EP0362139B1 - 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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EP0362139B1
EP0362139B1 EP89810714A EP89810714A EP0362139B1 EP 0362139 B1 EP0362139 B1 EP 0362139B1 EP 89810714 A EP89810714 A EP 89810714A EP 89810714 A EP89810714 A EP 89810714A EP 0362139 B1 EP0362139 B1 EP 0362139B1
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Prior art keywords
copper
process according
polyamide
undyed
formula
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German (de)
French (fr)
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EP0362139A1 (en
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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.
  • 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-hydrolybenzoyl 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 hydroxylamine.
  • the photochemically stabilized polyamide fiber material or mixtures thereof with other fibers form a further subject of the present invention.
  • 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 (4) are 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.
  • Example 1 6.05 g of 2,4-dihydroxybenzaldoxime are dissolved in 39.5 ml of sodium hydroxide solution at 40 ° C. 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 6.5 g (89.7%) are obtained after drying.
  • Example 3 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 with 20 g of quartz beads (diameter approx. 1 mm) ground with a stirrer 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 sieve and adjusted to 10% of the active substance with water. Stirring in 0.3% carboxymethyl cellulose stabilizes the dispersion.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

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 werden faserreaktive verbrückte 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. Die verbrückten Bisazomethin-Kupferkomplexe weisen nicht alle vorteilhaften Eigenschaften der erfindungsgemäss eingesetzten unverbrückten Bisazomethin-Kupferkomplex auf.In US-A-4,655,783 fiber reactive bridged 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. The bridged bisazomethine copper complexes do not have all the advantageous properties of the unbridged bisazomethine copper complex used according to the invention.

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-Hydrolybenzoylderivaten 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 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-hydrolybenzoyl 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 hydroxylamine.

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

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

Figure imgb0002

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 imgb0002
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 imgb0003

entsprechen.The focus of interest, however, is on copper complex compounds, that of the formula
Figure imgb0003
correspond.

Die Kupferkomplexverbindungen der Formel (4) sind 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 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.
Beispiel 1: 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 mach Trocknung 6,5 g (89,7 % d.Th.) eines dunkeloliven Komplexes der Formel

Figure imgb0004

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 %
Beispiel 2: 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 imgb0005
 als hellbraune Festsubstanz. Elementaranalyse berechnet C 48,5 % H 4,1 % Cu 16,0 % H 7,1 % gefunden C 48,5 % H 4,1 % Cu 16,0 % H 7,2 %
Beispiel 3: 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.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, unless otherwise noted, relate to the fiber material.
Example 1: 6.05 g of 2,4-dihydroxybenzaldoxime are dissolved in 39.5 ml of sodium hydroxide solution at 40 ° C. 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 6.5 g (89.7%) are obtained after drying. i.e.) a dark olive complex of the formula
Figure imgb0004
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%
Example 2: 6.68 g of resacetophenone oxime are dissolved at 40 ° C in 80 ml of 0.5 N sodium hydroxide solution and the solution is added with stirring a 40 ° C solution of 4.99 g of CuSO₄ · 5H₂O in 25 ml of water and stir at 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 imgb0005
 as a light brown solid. Elemental analysis calculated C 48.5% H 4.1% Cu 16.0% H 7.1% found C 48.5% H 4.1% Cu 16.0% H 7.2%
Example 3: 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 with 20 g of quartz beads (diameter approx. 1 mm) ground with a stirrer 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 sieve and adjusted to 10% of the active substance with water.
Stirring in 0.3% carboxymethyl cellulose stabilizes the dispersion.

Anwendungsbeispiele:Examples of use:


Beispiel 4: 5 Stränge von je 10 g eines Nylongarnes 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:

Flotte 1:
kein Zusatz (Vergleich)
Flotten 2-3:
0,05 %; 0,25 % der Verbindung der Formel
Figure imgb0006
Flotten 4-5:
0,05 %; 0,25 % der Verbindung (103)
Die Zusätze in den Flotten 2-5 werden als 10%-ige Dispersionen eingesetzt.
Von den beschriebenen fertiggestellten Färbungen werden der Cu-Gehalt bestimmt sowie Heissbelichtungen nach DIN 75.202 zur Ermittlung des photochemischen Abbaus durchgeführt.
In der folgenden Tabelle sind die Untersuchungsergebnisse aufgeführt.
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.
Example 4: 5 strands of 10 g each of a nylon yarn are treated in a dyeing machine with open treatment baths, for example an ®AHIBA dyeing machine, in liquors without added dye (liquor ratio 1:20) which contain 2% ammonium sulfate, 1 g / l of a dispersant, eg the condensation product of naphthalenesulfonic acid and formaldehyde, as well as the following additives:
Fleet 1:
no addition (comparison)
Fleets 2-3:
0.05%; 0.25% of the compound of the formula
Figure imgb0006
Fleets 4-5:
0.05%; 0.25% of compound (103)
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.
The test results are listed in the following table.
It can be clearly 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 h Fakra 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 (8)

  1. A process for the photochemical stabilization of undyed and dyed polyamide fibre material, or blends thereof with other fibre material, using photochemically stabilizing compositions based on copper compounds of phenols, which process comprises treating said polyamide fibre material with organic copper complexes, with affinity for the fibre, of the reaction products of o-hydroxybenzoyl derivatives of the formula
    Figure imgb0010
     wherein R is hydrogen or C₁-C₄alkyl and the OH substituent is located in the 3-, 4- or 5-position, with hydroxylamine.
  2. A process according to claim 1, wherein a copper complex compound of the formula
    Figure imgb0011
     is used, wherein R is hydrogen or C₁-C₄alkyl and the OH substituents are located in the 4- or 5-position.
  3. A process according to claim 2, wherein a copper complex compound of the formula
    Figure imgb0012
     is used.
  4. A process according to any one of claims 1 to 3, wherein the copper complex is added directly to the dyebath.
  5. A process according to claim 4, wherein the copper complex is used in an amount such that 5 to 200 µg of copper are used per g of polyamide.
  6. A process according to any one of claims 1 to 5, wherein dyeing is carried out continuously or batchwise at a temperature from 20 to 130°C and, in the continuous procedure, the copper complexes are fixed at a temperature from 100 to 200°C.
  7. A process according to claim 1, wherein fibre blends of polyamide and polyurethane are used.
  8. A dyed or undyed polyamide fibre material or fibre blend treated by a process according to any one of claims 1 to 7.
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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CH362188 1988-09-29
CH3621/88 1988-09-29

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EP0362139B1 true EP0362139B1 (en) 1993-10-13

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* Cited by examiner, † Cited by third party
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DE3941295A1 (en) * 1989-12-14 1991-06-20 Basf Ag METHOD FOR COLORING POLYAMIDE SUBSTRATES
US5069681A (en) * 1990-01-03 1991-12-03 Ciba-Geigy Corporation Process for the photochemical stabilization of dyed polyamide fibres with foamed aqueous composition of copper organic complexes
US6391065B1 (en) 1995-11-03 2002-05-21 Boehme Filatex, Inc. UV light absorber composition and method of improving the lightfastness of dyed textiles

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3247051A1 (en) * 1982-12-20 1984-06-20 Bayer Ag, 5090 Leverkusen METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS
DE3326640A1 (en) * 1983-07-23 1985-01-31 Basf Ag, 6700 Ludwigshafen METHOD FOR IMPROVING THE LIGHT FASTNESS OF COLORING WITH ACID OR METAL COMPLEX DYES ON POLYAMIDE
EP0185611B1 (en) * 1984-12-21 1988-09-21 Ciba-Geigy Ag Process for the photochemical stabilisation of synthetic fibrous materials containing polyamide fibres
DE3563462D1 (en) * 1985-05-09 1988-07-28 Ciba Geigy Ag Process for the photochemical stabilisation of undyed and dyed polyamide fibrous material and its mixtures
US4655830A (en) * 1985-06-21 1987-04-07 Tomotsu Akashi High density compacts
US4775386A (en) * 1986-05-05 1988-10-04 Ciba-Geigy Corporation Process for photochemical stabilization of undyed and dyed polyamide fibre material and blends thereof with other fibres: copper complex and light stabilizer treatment
US4874391A (en) * 1986-07-29 1989-10-17 Ciba-Geigy Corporation Process for photochemical stabilization of polyamide fiber material and mixtures thereof with other fibers: water-soluble copper complex dye and light-stabilizer

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ES2059820T3 (en) 1994-11-16
EP0362139A1 (en) 1990-04-04
JP2773919B2 (en) 1998-07-09
US4990164A (en) 1991-02-05
JPH02118174A (en) 1990-05-02
DE58905902D1 (en) 1993-11-18

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