EP0209787B1 - Process for the after-treatment of dyeings with reactive dyes on cellulosic fibrous materials - Google Patents
Process for the after-treatment of dyeings with reactive dyes on cellulosic fibrous materials Download PDFInfo
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- EP0209787B1 EP0209787B1 EP86109260A EP86109260A EP0209787B1 EP 0209787 B1 EP0209787 B1 EP 0209787B1 EP 86109260 A EP86109260 A EP 86109260A EP 86109260 A EP86109260 A EP 86109260A EP 0209787 B1 EP0209787 B1 EP 0209787B1
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- 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
- 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
- DE-A 3 217 835 discloses a method for improving the fastness properties of a dye or an optical brightener on textile materials made from cellulose fibers, in which, among other things, a textile material dyed or printed with reactive dyes is brought into contact with a post-treatment agent which (a ) a linear or branched polymer which contains, as repeating units, at least two quaternary ammonium groups which are bonded to one another by alkylene or arylene groups as bridge members, (b) optionally an N-methylol derivative of a urea, melamine, guanamine, triacinone, urone, carbamate or acid amide and contains as essential component (c) a catalyst for the crosslinking of N-methylol compounds according to (b) and then carries out a heat treatment in which the dyes are fixed and the cellulose fibers are simultaneously crosslinked (finishing).
- a post-treatment agent which (a ) a linear or branched polymer which contains, as repeating units,
- the present invention is based on the object of providing a process for the aftertreatment of dyeings with reactive dyes on cellulose fiber materials, in which textile materials dyed in deep tones are obtained which do not stain an untreated white cotton accompanying fabric when tested in the ironing test.
- the cellulose fiber materials can be in the form of fibers, yarns, fabrics or other piece goods.
- the fiber materials consist of cotton, linen or rayon.
- the cellulose fiber materials can optionally be in a mixture with synthetic fibers, such as polyamide, polyacrylonitrile or polyester fibers.
- the cellulose fibers are dyed with the commercially available reactive dyestuffs in the customary manner, for example at 20-100 ° C. using the exhaust process or at room temperature using the cold residence process. Following dyeing, the textile material is first rinsed with cold water, then washed twice with hot water (95-100 ° C) and, if necessary, once more with water at a temperature of 60-80 ° C. Only then is the cellulose material dyed with reactive dyes treated with the cationic condensation product to be used as aftertreatment agent in aqueous solution.
- the cationic condensation products to be used according to the invention can be obtained by reacting (a) bis-benzylpiperazine with (b) ethylene chloride, epihalohydrin, propylene chloride, 1,3-dichloro-2-hydroxypropane, bis-epoxy-butane, 1,4-dichlorobutane or their Mixtures in a: b molar ratio of 1: 0.5 to 1.1.
- the condensation of components (a) or (c) with (b) takes place in the pH range from 6.5 to 12, preferably 7 to 10.
- Bases such as. are used for the adjustment of the pH during the condensation Sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, calcium oxide, calcium hydroxide, barium oxide or barium hydroxide. If the compounds of group (a) or (c) are used in excess in the condensation, a pH in the alkaline range is established due to the basicity of these compounds.
- the condensation is carried out in aqueous or alcoholic solution at a solids content of the solution of usually 20-60% by weight and temperatures of 60-100 ° C.
- the alcoholic solvents used are, for example, ethylene glycol, propylene glycol, diglycol and / or neopentyl glycol.
- the water-soluble, not yet quaternized condensation products have a viscosity of at least 500 mPas in 45% aqueous solution at a temperature of 20 ° C.
- Effective cationic aftertreatment agents can be obtained by using the cationic condensation pro products - especially those from piperazine and epichlorohydrin or ethylene chloride - then quaternized with benzyl chloride.
- benzylation of the condensation products from components (c) and (b) 0.15 to 1.0, preferably 0.4 to 0.75 mol of benzyl chloride is used per N equivalent of component (c). This achieves a benzylation of 15-90% of the tertiary and - if present in the condensation product - the secondary nitrogen atoms in the condensation product. Condensation products with secondary and tertiary nitrogen atoms are formed when 1-aminoethylpiperazine or bis-1,4- (aminopropyl) piperazine is used as component (c).
- the benzylation is preferably carried out in an aqueous medium at temperatures of 60-100 ° C.
- Both the condensation reaction and the benzylation of the condensation products can be carried out at temperatures above 100 ° C. under pressure. This results in shorter response times.
- the aqueous or alcoholic solutions of the benzylated condensation products can be used directly as a cationic condensation product for the aftertreatment.
- the viscosity of the cationic condensation products containing benzyl groups is at least 75 mPas and is preferably in the range of 150-400 mPas.
- the aftertreatment of the cellulose fiber materials dyed with reactive dyes is carried out discontinuously in dyeing apparatus or continuously for roving in lissuses, or area material on foulards or wide-wash systems.
- the discontinuous aftertreatment of the colored materials with the aqueous liquors generally takes 5 to 30 minutes.
- the cationic aftertreatment agents are used in an amount of 0.1 to 5, preferably 0.2 to 3% by weight, based on the dry cellulose fiber material.
- the aftertreatment of the dyeing, which had previously been washed well with water, using reactive dyes on cellulose fiber materials is carried out at a temperature of the aqueous solution of 5 to 120 ° C., preferably 30 to 100 ° C.
- 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.
- 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 2 The procedure was as indicated under condensation product 2, but the benzylation was carried out not in ethylene glycol but after adding the same amount of diethylene glycol to the piperazine-epichlorohydrin condensation product. A clear solution of the condensation product 3 was obtained. The viscosity of a 24% solution was 300 mPas at 20 ° C. As with the condensation product 2, 70% of the nitrogen atoms were quaternized.
- the unfixed dyes migrate from the colored to the white material.
- the test method is very sensitive, since the smallest amounts of unfixed dyes stain the white material.
- the dyeings were subjected to this ironing test.
- the "sandwiches” were pressed 2 x 30 s each at 180 ° C in the ironing machine (Siemens Heimbügler special) and then dried while the machine was running.
- 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.
- 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).
- the fleet uptake was 80%.
- the knitted fabric was then dried at 120 ° C.
- Dyeing and aftertreatment were carried out as described in Example 2, but with the exception that the 3000 l dye liquor was 4.8 kg of the turquoise dye of the following formula contained in a commercial setting.
- the ironing test showed that a cotton calico accompanying fabric did not stain.
- an overflow dyeing machine 75 kg of bleached cotton jersey are put into 1200 l of dyeing liquor, the 2.475 kg of the scarlet-colored reactive dye of the formula 0.99 kg of the red reactive dye of the formula and 0.04 kg of the blue reactive dye of the formula each in a commercially available setting and containing 20 g / l of soda and 80 g / l of sodium chloride, dyed as follows: first dyeing at 25 ° C. for 15 minutes, then heating to 50 ° C. in 30 minutes, and then the dye bath for 20 minutes kept at this temperature. The mixture is then heated to 80 ° C. in 30 minutes and finished in 45 minutes.
- Rinsing is cold for 10 minutes, then 2x10 minutes at cooking temperature and then once for 10 minutes at 50 ° C.
- the goods are then aftertreated for 10 minutes at 60 ° C. with an aqueous solution which contained 1.5% of the condensation product 3 (24%) and had a pH of about 7.
- an undyed accompanying fabric made of cotton calico was not bled on.
- Example 4 Staining was carried out as described in Example 4. The colored material was then rinsed three times for 10 minutes at 25 ° C., then once for 10 minutes at the boiling temperature and then with an aqueous solution containing 1.5% of the condensation product 3 and 1.6% soda calc. contained and had a pH of about 10.5, aftertreated. The aftertreatment bath was entered at 40 ° C. and then heated to boiling temperature within 20 minutes. The ironing test showed that the cotton jersey treated in this way showed no bleeding of the accompanying fabric.
- the 5 kg of the red reactive dye of the formula contains in a commercial setting and 70 g / l sodium sulfate, 5 g / l soda and 2 g / l 44.8% aqueous sodium hydroxide solution.
- the material is dyed for 60 minutes at 80 ° C, then cold for 10 minutes, then 2x10 minutes at boiling temperature and then rinsed in the overflow for 10 minutes at 60 ° C.
- the ironing test showed that the accompanying fabric on the untreated cotton jersey (sample a) was heavily stained. Treatment c) reduced bleeding, but could not be prevented. Bleeding of the accompanying tissue was prevented only by treatment b).
- the ironing test shows that the accompanying material stains heavily on the untreated tissue (sample a) and the tissue which has been subjected to treatment b). Bleeding of the accompanying tissue could only be prevented by treatment c).
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
Aus der DE-OS 2 747 358 ist bekannt, Färbungen mit Reaktivfarbstoffen auf Cellulose-Fasermaterialien mit wäßrigen Lösungen von Kondensationsprodukten aus Polyaminen und Epichlorhydrin bei einem pH-Wert der wäßrigen Lösungen zwischen 3,5 und 11 und bei Temperaturen von vorzugsweise 65 bis 100°C nachzubehandeln. Die Anwendungsmengen an kationischen Kondensationsprodukten betragen zwischen 0,5 und 4 Gew.-%, bezogen auf das Trockengewicht des gefärbten Textilguts. Mit Hilfe einer solchen Behandlung werden die Naßechtheitseigenschaften von Reaktivfärbungen auf Cellulose verbessert, jedoch ist eine weitere Steigerung des Echtheitsniveaus der nachbehandelten Färbungen erwünscht.From DE-OS 2 747 358 it is known to dye with reactive dyes on cellulose fiber materials with aqueous solutions of condensation products from polyamines and epichlorohydrin at a pH of the aqueous solutions between 3.5 and 11 and at temperatures of preferably 65 to 100 ° C to treat. The amounts of cationic condensation products used are between 0.5 and 4% by weight, based on the dry weight of the dyed textile goods. With the help of such a treatment, the wet fastness properties of reactive dyeings on cellulose are improved, but a further increase in the fastness level of the aftertreated dyeings is desired.
Aus der DE-A 3 217 835 ist ein Verfahren zur Verbesserung der Echtheitseigenschaften eines Farbstoffes oder eines optischen Aufhellers auf Textilmaterialien aus Cellulosefasern bekannt, bei dem man unter anderem auch ein mit Reaktivfarbstoffen gefärbtes oder bedrucktes Textilmaterial mit einem Nachbehandlungsmittel in Kontakt bringt, das (a) ein lineares oder verzweigtes Polymer, das als wiederkehrende Einheiten wenigstens zwei quaternäre Ammoniumgruppen, die durch Alkylen- oder Arylengruppen als Brückenglieder miteinander verbunden sind, (b) gegebenenfalls ein N-Methylolderivat eines Harnstoffs, Melamins, Guanamins, Triacinons, Urons, Carbamats oder Säureamids und als wesentliche Komponente (c) einen Katalysator für die Vernetzung von N-Methylolverbindungen gemäß (b) enthält und anschließend eine Wärmebehandlung durchführt, bei der eine Fixierung der Farbstoffe und eine gleichzeitige Vernetzung der Cellulosefasern (Veredlung) erzielt wird.DE-A 3 217 835 discloses a method for improving the fastness properties of a dye or an optical brightener on textile materials made from cellulose fibers, in which, among other things, a textile material dyed or printed with reactive dyes is brought into contact with a post-treatment agent which (a ) a linear or branched polymer which contains, as repeating units, at least two quaternary ammonium groups which are bonded to one another by alkylene or arylene groups as bridge members, (b) optionally an N-methylol derivative of a urea, melamine, guanamine, triacinone, urone, carbamate or acid amide and contains as essential component (c) a catalyst for the crosslinking of N-methylol compounds according to (b) and then carries out a heat treatment in which the dyes are fixed and the cellulose fibers are simultaneously crosslinked (finishing).
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Nachbehandlung von Färbungen mit Reaktivfarbstoffen auf Cellulose-Fasermaterialien zur Verfügung zu stellen, bei dem man auch in tiefen Tönen gefärbte textile Materialien erhält, die bei der Prüfung beim Bügeltest ein unbehandeltes weißes Baumwollbegleitgewebe nicht anbluten.The present invention is based on the object of providing a process for the aftertreatment of dyeings with reactive dyes on cellulose fiber materials, in which textile materials dyed in deep tones are obtained which do not stain an untreated white cotton accompanying fabric when tested in the ironing test.
Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß man als Nachbehandlungsmittel ein kationisches Kondensationsprodukt einsetzt, das durch Umsetzung von
- (a) Bis-benzylpiperazin mit
- (b) Ethylenchlorid, Epihalogen-hydrin, Propylenchlorid, 1,3-Dichlor-2-hydroxy-propan, Bis-epoxibutan, 1,4-Dichlorbutan oder deren Gemische im Molverhältnis 1:0,5 bis 1,1 oder durch Umsetzung von
- (c) Piperazin, Bis-1,4-(aminopropyl)-piperazin, 1-Aminoethylpiperazin, 2-Hydroxyethylpiperazin, 1-Methylpiperazin oder deren Gemische
- mit den Verbindungen gemäß (b) im Molverhältnis 1:0,5 bis 1,1 und Benzylierung der Kondensationsprodukte erhältlich ist, wobei man bei der Benzylierung pro Äquivalent Stickstoff in der Komponente (c) 0,15-1,0 Mol Benzylchlorid einsetzt.
- (a) Bis-benzylpiperazine with
- (b) ethylene chloride, epihalohydrin, propylene chloride, 1,3-dichloro-2-hydroxypropane, bis-epoxybutane, 1,4-dichlorobutane or mixtures thereof in a molar ratio of 1: 0.5 to 1.1 or by reacting
- (c) piperazine, bis-1,4- (aminopropyl) piperazine, 1-aminoethylpiperazine, 2-hydroxyethylpiperazine, 1-methylpiperazine or mixtures thereof
- is available with the compounds according to (b) in a molar ratio of 1: 0.5 to 1.1 and benzylation of the condensation products, 0.15-1.0 mol of benzyl chloride being used in the component (c) for the equivalent of nitrogen in the benzylation.
Die Cellulose-Fasermaterialien können in Form von Fasern, Garnen, Gewebe oder anderen Stückwaren vorliegen. Die Fasermaterialien bestehen aus Baumwolle, Leinen oder Zellwolle. Die Cellulose-Fasermaterialien können gegebenenfalls in Mischung mit synthetischen Fasern, wie Polyamid-, Polyacrylnitril- oder Polyester-Fasern vorliegen.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.
Die Cellulose-Fasern werden mit den handelsüblichen Reaktivfarbstoffen in üblicher Weise gefärbt, z.B. bei 20-100°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 zweimal mit heißem Wasser (95-100°C) und gegebenenfalls ein weiteres Mal mit Wasser einer Temperatur von 60-80°C gereinigt. Erst danach wird das mit Reaktivfarbstoffen gefärbte Cellulose-Material mit dem als Nachbehandlungsmittel einzusetzenden kationischen Kondensationsprodukt in wäßriger Lösung behandelt.The cellulose fibers are dyed with the commercially available reactive dyestuffs in the customary manner, for example at 20-100 ° C. using the exhaust process or at room temperature using the cold residence process. Following dyeing, the textile material is first rinsed with cold water, then washed twice with hot water (95-100 ° C) and, if necessary, once more with water at a temperature of 60-80 ° C. Only then is the cellulose material dyed with reactive dyes treated with the cationic condensation product to be used as aftertreatment agent in aqueous solution.
Die erfindungsgemäß zu verwendenden kationischen Kondensationsprodukte sind erhältlich durch Umsetzung von (a) Bis-benzylpiperazin mit (b) Ethylenchlorid, Epihalogenhydrin, Propylenchlorid, 1,3-Dichlor-2-hydroxy-propan, Bis-epoxibutan, 1,4-Dichiorbutan oder deren Gemische im Molverhältnis a:b von 1:0,5 bis 1,1.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.
Sie sind außerdem erhältlich durch Umsetzung von (c) Piperazin, Bis-1,4-(aminopropyl)-piperazin, 1-Aminoethylpiperazin, 2-Hydroxyethylpiperazin, 1-Methylpiperazin oder deren Gemische mit den oben angegebenen bifunktionellen Vernetzern gemäß (b) und Benzylierung dieser Kondensationsprodukte, wobei man bei der Benzylierung pro Äquivalent Stickstoff in der Komponente (c) 0,15 bis 1,0 Mol Benzylchlorid einsetzt.They are also obtainable by reacting (c) piperazine, bis-1,4- (aminopropyl) piperazine, 1-aminoethylpiperazine, 2-hydroxyethylpiperazine, 1-methylpiperazine or mixtures thereof with the bifunctional crosslinking agents specified in (b) above and benzylation of these condensation products, 0.15 to 1.0 mol of benzyl chloride being used in the benzylation per equivalent of nitrogen in component (c).
Die Kondensation der Komponenten (a) bzw. (c) mit (b) erfolgt in dem pH-Bereich von 6,5 bis 12, vorzugsweise 7 bis 10. Für die Einstellung des pH-Wertes bei der Kondensation verwendet man gegebenenfalls Basen, wie Natronlauge, Kalilauge, Natriumcarbonat, Calciumoxid, Calciumhydroxid, Bariumoxid oder Bariumhydroxid. Sofern die Verbindungen der Gruppe (a) bzw. (c) im Überschuß bei der Kondensation eingesetzt werden, stellt sich aufgrund der Basizität dieser Verbindungen ein pH-Wert im alkalischen Bereich ein. Die Kondensation wird in wäßriger oder alkoholischer Lösung bei einem Feststoffgehalt der Lösung von üblicherweise 20-60 Gew-% und Temperaturen von 60-100°C durchgeführt. Als alkoholische Lösungsmittel verwendet man z.B. Ethylenglykol, Propylenglykol, Diglykol und/oder Neopentylglykol. Die wasserlöslichen noch nicht quaternierten Kondensationsprodukte haben in 45%iger wäßriger Lösung bei einer Temperatur von 20°C eine Viskosität von mindestens 500 mPas. Wirksame kationische Nachbehandlungsmittel erhält man, wenn man die kationischen Kondensationsprodukte - insbesondere diejenigen aus Piperazin und Epichlorhydrin bzw. Ethylenchlorid - anschließend mit Benzylchlorid quaternisiert.The condensation of components (a) or (c) with (b) takes place in the pH range from 6.5 to 12, preferably 7 to 10. Bases such as. Are used for the adjustment of the pH during the condensation Sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, calcium oxide, calcium hydroxide, barium oxide or barium hydroxide. If the compounds of group (a) or (c) are used in excess in the condensation, a pH in the alkaline range is established due to the basicity of these compounds. The condensation is carried out in aqueous or alcoholic solution at a solids content of the solution of usually 20-60% by weight and temperatures of 60-100 ° C. The alcoholic solvents used are, for example, ethylene glycol, propylene glycol, diglycol and / or neopentyl glycol. The water-soluble, not yet quaternized condensation products have a viscosity of at least 500 mPas in 45% aqueous solution at a temperature of 20 ° C. Effective cationic aftertreatment agents can be obtained by using the cationic condensation pro products - especially those from piperazine and epichlorohydrin or ethylene chloride - then quaternized with benzyl chloride.
Für die Benzylierung der Kondensationsprodukte aus den Komponenten (c) und (b) setzt man pro N-Äquivalent der Komponente (c) 0,15 bis 1,0, vorzugsweise 0,4 bis 0,75 Mol Benzylchlorid ein. Man erreicht damit eine Benzylierung von 15-90% der tertiären und - sofern im Kondensationsprodukt vorhanden - der sekundären Stickstoffatome im Kondensationsprodukt. Kondensationsprodukte mit sekundären und tertiären Stickstoffatomen entstehen, wenn man als Komponente (c) 1-Aminoethylpiperazin oder Bis-1,4-(aminopropyl)-piperazin einsetzt. Die Benzylierung erfolgt vorzugsweise in wäßrigem Medium bei Temperaturen von 60-100°C. Sowohl die Kondensationsreaktion als auch die Benzylierung der Kondensationsprodukte kann bei Temperaturen oberhalb 100°C unter Druck vorgenommen werden. Man erreicht dadurch kürzere Reaktionszeiten. Die wäßrigen bzw. alkoholischen Lösungen der benzylierten Kondensationsprodukte können direkt als kationisches Kondensationsprodukt zur Nachbehandlung verwendet werden. Die Viskosität der Benzylgruppen enthaltenden kationischen Kondensationsprodukte beträgt (gemessen in 24%iger wäßriger Lösung bei einer Temperatur von 20°C) mindestens 75 mPas und liegt vorzugweise in dem Bereich von 150-400 mPas.For the benzylation of the condensation products from components (c) and (b), 0.15 to 1.0, preferably 0.4 to 0.75 mol of benzyl chloride is used per N equivalent of component (c). This achieves a benzylation of 15-90% of the tertiary and - if present in the condensation product - the secondary nitrogen atoms in the condensation product. Condensation products with secondary and tertiary nitrogen atoms are formed when 1-aminoethylpiperazine or bis-1,4- (aminopropyl) piperazine is used as component (c). The benzylation is preferably carried out in an aqueous medium at temperatures of 60-100 ° C. Both the condensation reaction and the benzylation of the condensation products can be carried out at temperatures above 100 ° C. under pressure. This results in shorter response times. The aqueous or alcoholic solutions of the benzylated condensation products can be used directly as a cationic condensation product for the aftertreatment. The viscosity of the cationic condensation products containing benzyl groups (measured in 24% aqueous solution at a temperature of 20 ° C.) is at least 75 mPas and is preferably in the range of 150-400 mPas.
Die Nachbehandlung der mit Reaktivfarbstoffen gefärbten Cellulose-Fasermaterialien, die gegebenenfalls in Mischung mit anderen Fasern vorliegen können, erfolgt mit einer wäßrigen Flotte diskontinuierlich in Färbeapparaten oder kontinuierlich für Kammzug in Lisseusen, oder Flächengut auf Foulards oder Breitwaschanlagen. Die diskontinuierliche Nachbehandlung der gefärbten Materialien mit den wäßrigen Flotten dauert im allgemeinen 5 bis 30 Minuten. Die kationischen Nachbehandlungsmittel werden in einer Menge von 0,1 bis 5, vorzugsweise 0,2 bis 3 Gew.-%, bezogen auf das trockene Cellulose-Fasermaterial eingesetzt. Die Nachbehandlung der zuvor gut mit Wasser ausgewaschenen Färbung mit Reaktivfarbstoffen auf Cellulose-Fasermaterialien wird bei einer Temperatur der wäßrigen Lösung von 5 bis 120°C, vorzugsweise 30 bis 100°C und einem pH-Wert von 4 bis 11, vorzugsweise 5 bis 8 durchgeführt. Der von dem gefärbten Material entfernte Reaktivfarbstoff, der in hydrolysierter Form vorliegt, verbleibt in der Nachbehandlungsflotte und schlägt sich nicht auf dem gefärbten und nachbehandelten Material nieder. Die erfindungsgemäß nachbehandelten mit Reaktivfarbstoffen gefärbten Cellulose-Fasermaterialien zeigen nach der erfindungsgemäßen Behandlung 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. Nach der erfindungsgemäßen Behandlung wird das Cellulose-Fasermaterial gespült und dann getrocknet. Die Trocknungstemperatur hat keinen signifikanten Einfluß auf die Verbesserung der Naßechtheiten.The aftertreatment of the cellulose fiber materials dyed with reactive dyes, which may optionally be in a mixture with other fibers, is carried out discontinuously in dyeing apparatus or continuously for roving in lissuses, or area material on foulards or wide-wash systems. The discontinuous aftertreatment of the colored materials with the aqueous liquors generally takes 5 to 30 minutes. The cationic aftertreatment agents are used in an amount of 0.1 to 5, preferably 0.2 to 3% by weight, based on the dry cellulose fiber material. The aftertreatment of the dyeing, which had previously been washed well with water, using reactive dyes on cellulose fiber materials is carried out at a temperature of the aqueous solution of 5 to 120 ° C., preferably 30 to 100 ° C. and a pH of 4 to 11, preferably 5 to 8 . The reactive dye removed from the dyed material, which is in hydrolyzed form, remains in the aftertreatment liquor and does not deposit on the dyed and aftertreated material. The cellulose fiber materials aftertreated with reactive dyes according to the invention show no color brightening after the treatment according to the invention, so that there are no color shifts even in combination dyeings. In this way, dyeings are obtained which meet the strict requirements placed on dyeings in practice in terms of water fastness. After the treatment according to the invention, the cellulose fiber material is rinsed and then dried. The drying temperature has no significant influence on the improvement in wet fastness.
Die in den Beispielen angegebenen Teile sind Gewichtsteile, die Angaben in Prozent beziehen sich auf das Gewicht der Stoffe. Die Viskositäten wurden mit einem Rotationsviskosimeter gemessen. Als kationische Kondensationsprodukte wurden folgende Harzlösungen verwendet: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:
516 Teile Piperazin (6 Mol) in 644 Teilen Wasser wurden innerhalb von 50 Minuten mit 496,7 Teilen Epichlorhydrin versetzt. Man ließ hierbei die Reaktionstemperatur von 50 auf 88°C ansteigen. Anschließend wurde das Reaktionsgemisch weitere 4 Stunden bei 90 bis 95°C gehalten. Das Reaktionsprodukt hatte dann eine Viskosität von 4400 mPas (20°C) und einen Chloridgehalt von 3,25 mMol/g. Es wurde mit 414 Teilen Wasser versetzt und auf Raumtemperatur gekühlt (Viskosität 270 mPas (20°C)).516 parts of piperazine (6 mol) in 644 parts of water were mixed with 496.7 parts of epichlorohydrin within 50 minutes. The reaction temperature was allowed to rise from 50 to 88 ° C. The reaction mixture was then kept at 90 to 95 ° C. for a further 4 hours. The reaction product then had a viscosity of 4400 mPas (20 ° C) and a chloride content of 3.25 mmol / g. 414 parts of water were added and the mixture was cooled to room temperature (viscosity 270 mPas (20 ° C.)).
1750 Teile dieser Lösung wurden mit 3050 Teilen Propandiol-1,2 und 1050 Teilen Wasser versetzt, 400 Teile 50%ige Natronlauge zugegeben und dann bei 60 bis 70°C 882 Teile Benzylchlorid langsam eingetragen. Nach 5stündiger Reaktionsdauer bei 80°C hatte die klare Lösung einen Chloridgehalt von 1,59 mMol/g, einen pH-Wert von 3,9 und eine Viskosität von 90 mPas (20°C). Der Wirkstoffgehalt der Lösung des Kondensationsproduktes 1 lag bei 21,9%. Die Viskosität einer 24%igen Lösung des Kondensationsproduktes betrug 140 mPas bei 20°C. 70% der Stickstoffatome waren mit Benzylchlorid quaternisiert entsprechend 0,7 Mol Benzylchlorid pro Äquivalent Stickstoff im Piperazin.1750 parts of this solution were mixed with 3050 parts of 1,2-propanediol and 1050 parts of water, 400 parts of 50% sodium hydroxide solution were added and then 882 parts of benzyl chloride were slowly introduced at 60 to 70 ° C. After a reaction time of 5 hours at 80 ° C., the clear solution had a chloride content of 1.59 mmol / g, a pH of 3.9 and a viscosity of 90 mPas (20 ° C.). The active substance content of the solution of the condensation product 1 was 21.9%. The viscosity of a 24% solution of the condensation product was 140 mPas at 20 ° C. 70% of the nitrogen atoms were quaternized with benzyl chloride, corresponding to 0.7 mol of benzyl chloride per equivalent of nitrogen in the piperazine.
1730 Teile des Piperazin-Epichlorhydrin-Kondensationsproduktes, dessen Herstellung unter Kondensationsprodukt 1 beschrieben ist, wurden mit 2560 Teilen Ethylenglykol und 440 Teilen 50%iger wäßriger Natronlauge versetzt. Bei 60 bis 80°C wurden innerhalb 0,5 Stunden 882 Teile Benzylchlorid zugegeben und anschließend 5 Stunden bei 80°C gehalten. Nach Abkühlen auf Raumtemperatur hatte die klare Lösung einen pH-Wert von 4,3, einen Chloridgehalt von 2,05 mMol/g und eine Viskosität von 285 mPas (20°C). Der Wirkstoffgehalt betrug 27,8% an Kondensationsprodukt 2. Die Viskosität einer 24%igen Lösung des Kondensationsproduktes betrug 220 mPas bei 20°C. 70% der Stickstoffatome waren mit Benzylchlorid quaternisiert entsprechend 0,7 Mol Benzylchlorid pro Äquivalent Stickstoff im Piperazin.1730 parts of the piperazine-epichlorohydrin condensation product, the preparation of which is described under condensation product 1, were mixed with 2560 parts of ethylene glycol and 440 parts of 50% strength aqueous sodium hydroxide solution. At 60 to 80 ° C, 882 parts of benzyl chloride were added within 0.5 hours and then kept at 80 ° C for 5 hours. After cooling to room temperature, the clear solution had a pH of 4.3, a chloride content of 2.05 mmol / g and a viscosity of 285 mPas (20 ° C.). The active ingredient content was 27.8% of condensation product 2. The viscosity of a 24% solution of the condensation product was 220 mPas at 20 ° C. 70% of the nitrogen atoms were quaternized with benzyl chloride, corresponding to 0.7 mol of benzyl chloride per equivalent of nitrogen in the piperazine.
Man verfuhr wie unter Kondensationsprodukt 2 angegeben, führte jedoch die Benzylierung nicht in Ethylenglykol, sondern nach Zugabe der gleichen Menge an Diethylenglykol zu dem Piperazin-Epichlorhydrin-Kondensationsprodukt durch. Man erhielt eine klare Lösung des Kondensationsproduktes 3. Die Viskosität einer 24%igen Lösung betrug 300 mPas bei 20°C. Wie beim Kondensationsprodukt 2 wurden 70% der Stickstoffatome quaternisiert.The procedure was as indicated under condensation product 2, but the benzylation was carried out not in ethylene glycol but after adding the same amount of diethylene glycol to the piperazine-epichlorohydrin condensation product. A clear solution of the condensation product 3 was obtained. The viscosity of a 24% solution was 300 mPas at 20 ° C. As with the condensation product 2, 70% of the nitrogen atoms were quaternized.
Um die Naßechtheiten der Färbung zu testen, wurde der Bügeltest durchgeführt.In order to test the wet fastness of the dyeing, the ironing test was carried out.
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 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.
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 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.
Die Färbungen wurden diesem Bügeltest unterzogen. Die "Sandwiches" wurden 2 x je 30 s bei 180°C in der Bügelmaschine gepreßt (Siemens Heimbügler Spezial) und anschließend bei laufender Maschine getrocknet.The dyeings were subjected to this ironing test. The "sandwiches" were pressed 2 x 30 s each at 180 ° C in the ironing machine (Siemens Heimbügler special) and then dried while the machine was running.
In einem Stranggarnfärbeapparat werden 80 kg genetztes mercerisiertes Baumwollgarn in 1000 I Farbflotte, die 1,04 kg des gelben Reaktiv-Farbstoffes der Formel
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 2 I 44,8%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 2 l of 44.8% 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 Min. 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% des Kondensationsproduktes 1 (21,9%ig) enthält und einen pH-Wert von etwa 7 hat.
- c. Der dritte Teil des gefärbten Garns wird gemäß der Lehre der DE-OS 2 747 358 10 Min. bei Kochtemperatur mit einer wäßrigen Lösung nachbehandelt, die 2% des Kondensationsproduktes aus 1 Mol Methyldipropylentriamin und 0,87 Mol Epichlorhydrin (21,9%ig) enthält und einen pH-Wert von etwa 7 hat.
- a. Part of the dyed yarn is dried and subjected to the ironing test.
- b. The second part of the dyed yarn is aftertreated for 20 minutes at 40 ° C. with an aqueous solution which contains 2% of the condensation product 1 (21.9%) and has a pH of about 7.
- c. The third part of the dyed yarn is after-treated according to the teaching of DE-OS 2 747 358 for 10 minutes at boiling temperature with an aqueous solution which comprises 2% of the condensation product from 1 mol of methyldipropylenetriamine and 0.87 mol of epichlorohydrin (21.9%) contains and has a pH of about 7.
Der Bügeltest ergab, daß das Begleitgewebe bei dem unbehandelten Garn (Probe a) stark anblutet. Durch die Behandlung c) konnte das Anbluten zwar verringert, aber nicht verhindert werden. Nur durch die Behandlung b) wurde ein Anbluten des Begleitgewebes verhindert.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).
Auf einem JET-Färbeapparat werden 300 kg Baumwoll-Wirkware in 3000 I Farbflotte, die 4,5 kg des roten Reaktiv-Farbstoffes der Formel
- 4,5 kg m-Nitrobenzolsulfonsaures Natrium,
- 180 kg Natriumchlorid und
- 45 kg Natriumcarbonat
- enthält, 30 Min. bei 80°C gefärbt.
- 4.5 kg of sodium m-nitrobenzenesulfonate,
- 180 kg sodium chloride and
- 45 kg sodium carbonate
- contains, colored at 80 ° C for 30 min.
Gespült wird 10 Min. kalt, dann 2x10 Min. bei Kochtemperatur und anschließend wird geschleudert und getrocknet. Dann wurde das Baumwollgewirke auf dem Foulard mit einer wäßrigen Lösung behandelt, die folgende Zusätze enthielt:
- 10 g/I des Kondensationsproduktes 2 (27,8%ig),
- 4 g/I eines kationischen Weichmachers (Kondensationsprodukt aus Stearinsäure und Aminoethylethanolamin) und
- 10 g/1 eines G18-Fettalkoholoxethylates mit 80 Mol Ethylenoxid
- 10 g / l of the condensation product 2 (27.8%),
- 4 g / l of a cationic plasticizer (condensation product of stearic acid and aminoethylethanolamine) and
- 10 g / 1 of a G 18 fatty alcohol oxyethylate with 80 moles of ethylene oxide
Die Flottenaufnahme betrug 80%. Die Wirkware wurde anschließend bei 120°C getrocknet.The fleet uptake was 80%. The knitted fabric was then dried at 120 ° C.
Der Bügeltest ergab, daß die so behandelte Wirkware im Gegensatz zur unbehandelten Ware kein Anbluten des Begleitgewebes zeigte.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.
Gefärbt und nachbehandelt wurde wie im Beispiel 2 beschrieben, jedoch mit der Ausnahme, daß die 3000 I Farbflotte 4,8 kg des türkisfarbenen Farbstoffes folgender Formel
In einem Overflow-Färbeapparat werden 75 kg gebleichtes Baumwoll-Jersey in 1200 I Färbeflotte, die 2,475 kg des scharlachfarbenen Reaktiv-Farbstoffes der Formel
Gespült wird 10 Min. kalt, dann 2x10 Min. bei Kochtemperatur und anschließend einmal 10 Min. bei 50°C.Rinsing is cold for 10 minutes, then 2x10 minutes at cooking temperature and then once for 10 minutes at 50 ° C.
Anschließend wird die Ware 10 Min. bei 60°C mit einer wäßrigen Lösung nachbehandelt, die 1,5% des Kondensationsproduktes 3 (24%ig) enthielt und einen pH-Wert von etwa 7 hatte. Bei dem anschließenden Bügeltest wurde 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 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.
Gefärbt und gespült wurde wie in Beispiel 4 beschrieben. Nachbehandelt wurde 10 Min. bei Kochtemperatur mit einer wäßrigen Lösung, die 1,5% des Kondensationsproduktes 3 (24%ig) und 1,6% (= 1 g/I) Soda calc. enthielt und einen pH-Wert von etwa 10,5 hatte.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.
Beim anschließenden Bügeltest wurde ein ungefärbtes Begleitgewebe aus Baumwoll-Kaliko nicht angeblutet.During the subsequent ironing test, an undyed accompanying fabric made of cotton calico was not bled on.
Gefärbt wurde wie in Beispiel 4 beschrieben. Das gefärbte Material wurde dann dreimal 10 Min. bei 25°C, anschließend einmal 10 Min. bei Kochtemperatur gespült und danach mit einer wäßrigen Lösung, die 1,5% des Kondensationsproduktes 3 und 1,6% Soda calc. enthielt und einen pH-Wert von etwa 10,5 hatte, nachbehandelt. In das Nachbehandlungsbad wurde bei 40°C eingegangen und dann innerhalb von 20 Min. auf Kochtemperatur aufgeheizt. Der Bügeltest ergab, daß das so behandelte Baumwoll-Jersey kein Anbluten des Begleitgewebes zeigte.Staining was carried out as described in Example 4. The colored material was then rinsed three times for 10 minutes at 25 ° C., then once for 10 minutes at the boiling temperature and then with an aqueous solution containing 1.5% of the condensation product 3 and 1.6% soda calc. contained and had a pH of about 10.5, aftertreated. The aftertreatment bath was entered at 40 ° C. and then heated to boiling temperature within 20 minutes. The ironing test showed that the cotton jersey treated in this way showed no bleeding of the accompanying fabric.
In einem Overflow-Färbeapparat werden 100 kg Baumwoll-Trikot in 2000 I Färbeflotte, die 5 kg des roten Reaktiv-Farbstoffes der Formel
Anschließend wurde der Baumwoll-Trikot in 3 Teile geteilt:
- a) Ein Teil des gefärbten Baumwoll-Trikots wurde getrocknet und dem Bügeltest unterworfen.
- b) Der zweite Teil des gefärbten Baumwoll-Trikots wurde 10 Min. bei Kochtemperatur mit einer wäßrigen Lösung nachbehandelt, die 2% des Kondensationsproduktes 2 (27,8%ig) enthielt und einen pH-Wert von etwa 7 hatte.
- c) Der dritte Teil des gefärbten Baumwoll-Trikots wurde gemäß der Lehre der DE-OS 2 747 358 10 Minuten bei Kochtemperatur mit einer Lösung nachbehandelt, die 2% des Kondensationsproduktes aus 1 Mol Methyldipropylentriamin und 0,87 Mol Epichlorhydrin (27%ig) enthielt und einen pH-Wert von etwa 7 hatte.
- a) Part of the dyed cotton jersey was dried and subjected to the ironing test.
- b) The second part of the dyed cotton jersey was aftertreated for 10 minutes at boiling temperature with an aqueous solution which contained 2% of the condensation product 2 (27.8%) and had a pH of about 7.
- c) The third part of the dyed cotton jersey was after-treated according to the teaching of DE-OS 2 747 358 for 10 minutes at boiling temperature with a solution containing 2% of the condensation product from 1 mol of methyldipropylenetriamine and 0.87 mol of epichlorohydrin (27%) contained and had a pH of about 7.
Der Bügeltest ergab, daß das Begleitgewebe bei dem unbehandelten Baumwoll-Trikot (Probe a) stark anblutete. Durch die Behandlung c) konnte das Anbluten zwar verringert, aber nicht verhindert werden. Nur durch die Behandlung b) wurde ein Anbluten des Begleitgewebes verhindert.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).
Der Bügeltest ergibt, daß das Begleitmaterial bei dem unbehandeltem Gewebe (Probe a) und dem Gewebe, das der Behandlung b) unterworfen wurde, stark anblutet. Nur durch die Behandlung c) konnte ein Anbluten des Begleitgewebes verhindert werden.The ironing test shows that the accompanying material stains heavily on the untreated tissue (sample a) and the tissue which has been subjected to treatment b). Bleeding of the accompanying tissue could only be prevented by treatment c).
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86109260T ATE42591T1 (en) | 1985-07-22 | 1986-07-07 | PROCESS FOR THE POST-TREATMENT OF DYEING WITH REACTIVE DYE ON CELLULOSE FIBER MATERIALS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3526101 | 1985-07-22 | ||
| DE19853526101 DE3526101A1 (en) | 1985-07-22 | 1985-07-22 | METHOD FOR TREATING TREATMENTS WITH REACTIVE DYES ON CELLULOSE FIBER MATERIALS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0209787A2 EP0209787A2 (en) | 1987-01-28 |
| EP0209787A3 EP0209787A3 (en) | 1987-05-06 |
| EP0209787B1 true EP0209787B1 (en) | 1989-04-26 |
Family
ID=6276379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86109260A Expired EP0209787B1 (en) | 1985-07-22 | 1986-07-07 | Process for the after-treatment of dyeings with reactive dyes on cellulosic fibrous materials |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4704132A (en) |
| EP (1) | EP0209787B1 (en) |
| JP (1) | JPS6221883A (en) |
| AT (1) | ATE42591T1 (en) |
| DE (2) | DE3526101A1 (en) |
| DK (1) | DK344686A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5739246A (en) * | 1980-08-15 | 1982-03-04 | Teijin Ltd | Production of extensible fabric having cotton like feeling |
| JPS5739247A (en) * | 1980-08-15 | 1982-03-04 | Teijin Ltd | Spun like fabric |
| JPS5739249A (en) * | 1980-08-15 | 1982-03-04 | Teijin Ltd | Production of raised fabric having cotton like feeling |
| DE3609984A1 (en) * | 1986-03-25 | 1987-10-01 | Bayer Ag | METHOD FOR TREATING FIBER MATERIALS |
| DE3709766A1 (en) * | 1987-03-25 | 1988-10-06 | Hoechst Ag | METHOD FOR ALKALI-FREE DYEING WITH REACTIVE DYES |
| DE3743741A1 (en) * | 1987-12-23 | 1989-07-06 | Basf Ag | POLYMERS CONDITIONING AGENTS FOR THE PRE-TREATMENT OF NON-METAL SURFACES FOR CHEMICAL METALLIZATION |
| DE3829974A1 (en) * | 1988-09-03 | 1990-03-15 | Basf Ag | QUATERNATED CONDENSATION PRODUCTS |
| DE19643281A1 (en) * | 1996-10-21 | 1998-04-23 | Basf Ag | Use of polycationic condensation products as a color-fixing additive for detergents and laundry aftertreatment agents |
| JP3161343B2 (en) * | 1996-10-30 | 2001-04-25 | 株式会社村田製作所 | Filter device |
| AU9389898A (en) | 1997-09-15 | 1999-04-05 | Procter & Gamble Company, The | Laundry detergent and fabric conditioning compositions with oxidized cyclic ami ne based polymers |
| US6228828B1 (en) | 1997-09-15 | 2001-05-08 | The Procter & Gamble Company | Laundry detergent compositions with anionically modified, cyclic amine based polymers |
| US6251846B1 (en) * | 1997-09-15 | 2001-06-26 | The Procter & Gamble Company | Laundry detergent compositions with cyclic amine based polymers to provide appearance and integrity benefits to fabrics laundered therewith |
| US6147183A (en) * | 1997-09-15 | 2000-11-14 | Basf Aktiengesellschaft | Amphoteric amine based polymers having a net cationic charge and process for their production |
| DE112009000457T5 (en) * | 2008-03-07 | 2011-04-28 | Clariant Finance (Bvi) Ltd., Road Town | dyeing auxiliaries |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH1669775A4 (en) * | 1975-12-23 | 1977-06-30 | ||
| DE2747358C2 (en) * | 1977-10-21 | 1986-12-04 | Bayer Ag, 5090 Leverkusen | Process for the aftertreatment of reactive dyeings |
| DE2930738A1 (en) * | 1978-10-26 | 1980-05-08 | Sandoz Ag | Post-treating cellulosic textiles dyed with reactive dyes - with cationic cpds. to improve wet-fastness properties |
| FR2509302A1 (en) * | 1981-03-04 | 1983-01-14 | Vyzk Ustav Zuslechtovaci | QUATERNARY AMMONIUM COMPOUNDS, PROCESS FOR THEIR MANUFACTURE AND USE THEREOF IN TISSUE FINISHING PRACTICES |
| DE3217835A1 (en) * | 1981-05-16 | 1982-12-02 | Sandoz-Patent-GmbH, 7850 Lörrach | Dyeing products and method for aftertreating dyeings |
| DE3225877A1 (en) * | 1982-07-10 | 1984-01-12 | Basf Ag, 6700 Ludwigshafen | METHOD FOR COLORING TEXTILE MATERIALS FROM POLYACRYLNITRILE |
| DE3417240A1 (en) * | 1984-05-10 | 1985-11-14 | Basf Ag, 6700 Ludwigshafen | METHOD FOR TREATING DYED TEXTILE MATERIALS FROM NATURAL OR SYNTHETIC POLYAMIDES |
| DE3417239A1 (en) * | 1984-05-10 | 1985-11-14 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING FELT-RESISTANT EQUIPMENT, WHEREAS DYED WOOL |
-
1985
- 1985-07-22 DE DE19853526101 patent/DE3526101A1/en not_active Withdrawn
-
1986
- 1986-07-07 AT AT86109260T patent/ATE42591T1/en active
- 1986-07-07 DE DE8686109260T patent/DE3663047D1/en not_active Expired
- 1986-07-07 EP EP86109260A patent/EP0209787B1/en not_active Expired
- 1986-07-17 US US06/886,319 patent/US4704132A/en not_active Expired - Fee Related
- 1986-07-18 JP JP61168219A patent/JPS6221883A/en active Pending
- 1986-07-21 DK DK344686A patent/DK344686A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK344686D0 (en) | 1986-07-21 |
| DE3663047D1 (en) | 1989-06-01 |
| US4704132A (en) | 1987-11-03 |
| JPS6221883A (en) | 1987-01-30 |
| DK344686A (en) | 1987-01-23 |
| EP0209787A2 (en) | 1987-01-28 |
| ATE42591T1 (en) | 1989-05-15 |
| EP0209787A3 (en) | 1987-05-06 |
| DE3526101A1 (en) | 1987-01-22 |
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