EP0362139A1 - Process for the photochemical stabilisation of undyed and dyed fibrous polyamide material and mixtures thereof - Google Patents

Process for the photochemical stabilisation of undyed and dyed fibrous polyamide material and mixtures thereof Download PDF

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Publication number
EP0362139A1
EP0362139A1 EP89810714A EP89810714A EP0362139A1 EP 0362139 A1 EP0362139 A1 EP 0362139A1 EP 89810714 A EP89810714 A EP 89810714A EP 89810714 A EP89810714 A EP 89810714A EP 0362139 A1 EP0362139 A1 EP 0362139A1
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Prior art keywords
copper
formula
polyamide
fiber material
copper complex
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EP89810714A
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German (de)
French (fr)
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EP0362139B1 (en
Inventor
Helmut Dr. Huber-Emden
Gerhard Dr. Reinert
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Novartis AG
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Ciba Geigy AG
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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
    • 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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • 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
    • D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6423—Compounds containing azide or oxime groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/924—Polyamide fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/926—Polyurethane fiber

Definitions

  • the present invention relates to a process for the photochemical stabilization of undyed and dyed polyamide fiber material and its blends with other fibers by treating this material with photochemically stabilizing agents based on copper compounds of phenols.
  • fiber reactive bisazomethine copper complexes which e.g. from optionally substituted salicylaldehydes and aliphatic amines. Fiber materials treated with these complexes have high lightfastness properties and, at the concentrations used, no undesirable intrinsic color.
  • the present invention thus relates to a process for the photochemical stabilization of undyed and dyed polyamide fiber material, or its mixtures with other fibers with photochemically stabilizing agents based on copper compounds of phenols, which is characterized in that the polyamide fiber material with fiber-affine, organic copper complex compounds of the reaction products of o-hydroxybenzoyl derivatives of the formula wherein R is hydrogen or C1-C4-alkyl and the OH substituent is in the 3-, 4- or 5-position, treated with aliphatic diamines or hydroxylamine.
  • the polyamide fiber material stabilized photochemically by the present process or its mixtures with other fibers form a further subject of the present invention.
  • Preferred copper complex compounds of the reaction products of o-hydroxybenzoyl derivatives of the formula (1) with aliphatic diamines correspond to the formula where R has the meaning given above and X1 and Y1 each independently represent hydrogen or C1-C4-alkyl.
  • water-insoluble copper complex compounds in which X1 and Y1 are hydrogen and the OH substituent is in the 4- or 5-position, in particular in the 4-position, and that of the formula correspond.
  • Preferred copper complex compounds from the reaction products of o-hydroxybenzoyl derivatives of the formula (1) with hydroxylamine correspond to the formula wherein R has the meaning given above and wherein the hydroxy substituent is in the 4- or 5-position.
  • the copper complex compounds of formula (2) are partly from, for example, M. Calvin, J. Am. Chem. Soc. 68 , p. 949 (1946).
  • the compounds of the formulas (2) and (3) are known and can be obtained in a manner known per se by reacting 2 equivalents of the corresponding OH-substituted o-hydroxybenzoyl derivative with 1 equivalent of the corresponding diamine to give the Schiff base and subsequent metallization with copper salts.
  • the copper complexes of the formula (2) are expediently applied from an aqueous bath, these being used advantageously in an amount such that 5 to 200 ⁇ g, in particular 10 to 100 ⁇ g, copper are added to 1 g polyamide fiber material.
  • the compounds of the formula (2) are expediently used as finely divided dispersions which are obtained by grinding in the presence of customary dispersants.
  • the copper complex compounds of formula (4) are also known. They are obtainable by production processes known per se, which are described, for example, in J. Chem. Soc., P. 314 (1933). These compounds are obtained by reacting the reaction product of hydroxylamine with the corresponding OH-substituted o-hydroxybenzoyl derivative and a copper (II) salt, in particular with a salt of a mineral acid such as copper (II) chloride or copper (II) sulfate in preferably alcoholic, aqueous-alcoholic or aqueous medium.
  • a mineral acid such as copper (II) chloride or copper (II) sulfate in preferably alcoholic, aqueous-alcoholic or aqueous medium.
  • the fiber material can be treated with it before, during or after dyeing.
  • the copper complex is expediently added directly to the dyeing, padding liquor or printing pastes.
  • the dyeing is carried out continuously or batchwise at a temperature of 20 to 130 ° C.
  • the copper complexes can be fixed by steaming or heat at a temperature of 100 to 200 ° C.
  • Synthetic polyamide e.g. Polyamide-6, polyamide-6,6 or also polyamide-12 understood.
  • fiber mixtures made of polyurethane and polyamide are also considered, e.g. Jersey material made of polyamide / polyurethane in a mixing ratio of 70:30.
  • the pure or mixed polyamide material can be in various processing forms, e.g. as fiber, yarn, woven or knitted fabric.
  • light and heat-exposed polyamide material e.g. Is available as a car upholstery fabric or carpet, is particularly suitable for treatment according to the present method.
  • the coloring takes place in the usual way e.g. with metal complex dyes or also with anthraquinone dyes or azo dyes.
  • metal complex dyes or also with anthraquinone dyes or azo dyes.
  • the known types in particular the 1: 2 chromium or 1: 2 cobalt complexes of mono-, disazo or azomethine dyes, which are described in large numbers in the literature, are used as metal complex dyes.
  • dyes from other dye classes are of course also possible, such as Disperse or vat dyes.
  • 5 g of the compounds prepared according to regulation 1 or 2 are mixed with 5 g of the condensation product of naphthalenesulfonic acid and formaldehyde as a dispersant, which is dissolved in 7.5 ml of water, and 20 g of quartz beads (diameter approx. 1 mm) and with a stirrer milled at approx. 1600 revolutions per minute until the particle size is below 3 ⁇ m.
  • the dispersion is separated from the quartz beads using a fine mesh screen and adjusted to 10% of the active substance with water. Stirring in 0.3% carboxymethyl cellulose stabilizes the dispersion.
  • Both compounds are present as formulations with 10% active substance. All nylon patterns are treated in parallel. The treatment is initially carried out for 5 minutes at 50 ° C. Then the temperature with a heating rate of 2 ° C / min. increased to 95 ° C. Treat at this temperature for 60 minutes. It is then cooled to 70 ° C., rinsed warm at 40 ° C. and then cold, centrifuged and dried at 60 ° C. in a forced air oven.
  • the proportion of copper compounds remaining in the fleet is significantly lower, i.e. the wastewater is significantly less polluted.
  • the table also shows the analytically determined remaining copper content on the fiber.
  • the additives in fleets 2-5 are used as 10% dispersions.
  • the Cu content of the finished dyeings described is determined and hot exposures in accordance with DIN 75.202 are carried out to determine the photochemical degradation.

Abstract

Beschrieben wird ein Verfahren zur fotochemischen Stabilisierung von ungefärbtem und gefärbtem Polyamidfasermaterial und dessen Mischungen mit anderen Fasern mit photochemisch stabilisierenden Mitteln auf der Basis von Kupferverbindungen von Phenolen, das dadurch gekennzeichnet ist, dass man das Polyamidfasermaterial mit faseraffinen, organischen Kupferkomplexen der Umsetzungsprodukte von o-Hydroxybenzoylderivaten der Formel <IMAGE> worin R Wasserstoff oder C1-C4-Alkyl bedeutet und der OH-Substituent sich in 3-, 4- oder 5-Stellung befindet, mit aliphatischen Diaminen oder Hydroxylamin behandelt. Die Kupferkomplexverbindungen zeichnen sich durch eine hohe Ausziehrate auf das Polyamidfasermaterial aus, was in ökonomischer Hinsicht wegen des geringeren Produktverbrauches bedeutsam ist.A process is described for the photochemical stabilization of undyed and dyed polyamide fiber material and its mixtures with other fibers with photochemically stabilizing agents based on copper compounds of phenols, which is characterized in that the polyamide fiber material with fiber-affine, organic copper complexes of the reaction products of o-hydroxybenzoyl derivatives of the formula <IMAGE> in which R is hydrogen or C1-C4-alkyl and the OH substituent is in the 3-, 4- or 5-position, treated with aliphatic diamines or hydroxylamine. The copper complex compounds are characterized by a high extraction rate on the polyamide fiber material, which is economically significant because of the lower product consumption.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur fotochemischen Stabilisierung von ungefärbtem und gefärbtem Polyamidfasermaterial und dessen Mischungen mit anderen Fasern, indem man dieses Material mit photochemisch stabilisierenden Mitteln auf der Basis von Kupferver­bindungen von Phenolen behandelt.The present invention relates to a process for the photochemical stabilization of undyed and dyed polyamide fiber material and its blends with other fibers by treating this material with photochemically stabilizing agents based on copper compounds of phenols.

Die Verwendung von Kupfersalzen, wie z.B. Kupfersulfat, zur Verbesserung der Lichtechtheit von Färbungen auf Polyamidfasern mit Metallkomplex­farbstoffen ist allgemein bekannt; verwiesen wird auf den Artikel von I.B. HANES in ADR 3 (1980), Seiten 19 und 20. Anorganische oder organi­sche Kupfersalze haben jedoch vielfach den Nachteil, dass sie nur ungenügend und ungleichmässig auf die Polyamidfaser aufziehen und daher nur in hohen Konzentrationen den gewünschten Effekt erzielen. Normaler­weise können sie nur zur Nachbehandlung und in Diskontinueverfahren eingesetzt werden.The use of copper salts, such as copper sulfate, to improve the lightfastness of dyeings on polyamide fibers with metal complex dyes is generally known; Reference is made to the article by IB HANES in ADR 3 (1980), pages 19 and 20. However, inorganic or organic copper salts often have the disadvantage that they absorb the polyamide fiber insufficiently and unevenly and therefore only achieve the desired effect in high concentrations . Usually they can only be used for post-treatment and in discontinuous procedures.

In der US-A-4,655,783 sind faserreaktive Bisazomethin-Kupferkomplexe beschrieben, die z.B. aus gegebenenfalls substituierten Salicylaldehyden und aliphatischen Aminen erhältlich sind. Mit diesen Komplexen behandelte Fasermaterialien weisen hohe Lichtechtheitseigenschaften und bei den angewandten Konzentrationen keine unerwünschte Eigenfarbe auf.In US-A-4,655,783 fiber reactive bisazomethine copper complexes are described which e.g. from optionally substituted salicylaldehydes and aliphatic amines. Fiber materials treated with these complexes have high lightfastness properties and, at the concentrations used, no undesirable intrinsic color.

Es wurde nun gefunden, dass mit Kupferkomplexverbindungen von Bisazo­methinen und Oximen, die jeweils OH-substituierte Phenylreste aufweisen, eine höhere Ausziehrate als mit den entsprechenden unsubstituierten Verbindungen erzielt wird. Dies ist in ökonomischer Hinsicht bedeutsam, da bei Verwendung dieser Verbindungen deutlich weniger Produkt eingesetzt werden muss.It has now been found that with copper complex compounds of bisazomethines and oximes, each of which has OH-substituted phenyl radicals, a higher extraction rate than with the corresponding unsubstituted ones Connections is achieved. This is important from an economic point of view, since when using these compounds significantly less product has to be used.

Gegenstand vorliegender Erfindung ist somit ein Verfahren zur foto­chemischen Stabilisierung von ungefärbtem und gefärbtem Polyamidfaser­material, oder dessen Mischungen mit anderen Fasern mit photochemisch stabilisierenden Mitteln auf der Basis von Kupferverbindungen von Phenolen, das dadurch gekennzeichnet ist, dass man das Polyamidfaser­material mit faseraffinen, organischen Kupferkomplexverbindungen der Umsetzungsprodukte von o-Hydroxybenzoylderivaten der Formel

Figure imgb0001
worin R Wasserstoff oder C₁-C₄-Alkyl bedeutet und der OH-Substituent sich in 3-, 4- oder 5-Stellung befindet, mit aliphatischen Diaminen oder Hydroxylamin behandelt.The present invention thus relates to a process for the photochemical stabilization of undyed and dyed polyamide fiber material, or its mixtures with other fibers with photochemically stabilizing agents based on copper compounds of phenols, which is characterized in that the polyamide fiber material with fiber-affine, organic copper complex compounds of the reaction products of o-hydroxybenzoyl derivatives of the formula
Figure imgb0001
 wherein R is hydrogen or C₁-C₄-alkyl and the OH substituent is in the 3-, 4- or 5-position, treated with aliphatic diamines or hydroxylamine.

Das nach dem vorliegenden Verfahren photochemisch stabilisierte Polyamid­fasermaterial oder dessen Mischungen mit anderen Fasern bilden einen weiteren Gegenstand der vorliegenden Erfindung.The polyamide fiber material stabilized photochemically by the present process or its mixtures with other fibers form a further subject of the present invention.

Bevorzugte Kupferkomplexverbindungen der Umsetzungsprodukte von o-Hydroxybenzoylderivaten der Formel (1) mit aliphatischen Diaminen entsprechen der Formel

Figure imgb0002
wobei R die oben angegebene Bedeutung hat und X₁ und Y₁ unabhängig voneinander je Wasserstoff oder C₁-C₄-Alkyl bedeuten.Preferred copper complex compounds of the reaction products of o-hydroxybenzoyl derivatives of the formula (1) with aliphatic diamines correspond to the formula
Figure imgb0002
 where R has the meaning given above and X₁ and Y₁ each independently represent hydrogen or C₁-C₄-alkyl.

Im Vordergrund des Interesses stehen wasserunlösliche Kupferkomplexver­bindungen, bei denen X₁ und Y₁ Wasserstoff bedeuten und der OH-Substi­tuent sich in 4- oder 5-Stellung, insbesondere in 4-Stellung befindet und die der Formel

Figure imgb0003
entsprechen.In the foreground of interest are water-insoluble copper complex compounds in which X₁ and Y₁ are hydrogen and the OH substituent is in the 4- or 5-position, in particular in the 4-position, and that of the formula
Figure imgb0003
 correspond.

Bevorzugte Kupfer-Komplexverbindungen aus den Umsetzungsprodukten von o-Hydroxybenzoylderivaten der Formel (1) mit Hydroxylamin entsprechen der Formel

Figure imgb0004
worin R die oben angegebene Bedeutung hat und wobei sich der Hydroxy­substituent in 4- oder 5-Stellung befindet.Preferred copper complex compounds from the reaction products of o-hydroxybenzoyl derivatives of the formula (1) with hydroxylamine correspond to the formula
Figure imgb0004
 wherein R has the meaning given above and wherein the hydroxy substituent is in the 4- or 5-position.

Im Vordergrund des Interesses stehen indessen Kupferkomplexverbindungen, die der Formel

Figure imgb0005
entsprechen.The focus of interest, however, is on copper complex compounds, that of the formula
Figure imgb0005
 correspond.

Die Kupferkomplexverbindungen der Formel (2) sind zum Teil aus z.B. M. Calvin, J. Am. Chem. Soc. 68, S. 949 (1946) bekannt.The copper complex compounds of formula (2) are partly from, for example, M. Calvin, J. Am. Chem. Soc. 68 , p. 949 (1946).

Die Verbindungen der Formeln (2) und (3) sind bekannt und können auf an sich bekannte Weise durch Umsetzung von 2 Aequivalenten des ent­sprechenden OH-substituierten o-Hydroxybenzoylderivates mit 1 Aequi­valent des entsprechenden Diamins zur Schiffschen Base und anschliessende Metallisierung mit Kupfersalzen erhalten werden. Man kann aber auch zunächst den Kupferkomplex des entsprechenden Salicylaldehyds bilden und diesen anschliessend mit dem Diamin zum Kupferkomplex des Bisazomethins der Formel (2) umsetzen.The compounds of the formulas (2) and (3) are known and can be obtained in a manner known per se by reacting 2 equivalents of the corresponding OH-substituted o-hydroxybenzoyl derivative with 1 equivalent of the corresponding diamine to give the Schiff base and subsequent metallization with copper salts. However, one can also first form the copper complex of the corresponding salicylaldehyde and then react it with the diamine to form the copper complex of bisazomethine of the formula (2).

Es ist auch möglich, ohne Isolierung der Zwischenprodukte den ent­sprechenden Salicylaldehyd, das Diamin und das Kupfersalz in einem einzigen Schritt im sogenannten Eintopfverfahren direkt zur Verbindung der Formel (2) umzusetzen. Diese 3 Herstellungsmethoden sind von Pfeiffer in Liebigs Annalen der Chemie, 503, S. 84-130 (1933) beschrieben.It is also possible, without isolating the intermediates, to convert the corresponding salicylaldehyde, the diamine and the copper salt directly to the compound of the formula (2) in a single step in the so-called one-pot process. These 3 production methods are described by Pfeiffer in Liebigs Annalen der Chemie, 503 , pp. 84-130 (1933).

Die Kupferkomplexe der Formel (2) werden zweckmässigerweise aus wässrigem Bad appliziert, wobei diese vorteilhaft in einer Menge eingesetzt werden, dass auf 1 g Polyamidfasermaterial 5 bis 200 µg, insbesondere 10 bis 100 µg Kupfer kommen.The copper complexes of the formula (2) are expediently applied from an aqueous bath, these being used advantageously in an amount such that 5 to 200 μg, in particular 10 to 100 μg, copper are added to 1 g polyamide fiber material.

Die Verbindungen der Formel (2) werden zweckmässig als fein verteilte Dispersionen eingesetzt, die durch Mahlen in Gegenwart üblicher Dis­pergiermittel erhalten werden.The compounds of the formula (2) are expediently used as finely divided dispersions which are obtained by grinding in the presence of customary dispersants.

Die Kupferkomplexverbindungen der Formel (4) sind ebenfalls bekannt. Sie sind nach an sich bekannten Herstellungsverfahren erhältlich, die z.B. im J. Chem. Soc., S. 314 (1933) beschrieben sind. Man erhält diese Verbindungen durch Umsetzung des Reaktionsproduktes von Hydroxylamin mit dem entsprechenden OH-substituierten o-Hydroxybenzoylderivat und einem Kupfer(II)-salz, insbesondere mit einem Salz einer Mineralsäure wie Kupfer(II)chlorid oder Kupfer(II)sulfat in vorzugsweise alkoholischem, wässrig-alkoholischem oder wässrigem Medium.The copper complex compounds of formula (4) are also known. They are obtainable by production processes known per se, which are described, for example, in J. Chem. Soc., P. 314 (1933). These compounds are obtained by reacting the reaction product of hydroxylamine with the corresponding OH-substituted o-hydroxybenzoyl derivative and a copper (II) salt, in particular with a salt of a mineral acid such as copper (II) chloride or copper (II) sulfate in preferably alcoholic, aqueous-alcoholic or aqueous medium.

Werden die Kupferkomplexe zur Stabilisierung von gefärbtem Material verwendet, so kann das Fasermaterial vor, während oder nach der Färbung damit behandelt werden. Zweckmässigerweise wird der Kupferkomplex direkt den Färbe-, Klotzflotten oder Drückpasten zugesetzt. Die Färbung erfolgt kontinuierlich oder diskontinuierlich bei Temperatur von 20 bis 130°C. Bei kontinuierlicher Arbeitsweise kann die Fixierung der Kupferkomplexe durch Dämpfen oder Hitze bei einer Temperatur von 100 bis 200°C erfolgen.If the copper complexes are used to stabilize dyed material, the fiber material can be treated with it before, during or after dyeing. The copper complex is expediently added directly to the dyeing, padding liquor or printing pastes. The dyeing is carried out continuously or batchwise at a temperature of 20 to 130 ° C. In the case of continuous operation, the copper complexes can be fixed by steaming or heat at a temperature of 100 to 200 ° C.

Unter Polyamidmaterial wird synthetisches Polyamid, wie z.B. Polyamid-6, Polyamid-6,6 oder auch Polyamid-12, verstanden. Neben den reinen Poly­amidfasern kommen vor allem auch Fasermischungen aus Polyurethan und Polyamid in Betracht, so z.B. Trikotmaterial aus Polyamid/Polyurethan im Mischungsverhältnis 70:30. Grundsätzlich kann das reine oder gemischte Polyamidmaterial in verschiedenen Verarbeitungsformen vorliegen, wie z.B. als Faser, Garn, Gewebe oder Gewirke.Synthetic polyamide, e.g. Polyamide-6, polyamide-6,6 or also polyamide-12 understood. In addition to the pure polyamide fibers, fiber mixtures made of polyurethane and polyamide are also considered, e.g. Jersey material made of polyamide / polyurethane in a mixing ratio of 70:30. In principle, the pure or mixed polyamide material can be in various processing forms, e.g. as fiber, yarn, woven or knitted fabric.

Vor allem Licht und Hitze ausgesetztes Polyamidmaterial, das z.B. als Autopolsterstoff oder Teppich vorliegt, eignet sich im besonderen Masse dazu, nach dem vorliegenden Verfahren behandelt zu werden.Above all, light and heat-exposed polyamide material, e.g. Is available as a car upholstery fabric or carpet, is particularly suitable for treatment according to the present method.

Die Färbung erfolgt in üblicher Weise z.B. mit Metallkomplexfarbstoffen oder auch mit Anthrachinonfarbstoffen oder Azofarbstoffen. Als Metall­komplexfarbstoffe werden die bekannten Typen, insbesondere die 1:2-Chrom- oder 1:2-Kobaltkomplexe von Mono-, Disazo- oder Azomethinfarbstoffen eingesetzt, die in der Literatur in grosser Zahl beschrieben sind. Neben diesen kommen natürlich auch Farbstoffe aus anderen Farbstoffklassen in Frage, wie z.B. Dispersions- oder auch Küpenfarbstoffe.The coloring takes place in the usual way e.g. with metal complex dyes or also with anthraquinone dyes or azo dyes. The known types, in particular the 1: 2 chromium or 1: 2 cobalt complexes of mono-, disazo or azomethine dyes, which are described in large numbers in the literature, are used as metal complex dyes. In addition to these, dyes from other dye classes are of course also possible, such as Disperse or vat dyes.

Die folgenden Herstellungsvorschriften und Beispiele dienen der Veran­schaulichung der Erfindung. Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente. Die Prozentangaben betreffend die Zusätze der einzelnen Behandlungs- bzw. Färbebäder beziehen sich, wenn nicht anders vermerkt, auf das Fasermaterial.The following preparation instructions and examples serve to illustrate the invention. Parts mean parts by weight and percentages percent by weight. The percentages relating to the additions of the individual treatment or dye baths relate to the fiber material, unless stated otherwise.

Herstellungsvorschriften der Kupferkomplex-VerbindungenManufacturing regulations of copper complex connections Beispiel 1:Example 1:

Eine Lösung von 3,33 g Kupfer(II)acetat·H₂O in 50 ml Dimethylformamid wird bei 60°C zu einer Lösung von 5,0 g des Azomethins der Formel

Figure imgb0006
in 50 ml Dimethylformamid gegeben.A solution of 3.33 g of copper (II) acetate · H₂O in 50 ml of dimethylformamide at 60 ° C to a solution of 5.0 g of the azomethine of the formula
Figure imgb0006
 placed in 50 ml of dimethylformamide.

Anschliessend lässt man abkühlen, verdünnt mit 150 ml Ethanol, filtriert den Niederschlag ab, wäscht nach und erhält nach Trocknung 4,55 g (69 % d.Th.) des Komplexes der Formel

Figure imgb0007
Elementaranalyse berechnet C 48,4 % H 4,6 % N 7,0 % gefunden C 48,3 % H 4,6 % N 7,5 % The mixture is then allowed to cool, diluted with 150 ml of ethanol, the precipitate is filtered off, washed and, after drying, 4.55 g (69% of theory) of the complex of the formula are obtained
Figure imgb0007
 Elemental analysis calculated C 48.4% H 4.6% N 7.0% found C 48.3% H 4.6% N 7.5%

Beispiel 2:Example 2:

6,05 g 2,4-Dihydroxybenzaldoxim werden bei 40°C in 39,5 ml n Natriumhydroxid-Lösung gelöst. Man gibt unter Rühren eine Lösung von 4,93 g CuSO₄·5H₂O in 60 ml Wasser hinzu, rührt bei Raumtemperatur noch 1 Stunde, saugt vom ausgefällten Produkt ab, wäscht mit Wasser nach und erhält nach Trocknung 6,5 g (89,7 % d.Th.) eines dunkeloliven Komplexes der Formel

Figure imgb0008
6.05 g of 2,4-dihydroxybenzaldoxime are dissolved at 40 ° C in 39.5 ml of sodium hydroxide solution. A solution of 4.93 g of CuSO₄ · 5H₂O in 60 ml of water is added with stirring, the mixture is stirred at room temperature for 1 hour, the precipitated product is filtered off with suction, washed with water and, after drying, 6.5 g (89.7% i.e.) a dark olive complex of the formula
Figure imgb0008

Eine Probe der Substanz wird aus einem Dimethylformamid-Wasser-Gemisch (Verhältnis 1:1) umkristallisiert, mit Ethanol gewaschen und getrocknet. Man erhält ein hellbraunes Pulver mit einem Schmelzpunkt von 214°C (Zersetzung). Elementaranalyse berechnet C 45,7 % H 3,3 % Cu 17,3 % N 7,6 % gefunden C 45,8 % H 3,6 % Cu 17,0 % N 7,6 % A sample of the substance is made from a dimethylformamide-water mixture (Ratio 1: 1) recrystallized, washed with ethanol and dried. A light brown powder with a melting point of 214 ° C. (decomposition) is obtained. Elemental analysis calculated C 45.7% H 3.3% Cu 17.3% N 7.6% found C 45.8% H 3.6% Cu 17.0% N 7.6%

Beispiel 3:Example 3:

8 g 2,5-Dihydroxybenzaldehyd werden bei 60°C in 40 ml Dimethylformamid gelöst. Man gibt unter Rühren 1,74 g Ethylendiamin und dann eine 60°C warme Lösung von 5,8 g Kupfer-(II)-acetat·H₂O in 80 ml Dimethylformamid zu und rührt während einer Stunde bei 60°C. Nach dem Abkühlen saugt man den Niederschlag ab, wäscht mit Dimethylformamid und Ethanol nach und erhält nach Trocknung 10,4 g (82 % d. Th.) des Komplexes der Formel

Figure imgb0009
mit 1 Mol Dimethylformamid als Kristallsolvens, als dunkel-graugrüner Feststoff. Elementaranalyse berechnet C 52,3 % H 4,9 % N 9,7 % gefunden C 52,5 % H 4,9 % N 9,6 % 8 g of 2,5-dihydroxybenzaldehyde are dissolved in 40 ml of dimethylformamide at 60 ° C. 1.74 g of ethylenediamine are added with stirring and then a 60 ° C. solution of 5.8 g of copper (II) acetate · H₂O in 80 ml of dimethylformamide is added and the mixture is stirred at 60 ° C. for one hour. After cooling, the precipitate is filtered off, washed with dimethylformamide and ethanol and, after drying, 10.4 g (82% of theory) of the complex of the formula
Figure imgb0009
 with 1 mol of dimethylformamide as a crystal solvent, as a dark gray-green solid. Elemental analysis calculated C 52.3% H 4.9% N 9.7% found C 52.5% H 4.9% N 9.6%

Beispiel 4:Example 4:

5,52 g 2,3-Dihydroxybenzaldehyd werden in 50 ml wasserfreiem Ethanol gelöst. Man gibt unter Rühren 1,2 g Ethylendiamin zu und erhitzt während 15 Minuten am Rückfluss. Anschliessend lässt man abkühlen, filtriert den Niederschlag ab und erhält nach dem Trocknen 5,77 g (96 % d. Th.) der Verbindung der Formel

Figure imgb0010
als gelboranges Pulver vom Smp. 231-234°C.5.52 g of 2,3-dihydroxybenzaldehyde are dissolved in 50 ml of anhydrous ethanol. 1.2 g of ethylenediamine are added with stirring and the mixture is heated under reflux for 15 minutes. The mixture is then allowed to cool, the precipitate is filtered off and, after drying, 5.77 g (96% of theory) of the compound of the formula are obtained
Figure imgb0010
 as a yellow-orange powder of mp. 231-234 ° C.

5 g der Verbindung der Formel (105) werden bei 50°C in 40 ml Dimethyl­formamid gelöst. Dieser Lösung gibt man unter Rühren eine 50°C warme Lösung von 3,32 g Kupfer-(II)-acetat·H₂O in 60 ml Dimethylformamid zu und rührt während einer Stunde bei 50°C. Anschliessend gibt man 100 ml Ethanol und 100 ml Wasser zu, filtriert den entstandenen Niederschlag ab, wäscht mit Ethanol nach und erhält nach dem Trocknen 5,55 g (92 % d. Th.) des Komplexes der-Formel

Figure imgb0011
als dunkelrosa Pulver. Elementaranalyse berechnet C 53,1 % H 3,9 % Cu 17,6 % N 7,7 % gefunden C 53,0 % H 4,0 % Cu 17,7 % N 7,8 % 5 g of the compound of formula (105) are dissolved in 40 ml of dimethylformamide at 50 ° C. This solution is added while stirring a 50 ° C warm solution of 3.32 g of copper (II) acetate · H₂O in 60 ml of dimethylformamide and stirred at 50 ° C for one hour. 100 ml of ethanol and 100 ml of water are then added, the precipitate formed is filtered off, washed with ethanol and, after drying, 5.55 g (92% of theory) of the complex of the formula are obtained
Figure imgb0011
 as a dark pink powder. Elemental analysis calculated C 53.1% H 3.9% Cu 17.6% N 7.7% found C 53.0% H 4.0% Cu 17.7% N 7.8%

Beispiel 5:Example 5:

6,68 g Resacetophenon-oxim werden bei 40°C in 80 ml 0,5 n Natronlauge gelöst und der Lösung gibt man unter Rühren eine 40°C warme Lösung von 4,99 g CuSO₄·5H₂O in 25 ml Wasser zu und rührt bei dieser Temperatur 1 Stunde lang. Nach dem Abkühlen filtriert man den ent­standenen Niederschlag ab, wäscht mit Wasser sulfatfrei nach und erhält nach dem Trocknen 7,58 g des Komplexes der Formel

Figure imgb0012
als hellbraune Festsubstanz. Elemantaranalyse berechnet C 48,5 % H 4,1 % Cu 16,0 % N 7,1 % gefunden C 48,5 % H 4,1 % Cu 16,0 % N 7,2 % 6.68 g of resacetophenone oxime are dissolved at 40 ° C in 80 ml of 0.5N sodium hydroxide solution and the solution is added with stirring a 40 ° C warm solution of 4.99 g of CuSO₄ · 5H₂O in 25 ml of water and stirred this temperature for 1 hour. After cooling, the precipitate formed is filtered off, washed with sulfate-free water and, after drying, 7.58 g of the complex of the formula are obtained
Figure imgb0012
 as a light brown solid. Elemental analysis calculated C 48.5% H 4.1% Cu 16.0% N 7.1% found C 48.5% H 4.1% Cu 16.0% N 7.2%

Beispiel 6:Example 6:

5 g der gemäss Vorschrift 1 bzw. 2 hergestellten Verbindungen werden mit 5 g des Kondensationsproduktes aus Naphthalinsulfonsäure und Formaldehyd als Dispergator, das in 7,5 ml Wasser gelöst ist und mit 20 g Quarzkügelchen (Durchmesser ca. 1 mm) versetzt und mit einem Rührer mit ca. 1600 Umdrehungen pro Minute so lange gemahlen, bis die Teilchengrösse unter 3 µm liegt. Die Dispersion wird von den Quarzkügelchen mittels eines feinen Maschensiebes abgetrennt und mit Wasser auf 10 % an Wirk­substanz eingestellt.
Das Einrühren von 0,3 % Carboxymethylcellulose bewirkt eine Stabili­sierung der Dispersion.5 g of the compounds prepared according to regulation 1 or 2 are mixed with 5 g of the condensation product of naphthalenesulfonic acid and formaldehyde as a dispersant, which is dissolved in 7.5 ml of water, and 20 g of quartz beads (diameter approx. 1 mm) and with a stirrer milled at approx. 1600 revolutions per minute until the particle size is below 3 µm. The dispersion is separated from the quartz beads using a fine mesh screen and adjusted to 10% of the active substance with water.
Stirring in 0.3% carboxymethyl cellulose stabilizes the dispersion.

Anwendungsbeispiele:Examples of use: Beispiel 7:Example 7:

Sechs Muster aus Nylontrikot von je 10 g werden in einem Färbeapparat mit offenen Behandlungsbädern, z.B. einem ®AHIBA-Färbe­apparat, in Flotten ohne Farbstoffzusatz (Flottenverhältnis 1:20) behandelt, die 2 % Ammoniumsulfat, 1 g/l eines Dispergators, z.B. des Kondensationsproduktes aus Naphthalinsulfonsäure und Formaldehyd, sowie folgende Zusätze enthalten:

  • Flotten 1-3: 0,01 %; 0,04 % und 0,1 % der Verbindung der Formel
    Figure imgb0013
  • Flotten 4-6: 0,01 %; 0,04 % und 0,1 % der Verbindung der Formel (102).
Six samples of nylon tricot of 10 g each are treated in a dyeing machine with open treatment baths, for example an ®AHIBA dyeing machine, in liquors without dye addition (liquor ratio 1:20), the 2% ammonium sulfate, 1 g / l of a dispersant, for example the condensation product from naphthalenesulfonic acid and formaldehyde, as well as the following additives:
  • Liquors 1-3: 0.01%; 0.04% and 0.1% of the compound of the formula
    Figure imgb0013
  • Fleets 4-6: 0.01%; 0.04% and 0.1% of the compound of formula (102).

Beide Verbindungen liegen als Formulierungen mit 10 % an Aktivsubstanz vor. Alle Nylonmuster werden parallel behandelt. Die Behandlung erfolgt zunächst 5 Minuten bei 50°C. Sodann wird die Temperatur mit einer Aufheizrate von 2°C/Min. auf 95°C erhöht. Bei dieser Temperatur behandelt man 60 Minuten. Danach wird auf 70°C abgekühlt, bei 40°C warm und dann kalt gespült, zentrifugiert und bei 60°C in einem Umluftofen getrocknet.Both compounds are present as formulations with 10% active substance. All nylon patterns are treated in parallel. The treatment is initially carried out for 5 minutes at 50 ° C. Then the temperature with a heating rate of 2 ° C / min. increased to 95 ° C. Treat at this temperature for 60 minutes. It is then cooled to 70 ° C., rinsed warm at 40 ° C. and then cold, centrifuged and dried at 60 ° C. in a forced air oven.

Die folgende Tabelle zeigt die aus den Kupfer-Analysen der Muster ermittelten Ausbeuten.

Figure imgb0014
The following table shows the yields determined from the copper analyzes of the samples.
Figure imgb0014

Die Analysewerte zeigen, dass die Verbindung (102) deutlich besser auf das Polyamid-Trikot auszieht als Verbindung (108).The analysis values show that the compound (102) extends significantly better to the polyamide jersey than compound (108).

Der in der Flotte verbleibende Anteil an Kupferverbindungen ist wesent­lich geringer, d.h. das Abwasser wird deutlich geringer belastet.The proportion of copper compounds remaining in the fleet is significantly lower, i.e. the wastewater is significantly less polluted.

Beispiel 8:Example 8:

5 Stränge von je 10 g eines Nylonstapelgarnes werden in 5 Ansätzen mit folgenden Farbstoffen zu einem Grau gefärbt

Figure imgb0015
5 strands of 10 g each of a nylon staple yarn are dyed a gray in 5 batches with the following dyes
Figure imgb0015

Zu den einzelnen Flottenansätzen werden 0 bzw. 0,01 % und 0,06 %der Verbindungen (108) und (102) gegeben. Die Durchführung der Färbungen erfolgt wie in Beispiel 7 angegeben. Die fertigen Färbungen werden auf ihre Lichtechtheiten nach SN-ISO 105-B02 (=Xenon), sowie nach DIN 75.202 (=Fakra) geprüft. Der fotochemische Faserabbau wird durch Bestimmung der Zugfestigkeit und Bruchdehnung nach SNV 97.461 von Färbungen bestimmt, die 150 Stunden nach DIN 75.202 belichtet wurden.0, 0.01% and 0.06% of the compounds (108) and (102) are added to the individual liquor batches. The dyeings are carried out as indicated in Example 7. The finished dyeings are tested for light fastness according to SN-ISO 105-B02 (= xenon) and DIN 75.202 (= Fakra). The photochemical fiber degradation is determined by determining the tensile strength and elongation at break according to SNV 97.461 of dyeings which have been exposed for 150 hours in accordance with DIN 75.202.

Die Tabelle zeigt neben diesen Versuchsergebnissen auch den analytisch ermittelten verbliebenen Kupfer-Gehalt auf der Faser. Färbung / Zusatz Cu-Gehalt µg/g PA Lichtechtheiten* Zugfestigkeit / Dehnung ** in % nach Belichtung Xenon F. 96 h F. 192 h 1. kein Zusatz - -6-7 -6 5 12,6 / 13,7 2. + 0,01 % Verbindung (108) 11 6-7+ 6-7 -6 49,6 / 48,6 3. + 0,06 % Verbindung (108) 63 6-7+ 6-7+ -6-7 62,7 / 62,5 4. + 0,01 % Verbindung (102) 17,5 6-7+ 6-7+ 6-7 55 / 53,5 5. + 0,06 % Verbindung (102) 101 7 6-7+ 6-7 66,8 / 69 * F = Fakra (= DIN 75.202) ** unbelichtetes Ausgangsmaterial als Standard In addition to these test results, the table also shows the analytically determined remaining copper content on the fiber. Coloring / addition Cu content µg / g PA Lightfastness * Tensile strength / elongation ** in% after exposure xenon F. 96 h F. 192 h 1. no addition - -6-7 -6 5 12.6 / 13.7 2nd + 0.01% connection (108) 11 6-7 + 6-7 -6 49.6 / 48.6 3rd + 0.06% connection (108) 63 6-7 + 6-7 + -6-7 62.7 / 62.5 4th + 0.01% connection (102) 17.5 6-7 + 6-7 + 6-7 55 / 53.5 5. + 0.06% connection (102) 101 7 6-7 + 6-7 66.8 / 69 * F = Fakra (= DIN 75.202) ** unexposed source material as standard

Die bei den Untersuchungen erzielten Unterschiede in den einzelnen Färbungen resultieren aus den unterschiedlichen Kupfer-Gehalten.The differences in the individual colors obtained in the investigations result from the different copper contents.

Beispiel 9:Example 9:

5 Stränge von je 10 g eines Nylongarnes werden, wie in Beispiel 4 erläutert, in einem ®Ahiba-Färbeapparat in Flotten ohne Farbstoff behandelt, wobei die einzelnen Flotten neben Ammoniumsulfat und Dispergator noch folgende Zusätze enthalten:

  • Flotte 1: kein Zusatz (Vergleich)
  • Flotten 2-3: 0,05 %; 0,25 % der Verbindung der Formel
    Figure imgb0016
  • Flotten 4-5: 0,05 %; 0,25 % der Verbindung (103)
5 strands of 10 g each of a nylon yarn, as explained in Example 4, are treated in a ®Ahiba dyeing machine in liquors without dye, the individual liquors also containing the following additives in addition to ammonium sulfate and dispersant:
  • Fleet 1: no addition (comparison)
  • Liquors 2-3: 0.05%; 0.25% of the compound of the formula
    Figure imgb0016
  • Fleets 4-5: 0.05%; 0.25% of compound (103)

Die Zusätze in den Flotten 2-5 werden als 10%-ige Dispersionen einge­setzt.The additives in fleets 2-5 are used as 10% dispersions.

Von den beschriebenen fertiggestellten Färbungen werden der Cu-Gehalt bestimmt sowie Heissbelichtungen nach DIN 75.202 zur Ermittlung des photochemischen Abbaus durchgeführt.The Cu content of the finished dyeings described is determined and hot exposures in accordance with DIN 75.202 are carried out to determine the photochemical degradation.

In der folgenden Tabelle sind die Untersuchungsergebnisse aufgeführt.The test results are listed in the following table.

Es ist deutlich zu ersehen, dass die photochemische Stabilität des Fasermaterials einerseits von der aufgezogenen Menge an Kupferkomplex abhängt, andererseits, dass dessen Affinität zur Faser bestimmend ist. Flotte Behandlung mit Cu [µg/g PA] *Zugfestigkeit / Dehnung [%] nach 192 h Fakra nach 288 h Fakra 1 ohne Cu-Komplex - 10,6 / 13,8 zerstört 2 0,05 % (109) ** 5,2 zerstört zerstört 3 0,25 % (109) ** 39 50,9 / 47,9 30,6 / 35,6 4 0,05 % (103) ** 9,2 25,9 / 24,9 zerstört 5 0,25 % (103) ** 45 61,0 / 59,0 48,4 / 51,4 * unbelichtetes Ausgangsmaterial als Standard ** als ca. 10%-ige Dispersion eingesetzt. It can clearly be seen that the photochemical stability of the fiber material depends on the one hand on the amount of copper complex drawn up, and on the other hand that its affinity for the fiber is decisive. fleet Treatment with Cu [µg / g PA] * Tensile strength / elongation [%] after 192 hrs after 288 h Fakra 1 without Cu complex - 10.6 / 13.8 destroyed 2nd 0.05% (109) ** 5.2 destroyed destroyed 3rd 0.25% (109) ** 39 50.9 / 47.9 30.6 / 35.6 4th 0.05% (103) ** 9.2 25.9 / 24.9 destroyed 5 0.25% (103) ** 45 61.0 / 59.0 48.4 / 51.4 * unexposed source material as standard ** used as an approx. 10% dispersion.

Claims (10)

1. Verfahren zur photochemischen Stabilisierung von ungefärbtem und gefärbtem Polyamidfasermaterial oder dessen Mischungen mit anderem Fasermaterial mit photochemisch stabilisierenden Mitteln auf der Basis von Kupferverbindungen von Phenolen, dadurch gekennzeichnet, dass man das Polyamidfasermaterial mit faseraffinen, organischen Kupferkomplexen der Umsetzungsprodukte von o-Hydroxybenzoylderivaten der Formel
Figure imgb0017
 worin R Wasserstoff oder C₁-C₄-Alkyl bedeutet und der OH-Substituent sich in 3-, 4- oder 5-Stellung befindet, mit aliphatischen Diaminen oder Hydroxylamin behandelt.1. A method for the photochemical stabilization of undyed and dyed polyamide fiber material or its mixtures with other fiber material with photochemically stabilizing agents based on copper compounds of phenols, characterized in that the polyamide fiber material with fiber-affine, organic copper complexes of the reaction products of o-hydroxybenzoyl derivatives of the formula
Figure imgb0017
 wherein R is hydrogen or C₁-C₄-alkyl and the OH substituent is in the 3-, 4- or 5-position, treated with aliphatic diamines or hydroxylamine. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man als Kupferkomplex eine Verbindung der Formel
Figure imgb0018
 verwendet, worin R Wasserstoff oder C₁-C₄-Alkyl und X₁ und Y₁ unabhängig voneinander je Wasserstoff oder C₁-C₄-Alkyl bedeuten und wobei sich die OH-Substituenten in 3-, 4- oder 5-Stellung befinden.2. The method according to claim 1, characterized in that as a copper complex, a compound of the formula
Figure imgb0018
 used, wherein R is hydrogen or C₁-C₄-alkyl and X₁ and Y₁ are each independently hydrogen or C₁-C₄-alkyl and the OH substituents are in the 3-, 4- or 5-position. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass man als Verbindung einen Kupferkomplex der Formel
Figure imgb0019
 verwendet.3. The method according to claim 2, characterized in that the compound is a copper complex of the formula
Figure imgb0019
 used. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man eine Kupferkomplexverbindung der Formel
Figure imgb0020
 verwendet, worin R Wasserstoff oder C₁-c₄-Alkyl bedeutet und wobei sich die OH-Substituenten in 4- oder 5-Stellung befinden.4. The method according to claim 1, characterized in that a copper complex compound of the formula
Figure imgb0020
 used, wherein R is hydrogen or C₁-C₄-alkyl and wherein the OH substituents are in the 4- or 5-position. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass man eine Kupferkomplexverbindung der Formel
Figure imgb0021
 verwendet.5. The method according to claim 4, characterized in that a copper complex compound of the formula
Figure imgb0021
 used. 6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man den Kupferkomplex direkt dem Färbebad zusetzt.6. The method according to any one of claims 1 to 5, characterized in that the copper complex is added directly to the dyebath. 7. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass man den Kupferkomplex in einer Menge einsetzt, dass auf 1 g Polyamid 5 bis 200 µg Kupfer kommen.7. The method according to claim 5, characterized in that the copper complex is used in an amount such that 5 to 200 ug copper come to 1 g of polyamide. 8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Färbung kontinuierlich oder diskontinuierlich bei einer Temperatur von 20 bis 130°C und bei kontinuierlicher Arbeitsweise die Fixierung der Kupferkomplexe bei einer Temperatur von 100 bis 200°C erfolgt.8. The method according to any one of claims 1 to 7, characterized in that the coloring is carried out continuously or discontinuously at a temperature of 20 to 130 ° C and in a continuous procedure, the fixing of the copper complexes at a temperature of 100 to 200 ° C. 9. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass man Faser­mischungen aus Polyamid und Polyurethan einsetzt.9. The method according to claim 5, characterized in that fiber mixtures made of polyamide and polyurethane are used. 10. Das nach dem Verfahren gemäss einem der Ansprüche 1 bis 8 behandelte gefärbte oder ungefärbte Polyamidfasermaterial sowie Fasermischungen.10. The dyed or undyed polyamide fiber material and fiber mixtures treated by the method according to one of claims 1 to 8.
EP89810714A 1988-09-29 1989-09-20 Process for the photochemical stabilisation of undyed and dyed fibrous polyamide material and mixtures thereof Expired - Lifetime EP0362139B1 (en)

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US4655783A (en) * 1985-05-09 1987-04-07 Ciba-Geigy Corporation Process for photochemical stabilization of non-dyed and dyed polyamide fibre material and mixtures thereof
EP0245204A1 (en) * 1986-05-05 1987-11-11 Ciba-Geigy Ag Process for the photochemical stabilization of undyed and dyed fibrous polyamide material and its mixture with other fibres

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