einer Temperatur von 20°C eine Viskosität von mindestens 300 mPa.s haben.The cationic condensation products according to a) to be used according to the invention are prepared by condensing 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 at 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 barium hydroxide are optionally used to adjust the pH. If methylamine is used in excess in the condensation, a pH in the alkaline range is established due to the basicity of the methylamine. The condensation is carried out to such an extent 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.

Die erfindungsgemäss zu verwendenden kationischen Kondensationsprodukte gemäss b), die durch Erhitzen von Triethanolamin und/oder Triisopropanoiamin in Gegenwart von sauren Katalysatoren bei Temperaturen von normalerweise 120 bis 280°C erhältlich sind, sind ebenfalls bekannte Verbindungen, vgl. DE-B-1 127 084 und DE-B-1 243 874. Als saure Katalysatoren verwendet man beispielsweise Ameisensäure, Oxalsäure sowie die Salze und Ester dieser Säuren, phosphorige Säure bzw. deren Ammonium- und Aminsalze, Halogenide, Di- und Triester der phosphorigen Säure, Amide der phosphorigen Säure, Esteramide oder phosphonige Säure bzw. deren Halogenide, Ester, Amide oder Esteramide. Die Kondensation von Triethanolamin, Triisopropanoiamin oder Gemischen der genannten Verbindungen wird vorzugsweise in Gegenwart von phosphoriger Säure bzw. unterphosphoriger Säure durchgeführt. Die sauren Katalysatoren werden in einer Menge von normalerweise 0,1 bis 1,0 Gew.-%, bezogen auf das zu kondensierende Hydroxyalkylamin, eingesetzt. Man erhält auf diese Weise die Kondensationsprodukte b), die 100%ig, bei einer Temperatur von 20°C eine Viskosität von mindestens 40.000 mPa.s, vorzugsweise 40.000 bis 60.000 mPa.s haben.The cationic condensation products according to b) to be used according to the invention, which are obtainable by heating triethanolamine and / or triisopropanoiamine in the presence of acidic catalysts at temperatures of normally 120 to 280 ° C., are also known compounds, cf. DE-B-1 127 084 and DE-B-1 243 874. Examples of acidic catalysts used are formic acid, oxalic acid and the salts and esters of these acids, phosphorous acid or its ammonium and amine salts, halides, di- and triesters phosphorous acid, amides of phosphorous acid, ester amides or phosphonous acid or their halides, esters, amides or ester amides. The condensation of triethanolamine, triisopropanoiamine 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 normally 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.

Die oben beschriebenen wasserlöslichen kationischen Kondensationsprodukte a) und b) werden in einer zweiten Reaktionsstufe quaternisiert, wobei man, jeweils bezogen auf 1 Mol Amin im Kondensationsprodukt a) bzw. b), 0,25 bis 1 Mol, vorzugsweise 0, bis 1 Moi Benzylchlorid einsetzt. Die Quaternisierung erfolgt in wässrigem, vorzugsweise in wässrig-alkoholischem Medium bei Temperaturen von 60 bis 100°C, kann jedoch auch bei höheren Temperaturen vorgenommen werden, wobei dann jedoch unter Druck gearbeitet werden muss. Die Umsetzung der Kondensationsprodukte a) und b) kann in Gegenwart von Alkoholen als Lösungsvermittler durchgeführt werden. Die wässrigen bzw. alkoholischen Lösungen der benzylierten Kondensationsprodukte a) und b) können direkt zur Nachbehandlung von Reaktivfärbungen auf Cellulosefasern enthaltende textile Materialien verwendet werden. Die Viskosität der mit Benzylchlorid umgesetzten Kondensationsprodukte a) und b) beträgt in 20%iger wässriger Lösung bei 20°C mindestens 6 mPa.s und liegt vorzugsweise in dem Bereich von 8 bis 200 mPa.s.The water-soluble cationic condensation products a) and b) described above are quaternized in a second reaction step, wherein 0.25 to 1 mol, preferably 0 to 1 mol, of benzyl chloride are used, based in each case on 1 mol of amine in the condensation product a) or b). The quaternization is carried out 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 it is then necessary to work under pressure. 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.

Die Nachbehandlung der mit Reaktivfarbstoffen gefärbten Cellulosefasermaterialien, die gegebenenfalls in Mischung mit anderen Fasern vorliegen können, erfolgt mit einer wässrigen Flotte der benzylierten Kondensationsprodukte a) bzw. b) diskontinuierlich in Färbeapparaten oder kontinuierlich für Kardenband in Lisseusen, oder Flächengut auf Foulards oder Breitwaschanlagen. Die diskontinuierliche Nachbehandlung der gefärbten Materialien mit den wässrigen Flotten dauert im allgemeinen 5 bis 30 min. Die Konzentration der wasserlöslichen quatären Harze in der Nachbehandlungsflotte beträgt 0,1 bis 5, vorzugsweise 0,25 bis 2 g/I. Das Flottenverhältnis liegt in dem Bereich von 1:5 bis 50, vorzugsweise 1:10 bis 20. Die Nachbehandlungsflotte hat einen pH-Wert in dem Bereich von 4 bis 11, vorzugsweise 5 bis 8. Die quaternierten Harze können jedoch auch auf die Ware, die nachbehandelt werden soll, aufgeklotzt werden.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 apparatuses a) or b) in dyeing machines or continuously for card sliver in lisseuses, or area material on foulards or wide-wash systems. 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.

Beim Klotzen verwendet man im allgemeinen wässrige Lösungen des benzylierten Harzes in einer Konzentration von 1 bis 50 g/I, vorzugsweise 2,5 bis 15 g/I.Blocking generally uses aqueous solutions of the benzylated resin in a concentration of 1 to 50 g / l, preferably 2.5 to 15 g / l.

Bevor die mit Reaktivfarbstoffen gefärbten Cellulosefasermaterialien mit den benzylierten, kationischen Harzen nachbehandelt werden, werden sie gut mit Wasser gespült, zweckmässigerweise zunächst mindestens einmal mit kaltem Wasser und anschliessend mindestens einmal mit Wasser einer Temperatur von 70 bis 100°C. Die vom Textilgut ausgewaschenen hydrolisierten Reaktivfarbstoffe ergeben in Gegenwart der erfindungsgemäss zu verwendenden Produkte keine Ausfällungen. Verwendet man dagegen Kondensationsprodukte aus Dimethylamin und Epichlorhydrin, so kommt es in der Nachbehandlungsflotte zu störenden Ausfällen.Before the cellulose fiber materials dyed with reactive dyes are aftertreated with the benzylated, cationic resins, they are rinsed well with water, expediently 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 made from dimethylamine and epichlorohydrin are used, annoying failures occur in the aftertreatment liquor.

Die erfindungsgemässe Nachbehandlung kann in dem Temperaturbereich von 5 bis 100°C vorgenommen werden und erfolgt in einer einem Ausziehverfahren analogen Verfahrensweise vorzugsweise bei Temperaturen von 40 bis 70°C. Man kann auch so verfahren, dass das mit den Reaktivfarbstoffen eingefärbte Cellulosematerial zuerst mit kaltem und heissem Wasser ausgespült, dann mit der wässrigen Lösung des benzylierten Harzes nahe Siedetemperatur behandelt und anschliessend mit Wasser gespült wird. Das erfindungsgemäss nachbehandelte Cellulosefasern enthaltende Textilmaterial zeigt keine Farbaufhellungen, so dass auch bei Kombinationsfärbungen keine Farbtonverschiebungen resultieren. Man erhält auf diese Weise Färbungen, die bezüglich der Wasserechtheit den strengen Anforderungen, die an Färbungen in der Praxis gestellt werden, genügen. Die Lichtechtheit und Reibechtheit der Färbungen wird durch die erfindungsgemässe Nachbehandlung praktisch nicht verschlechtert. Im Anschluss an die erfindungsgemässe Nachbehandlung kann das Cellulosefasern enthaltende Textilmaterial gespült werden. Danach wird es getrocknet.The aftertreatment according to the invention can be carried out in the temperature range from 5 to 100 ° C. and is carried out in a procedure analogous to an exhaust process, preferably at temperatures from 40 to 70 ° C. One can also proceed in such a way 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. Obtained in this way dyeings which, relative to satisfy the Wasserechthei t the strict requirements which are imposed on dyes in practice. 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.

Die in den Beispielen angegebenen Teile sind Gewichtsteile, die Angaben in Prozent beziehen sich auf das Gewicht. Die Viskositäten wurden in einem Rotationsviskosimeter (Haake, Rotavisco) gemessen. Als benzylierte kationische Harze wurden folgende Produkte verwendet: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:

Harz 1 (Kondensationsprodukt aus Methylamin und Epichlorhydrin)Resin 1 (condensation product of methylamine and epichlorohydrin)

606 g einer 40,9%igen wässrigen Methylaminlösung (8 Mol) werden mit 636 g Wasser verdünnt und bei 20 bis 40°C unter Kühlung innerhalb von 30 Minuten mit 333 g Epichlorhydrin (3,6 Mol) und 288 g 50%iger wässriger Natronlauge versetzt. Sobald die exotherme Reaktion abgeklungen ist, werden weitere 348 g Epichlorhydrin (3,76 Mol) innerhalb von 30 Minuten zugetropft und die Temperatur hierbei von 40 auf 90°C angehoben. Nach beendeter Epichlorhydrinzugabe wird 1 Stunde bei 90°C gehalten, 144 g 50%ige Natronlauge zugesetzt und weitere 2 Stunden bei 90°C kondensiert. Anschliessend wird auf 40°C gekühlt und 810 g Wasser und 144 g Natronlauge zugesetzt.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 dropwise over the course of 30 minutes and the temperature is raised from 40 to 90.degree. 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.

Das Harz hat eine Viskosität von 350 mPa.s (20°C, Dk: 74s-1) einen Chlorgehalt von 2,22 mMol/g und einen Brechungsindex von nD 20: 1,393.The resin has a viscosity of 350 mPa.s (20 ° C, D k : 74s- 1 ), a chlorine content of 2.22 mmol / g and a refractive index of nD 20: 1.393.

3300 g dieses Methylamin-Epichlorhydrinkondensationsproduktes werden mit 1620 Diglykol und 65 g 50%iger Natronlauge versetzt, auf 60 bis 70°C erwärmt, bei dieser Temperatur innerhalb von 0,5 Stunden 1008 g Benzylchlorid zugetropft und dann 3 Stunden bei 80°C gerührt. Es wird mit 53 g (99%iger) Ameisensäure auf pH 4,0 gestellt, mit 2459 g Diglykol verdünnt und auf Raumtemperatur gekühlt. Das kationische Harz zeigt einen Chloridgehalt von 1,83 mMoi/g, eine Säurezahl (alkoholische KOH) von 0,30 mMol/g, eine Viskosität (Haake Rotavisco) von 150 mPa.s (bei 20°C gemessen). (Dk: 26,4 s-1), einen Brechungsindex von 1,4546 und einen pH-Wert von 4,0.3300 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 mPa.s (measured at 20 ° C.). (D k : 26.4 s- 1 ), a refractive index of 1.4546 and a pH of 4.0.

Harz 2 (kondensiertes Triethanolamin)Resin 2 (condensed triethanolamine)

1790 g Triethanolamin (12 Mol) und 12 g hypophosphorige Säure (H3P02, 50%ig wässrig) werden in einem Rektionsgefäss mit Rühr- und Destillationseinrichtung unter Stickstoff auf 230°C erwärmt. Innerhalb von 4 bis 5 Stunden steigt die Viskosität der Reaktionslösung unter Wasserabspaltung auf 42.000 bis 44.000 mPa.s (gemessen bei 20°C, Dk 12 s-1 in einem Kegel-Platte-Rotationsviskosimeter). Es werden 1610 g Polyaminopolyether erhalten. Aminzahl: 7,44 mMol/g.1790 g of triethanolamine (12 mol) and 12 g of hypophosphorous acid (H 3 P0 2 , 50% aqueous) are heated to 230 ° C. in a reaction vessel with a stirring and distillation device under nitrogen. Within 4 to 5 hours the viscosity of the reaction solution rises to 42,000 to 44,000 mPa.s 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 dieses Triethanolaminpolyethers werden im 2880g Wasser versetzt, auf 60 bis 70°C erwärmt und dann innerhalb einer Stunde bei 80°Cmit 1386 g Benzylchlorid quaterniert. Man lässt 3 Stunden bei 80°C nachreagieren und kühlt dann auf Raumtemperatur. Chloridgehalt der Lösung: 1,92 mMol/g. Viskosität (Rotavisco v. Haake): 140 mPa.s (20°C; Dk: 76,8 s-1).1480 g of this triethanolamine polyether are added to 2880 g of water, heated to 60 to 70 ° C and then quaternized with 1386 g of benzyl chloride at 80 ° C 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 mPa.s (20 ° C; D k : 76.8 s-1).

Beispiel 1example 1

Maschenware aus Baumwolle wird, bezogen auf die Ware, mit 5% des orangefarbenen Reaktivfarbstoffes der Color Index Nr. 18260 im Flottenverhältnis 1:20 mit einer Flotte gefärbt, die ausser Farbstoff 60 g/I Natriumchlorid, 9 g/I Natriumcarbonat und 1 g/l Natriumbicarbonat enthält. Nach einer Färbedauer von 30 min wird die Flotte abgelassen, das Material dann mit kaltem Wasser im Flottenverhältnis 1:20 gespült, die Spülflotte abgelassen und das Material dann 10 min mit Wasser bei 95°C behandelt. Das Wasser wird wiederum abgelassen und das gefärbtetextile Material mit einer wässrigen Lösung behandelt, die 2 g/I des Harzes 1 enthält. Die Nachbehandlung mit der wässrigen Lösung des Harzes 1 beträgt 10 min bei Siedetemperatur. Der pH-Wert der Flotte wird auf 5 bis 6 eingestellt. Nach der 10minütigen Behandlung ist die ursprünglich farblose Flotte deutlich angefärbt. Sie wird abgelassen und das damit nachbehandelte Gut mit kaltem Wasser gespült und anschliessend getrocknet.Knitwear made of cotton is dyed, based on the goods, 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. After a dyeing time of 30 minutes, 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.

Man erhält eine Färbung, die bei der Wasserechtheit schwer (nach DIN 54 006, Anbluten des Baumwollbegleitgewebes) die Note 4 bis 5 erreicht und damit um 1, 5 Noten besser zu beurteilen ist als eine Färbung, die mit einem üblichen anionischen oder nichtionischen Waschmittel nachbehandelt wird. Hierfür ermittelt man für die Wasserechtheit schwer die Note 3.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 aftertreated with a conventional anionic or nonionic detergent becomes. For this it is difficult to determine the grade 3 for water justice.

Die Trockenreibechtheiten (nach DIN 54 021) und die Lichtechtheiten nach Xenotest-Beleuchtung (DIN 54 004) sind bei dem erfindungsgemäss nachbehandelten Material praktisch nicht verändert. Ähnliche Verbesserungen wie bei der Wasserechtheit werden auch erhalten, wenn man die nasse Färbung zwischen zwei Gewebestücken aus Baumwolle in standardisierter Weise nach dem im folgenden beschriebenen Bügeltest trockenbügelt.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 in accordance with 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.

BügeltestIroning test

In der Praxis wird häufig der Endpunkt eines Nachwaschprozesses bei einer Reaktivfärbung in der Weise geprüft, dass man ein Stück des gefärbten noch nicht getrockneten Materials zwischen zwei angefeuchtete weisse Baumwollgewebe legt und diese «Sandwiches» bis zur Trockene bügelt.In practice, the end point of a post-washing process for reactive dyeing is often checked by placing a piece of the dyed, not yet dried material between two damp white cotton fabrics and ironing these "sandwiches" to dryness.

Durch diese Behandlung wandern die nicht fixierten Farbstoffe vom gefärbten auf das weisse Material. Die Prüfmethode ist sehr empfindlich, da dabei die geringsten Mengen nicht fixierter Farbstoffe das Weissmaterial anschmutzen.As a result of this treatment, the non-fixed 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.

Die Färbungen werden diesem Bügeltest unterzogen. Die «Sandwiches» werden 2 x je 30 s bei 180°C in der Bügelmaschine gepresst (Siemens Heimbügler Spezial) und anschliessend bei laufender Maschine getrocknet.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.

Es werden ähnliche Ergebnisse erzielt wie bei der Wasserechtheit schwer. Das gleiche Resultat wird erhalten, wenn man anstelle der Maschenware ein Baumwollgewebe verwendet.Similar results are achieved as with water justice. The same result is obtained if a cotton fabric is used instead of the knitted fabric.

Beispiel 2Example 2

Eine Baumwollmaschenware wird wie im Beispiel 1 beschrieben gefärbt und anschliessend mit kaltem und heissem Wasser gespült. Die Ware wird dann mit einer wässrigen Lösung nachbehandelt, die 2 g/l des Harzes 2 gelöst enthält. Die Nachbehandlung erfolgt bei 100°C innerhalb von 10 min. Die Ware wird dann einmal mit kaltem Wasser gespült und getrocknet.A cotton knitted fabric 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.

Bei der Prüfung der Wasserechtheit schwer (nach DIN 54 006, Anbluten des Baumwollbegleitgewebes) wird die Note 4 bis 5 erreicht.When testing the water fastness difficult (according to DIN 54 006, staining of the cotton fabric), the grade 4 to 5 is achieved.

Beispiel 3Example 3

Unter Verwendung des roten Farbstoffs der Formel

Figure imgb0001
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/I Natriumchlorid und 20 g/l Natriumcarbonat enthält. Die Ware wird in dieser Flotte innerhalb von 40min 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
Figure imgb0001
 3% dyeing on knitted cotton fabric is produced by dyeing in a liquor ratio of 1:20 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. within 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.

Lagertman dieerfindungsgemäss nachbehandelte Ware 3 Tage bei 80°C in gesättigter Feuchtigkeit (Tropentest), so tritt danach keine Verschlechterung der Wasserechtheit schwer ein.If the goods treated 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.

Beispiel 4Example 4

In einem Stranggarnfärbeapparat werden 80 kg genetztes mercerisiertes Baumwollgarn in 1000 1 Farbflotte, die 1,04 kg des gelben Reaktiv-Farbstoffes der Formel 5

Figure imgb0002
und 1,6 kg des roten Reaktiv-Farbstoffes der Formel
Figure imgb0003
in handelsüblicher Einstellung enthält, wie folgt gefärbt:80 kg of crosslinked mercerized cotton yarn are mixed in 1000 l of dye liquor, the 1.04 kg of the yellow reactive dye of the formula 5, in a strand yarn dyeing apparatus
Figure imgb0002
 and 1.6 kg of the red reactive dye of the formula
Figure imgb0003
 contains in the commercial setting, colored as follows:

Das Färbebad wird innerhalb von 20 Min. auf 95°C aufgeheizt. Nach einer Verweilzeit von 10 Min. bei 95°C werden 30 kg Natriumchlorid zugesetzt und anschliessend die Temperatur weitere 5 Min. bei 95°C gehalten. Innerhalb von 10 Min. wird auf 80°C abgekühlt. Dann werden 4 kg Soda und 2144,8%ige wässrige Natronlauge zugegeben.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 2144.8% aqueous sodium hydroxide solution are added.

Anschliessend wird das Färbebad noch 30 Min. bei 80°C gehalten und dann abgelassen. Gespült wird 10 Min. kalt mit Überlauf.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.

Danach wird zweimal 10 Min. bei 98°C und einmal 10 Minuten bei 70°C gereinigt.Then it is cleaned twice for 10 minutes at 98 ° C. and once for 10 minutes at 70 ° C.

Das Garn wird sodann in 3 Teile geteilt:

  • 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 2 747 358 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 2 747 358 for 10 minutes at boiling temperature with an aqueous solution containing 2%, based on the weight of the yarn, of the condensation product of 1 mol of methyldipropylenetriamine and 0.87 mol Contains epichlorohydrin (21.9%) and has a pH of about 7.

Der Bügeltest ergibt, dass das Begleitgewebe bei dem unbehandelten Garn (Probe a) stark anblutet. Durch die Behandlung c) kann das Anbluten zwar verringert, aber nicht verhindert werden. Nur durch die Behandlung b) wird ein Anbluten des Begleitgewebes verhindert.The ironing test shows that the accompanying fabric on the untreated yarn (sample a) is heavily stained. Treatment c) can reduce bleeding, but it cannot be prevented. Bleeding of the accompanying tissue is prevented only by treatment b).

Beispiel 5Example 5

In einem Overflow-Färbeapparat werden 75 kg gebleichtes Baumwoll-Jersey in 1200 Färbeflotte, die 2,475 kg des scharlachfarbenen Reaktiv-Farbstoffes der Formel

Figure imgb0004
In an overflow dyeing machine, 75 kg of bleached cotton jersey are put into 1200 dyeing liquors, and the 2.475 kg of the scarlet-colored reactive dye of the formula
Figure imgb0004

0,99 kg des roten Reaktionsfarbstoffes der Formel

Figure imgb0005
0.99 kg of the red reaction dye of the formula
Figure imgb0005

und 0,04 kg des blauen Reaktionsfarbstoffes der Formel

Figure imgb0006
jeweils in handelsüblicher Einstellung sowie 20 g/I Soda und 80 g/I Natriumchlorid enthielt, wie folgt gefärbt.and 0.04 kg of the blue reaction dye of the formula
Figure imgb0006
 each contained in a commercial setting and 20 g / l of soda and 80 g / l of sodium chloride, colored as follows.

Zunächst wird 15 Min. bei 25°C gefärbt, dann in 30 Min. auf 50°C erwärmt, und das Färbebad 20 Min. bei dieser Temperatur gehalten. Anschliessend wird in 30 Min. auf 80°C aufgeheizt und in 45 Min. zu Ende gefärbt.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.

Gespült wird 10 Min. kalt, dann 2 x 10 Min. bei Kochtemperatur und anschliessend einmal 10 Min. bei 50°C.Rinsing is cold for 10 minutes, then 2 x 10 minutes at cooking temperature and then once for 10 minutes at 50 ° C.

Danach wird die Ware 10 Minuten bei 60°C mit einer wässrigen Lösung nachbehandelt, die 1,5% des Harzes enthielt und einen pH-Wert von etwa 7 hatte. Bei dem anschliessenden Bügeltest wird ein ungefärbtes Begleitgewebe aus Baumwoll-Kaliko nicht angeblutet.The goods are then aftertreated for 10 minutes at 60 ° C. with an aqueous solution which contained 1.5% of the resin and had a pH of about 7. In the subsequent ironing test, an undyed accompanying fabric made from cotton calico is not bled on.

Claims (5)

1. A process for the aftertreatment of a reactive dyeing on a textile material containing cellulose fibres, in which the dyed textile material is rinsed with water, aftertreated with an aqueous solution of a cationic condensate at from 5 to 100°C and then rinsed again with water, wherein the cationic condensate used is a water-soluble, quaternized resin which is obtainable
a) by condensation of methylamine and epichlorohydrin or
b) by heating triethanolamine and/or triisopropanolamine in the presence of an acidic catalyst and has been reacted with from 0.25 to 1 mole of benzyl chloride per mole of amine in the condensate.
2. A process as claimed in claim 1, wherein the water-soluble, benzylated resin used is obtainable by reacting the condensate a) or b) with from 0.5 to 1 mole of benzyl chloride per mole of amine in the condensate.
3. A process as claimed in claim 1 or 2, wherein the concentration of the water-soluble, benzylated resin in the aqueous solution is from 0.1 1 to 5 g/I and the liquor ratio is from 1:5 to 1:50.
4. A process as claimed in claim 1 or 2, wherein the water-soluble benzylated resin is applied onto the cellulose fiber material by padding with an aqueous solution which contains from 1 to 50 g/I of the resin.
5. A process as claimed in claim 1 or 2 or 3, wherein the dyed textile material is first rinsed at least once with cold water and then rinsed at least once with water at from 70 to 100°C, and the aftertreatment is then carried out from 90 to 100°C.
EP86114237A 1985-10-22 1986-10-15 Process for the aftertreatment of reactive dyeings on cellulosic fibres Expired EP0223064B1 (en)

Priority Applications (1)

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AT86114237T ATE39506T1 (en) 1985-10-22 1986-10-15 POST-TREATMENT OF REACTIVE DYEING ON CELLULOSE FIBERS.

Applications Claiming Priority (2)

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DE19853537458 DE3537458A1 (en) 1985-10-22 1985-10-22 METHOD FOR TREATING REACTIVE COLORING ON CELLULOSE FIBERS
DE3537458 1985-10-22

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EP0223064A1 EP0223064A1 (en) 1987-05-27
EP0223064B1 true EP0223064B1 (en) 1988-12-28

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US4872881A (en) * 1987-06-30 1989-10-10 Mitsubishi Kasei Corporation Mixtures of water-soluble red and yellow or blue reactive dyes and a method of dyeing cellulosic fibers using such dye mixtures
DE3829974A1 (en) * 1988-09-03 1990-03-15 Basf Ag QUATERNATED CONDENSATION PRODUCTS
DE3914381A1 (en) * 1989-04-29 1990-10-31 Basf Ag METHOD FOR TREATING TREATMENTS WITH REACTIVE DYES ON TEXTILE MATERIALS FROM CELLULOSE FIBERS
DE4003243A1 (en) * 1990-02-03 1991-08-08 Basf Ag Use of tri:alkanolamine polyether(s) as demulsifiers in o/w emulsions - obtainable by condensing tri:alkanol:amine(s) in presence of (hypo)phosphorous acid
DE4006255A1 (en) * 1990-02-28 1991-08-29 Basf Ag CONDENSATION PRODUCTS SUITABLE AS EMULGATORS OF OIL-IN-WATER EMULSIONS
US5224963A (en) * 1990-03-03 1993-07-06 Basf Aktiengesellschaft Quaternized condensation products for aftertreating dyed leather
US5573553A (en) * 1992-04-24 1996-11-12 Milliken Research Corporation Method for improving the bleach resistance of dyed textile fiber and product made thereby
CA2116299A1 (en) * 1993-02-24 1994-08-25 Daniel Taylor Mcbride Method for improving the bleach resistance of dyed textile fiber and product made thereby
US20030105753A1 (en) * 2001-11-27 2003-06-05 Judson Lee Expert system for dyeing cotton fabrics with reactive dyes
JP5414679B2 (en) * 2007-10-09 2014-02-12 ビーエーエスエフ ソシエタス・ヨーロピア Use of highly functional multi-branched polyetheramine polyols for coating surfaces
CN103074715B (en) * 2013-01-16 2014-06-25 广东兴泰发展有限公司 Yarn for high-flame-retardant acrylic cotton protective garment plus material and cheese yarn dyeing method and weaving method of yarn

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DE743563C (en) * 1934-11-01 1944-03-31 Sandoz Ag Process for improving the fastness of dyeings with substantive dyes on cellulose fibers against non-alkaline treatment
CH539732A (en) * 1971-07-27 1973-01-31 Sandoz Ag Process for improving the heat resistance of textile dyeings
DE2747358C2 (en) * 1977-10-21 1986-12-04 Bayer Ag, 5090 Leverkusen Process for the aftertreatment of reactive dyeings
JPS60134080A (en) * 1983-12-16 1985-07-17 一方社油脂工業株式会社 Improvement in dyeability of fiber material, cationic fiber reactive product and its producton
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DE3416693A1 (en) * 1984-05-05 1985-11-07 Bayer Ag, 5090 Leverkusen METHOD FOR TREATING CELLULOSIC FIBER MATERIALS

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JPS62104987A (en) 1987-05-15
DE3537458A1 (en) 1987-04-23
DE3661555D1 (en) 1989-02-02
EP0223064A1 (en) 1987-05-27
ATE39506T1 (en) 1989-01-15

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