EP0113856B1 - Process for improving the fastness to light of polyamide dyeings - Google Patents

Process for improving the fastness to light of polyamide dyeings Download PDF

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Publication number
EP0113856B1
EP0113856B1 EP83112324A EP83112324A EP0113856B1 EP 0113856 B1 EP0113856 B1 EP 0113856B1 EP 83112324 A EP83112324 A EP 83112324A EP 83112324 A EP83112324 A EP 83112324A EP 0113856 B1 EP0113856 B1 EP 0113856B1
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Prior art keywords
copper
process according
copper compounds
polyamide
light fastness
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German (de)
French (fr)
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EP0113856A1 (en
Inventor
Klaus-Peter Dr. Heise
Robert Dr. Kuth
Karl Dr. Neufang
Hellmuth Dipl.-Ing. Pantke
Karlfried Dr. Wedemeyer
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Bayer AG
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Bayer AG
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    • 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
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/376—Oximes
    • 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
    • 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

Definitions

  • C.A. 97, 93875e known to use copper chelates of glycinates as light fastness improvers.
  • This acid stability is of crucial importance because, in practice, after the dyeing, additives in the acidic range at pH 4 to 6 are often necessary for the final completion of the dye.
  • Another advantage of the copper compounds according to the invention is their compared to e.g. with copper complexes from Schiff bases mentioned above, less self-coloring.
  • the copper compounds according to the invention are used in amounts of 0.01-2%, preferably 0.05 to 0.1%, based on the weight of the polyamide. It is preferably added to the dyebath.
  • the copper compounds to be used according to the invention are known (for example the salicylaldoxime-copper (11) complex from Ber. 63, 1928-30 (1930), the 2-hydroxyacetophenone oxime-copper (11) complex from Ber. 64, 1210-1215 (1931)) or in a manner known per se by reacting compounds of the formula with a copper (II) salt, in particular with a salt of a mineral acid such as copper (II) chloride or copper (II) sulfate, or copper (II) oxide ( hydroxide) is preferably obtainable in an alcoholic, aqueous alcoholic or aqueous medium. 1 to 2 moles of compound I are preferably reacted per mole of copper compound. Accordingly, the reaction products are the corresponding 1: 1 and 1: 2 copper complexes or (in the case of the hydroxamic acid derivatives) presumably the corresponding acidic and neutral copper salts.
  • a copper (II) salt in particular with a salt of a mineral acid such as copper
  • transition metal complexes of the compounds (I) as light fastness improvers is also known in principle, but so far these have always been used for other substrates, such as e.g. Cellulose fibers (see GB 1 321 645 and 1 392 953), modified polyolefin and polyacetal fibers (see US 3 203 752) or ethyl cellulose polymers (see DE-A 2 625 386).
  • these patents did not describe the copper complexes mentioned at most, but almost exclusively the nickel complexes as examples and as particularly preferred, from which it had to be concluded that the copper complexes are less suitable.
  • Polyamide is preferably understood to mean synthetic polyamide fibers.
  • the dyeings on these fibers can be produced in a conventional manner using both metal complex dyes and acid dyes.
  • the metal complex dyes in particular the 1: 2 chromium or 1: 2 cobalt complexes of mono- or diazo compounds, which are described in large numbers in the literature and are commercially available, are preferred. These dyes can also contain 1-2 sulfo groups.
  • Suitable acid dyes are, in particular, those types which are usually used in combination with the metal complex dyes.
  • the treatment of the polyamide materials with the copper compounds to be used according to the invention can take place before, during or after, preferably during the dyeing.
  • the copper compounds normally produced separately are of course used in finely divided form, as is obtained by grinding in the presence of customary dispersants.
  • this is carried out, as it were, in a "one-pot", in that the fiber materials are not treated directly with the copper compounds isolated in solid form, but - in principle in any order - are produced in situ from the corresponding starting materials on the fiber.
  • the fibers are preferably first dyed with a dyeing liquor which, in addition to the dye and customary dyeing auxiliaries, contains the metal-free compounds of the formula 1 and is subsequently treated with a copper (II) salt solution.
  • the copper content in the product was determined to be 28.9%.
  • the coloring treated with (1) shows a considerably better light fastness than the comparison.
  • the dyeing liquor is adjusted to pH 6 with a buffer mixture consisting of monosodium phosphate and acetic acid. It is treated for 1 hour at 98-100 ° C., rinsed and dried.
  • the dyeing produced in this way shows a significantly better light fastness after 250 h exposure time in the Opel test than one produced without (1).
  • a polyamide 6 dyeing with the dye Acid Yellow 151 (C.I. 14 906) is prepared in a known manner from a long liquor and dried.
  • This dyeing is impregnated with 1 g / l of a 10% aqueous dispersion of the copper complex described in Example 1 on the padder in such a way that the increase in wet weight is 100%.
  • a pH of 8 is set by adding disodium phosphate and monosodium phosphate.
  • the liquor temperature is then slowly increased to 98-100 ° C. while moving the material to be dyed and left at this temperature for 1 hour.
  • the dyeing is then rinsed and dried.
  • the coloring is exposed together with a coloring produced without (2).
  • the coloring treated with (2) shows a considerably better light fastness.
  • Example 1a If dyeing is carried out as described in Example 1a, but instead of the copper complex (1) the corresponding nickel complex is used at 0.1% based on the fiber weight, no improvement in light fastness is obtained either at pH 6 or at pH 8. When exposed to light, the coloring behaves as if no light stabilizer has been added to the dyeing liquor.
  • the polyamide material is removed, rinsed briefly and added to 2000 parts of fresh dye liquor which contain 0.1 part of CuS0 4. 5H 20. After gradually warming the liquor to 98-100 ° C, it is treated for 30 minutes at this final temperature. The material to be dyed is moved evenly throughout the treatment.
  • the material to be dyed is removed, rinsed and dried.
  • the dyeing is exposed together with a dye prepared without salicylaldoxime / copper sulfate aftertreatment according to the "Opel test".
  • the dyeing produced with two baths with salicylaldoxime / CuS0 4 .5H 2 0 shows a much better light fastness.
  • the dyeings produced according to 7 a and 7 b are subjected to a heat-setting which is customary in the textile industry as a final treatment for 30 s at 180 ° C., the light fastness is not adversely affected.

Description

Im Automobilsektor werden seit einigen Jahren immer höhere Anforderungen an die Lichtechtheit von gefärbten Textilmaterialien auf der Basis von vorzugsweise synthetischen Polyamidfasern zur Herstellung von Sitzbezügen gestellt. Ein solch hohes Echtheitsniveau wird jedoch von den meisten handelsüblichen Polyamidfarbstoffen nicht erreicht. Das gilt im besonderen auch für die wegen ihrer überragenden Lichtechtheit fast ausschließlich für den genannten Zweck eingesetzten Metallkomplexfarbstoffe. Es ist daher bereits vorgeschlagen worden, diese Farbstoffe gemeinsam mit UV-Absorbern einzusetzen, um den hohen Anforderungen der Automobilhersteller gerecht zu werden.In the automotive sector, there have been increasing demands on the light fastness of dyed textile materials on the basis of preferably synthetic polyamide fibers for the manufacture of seat covers. However, most commercially available polyamide dyes do not achieve such a high level of fastness. This applies in particular to the metal complex dyes used almost exclusively for the stated purpose because of their outstanding light fastness. It has therefore already been proposed to use these dyes together with UV absorbers in order to meet the high demands of automobile manufacturers.

So ist beispielsweise aus C.A. 97, 93875e bekannt, Kupfer-Chelate von Glycinaten als Lichtechtheitsverbesserer zu verwenden.For example, C.A. 97, 93875e known to use copper chelates of glycinates as light fastness improvers.

Weiterhin wird gemäß DE-A 3 041 153 empfohlen, die Polyamidtextilmaterialien vor, während oder nach der Färbung mit Rupferkomplexen von Schiffschen Basen zu behandeln.Furthermore, according to DE-A 3 041 153, it is recommended to treat the polyamide textile materials with, before, during or after the dyeing, with plucking complexes from Schiff bases.

Diese an sich bewährte Methode weist jedoch den Nachteil auf, daß die dabei verwendeten Lichtechtheltsverbesserer eine unerwünschte Eigenfarbe und eine nicht ganz ausreichende Säurestabilität aufweisen.However, this method, which is proven per se, has the disadvantage that the light fastness improvers used have an undesirable intrinsic color and an insufficient acid stability.

Diese Säurestabilität ist deshalb von entscheidender Wichtigkeit, weil in der Praxis häufig nach dem Färben Avivagen im sauren Bereich bei pH 4 bis 6 zum endgültigen Fertigstellen des Färbegutes notwendig sind.This acid stability is of crucial importance because, in practice, after the dyeing, additives in the acidic range at pH 4 to 6 are often necessary for the final completion of the dye.

Es wurde nun gefunden, daß man die Lichtechtheit von Polyamidfärbungen mit vorzugsweise Metallkomplexfarbstoffen verbessern kann, ohne die vorstehend genannten Nachteile bei einer Nachbehandlung im sauren Milieu in Kauf nehmen zu müssen, indem man Kupferverbindungen von Phenolen der Formel

Figure imgb0001
worin R = H, OH oder C1-C4-Alkyl bedeutet, verwendet.It has now been found that the lightfastness of polyamide dyeings, preferably with metal complex dyes, can be improved without having to accept the disadvantages mentioned above in an aftertreatment in an acidic environment by using copper compounds of phenols of the formula
Figure imgb0001
 wherein R = H, OH or C 1 -C 4 alkyl used.

Ein weiterer Vorteil der erfindungsgemäßen Kupferverbindungen ist ihre, verglichen z.B. mit oben erwähnten Kupferkomplexen von Schiffschen Basen, geringere Eigenfärbung.Another advantage of the copper compounds according to the invention is their compared to e.g. with copper complexes from Schiff bases mentioned above, less self-coloring.

Die erfindungsgemäßen Kupferverbindungen werden in Mengen von 0,01 - 2 %, vorzugsweise 0,05 bis 0,1 %, bezogen auf das Gewicht des Polyamids, eingesetzt. Vorzugsweise erfolgt ein Zusatz zum Färbebad.The copper compounds according to the invention are used in amounts of 0.01-2%, preferably 0.05 to 0.1%, based on the weight of the polyamide. It is preferably added to the dyebath.

Die erfindungsgemäß zu verwendenden Kupferverbindungen sind bekannt, (z.B. der Salicylaldoxim-Kupfer(11)-komplex aus Ber. 63, 1928-30 (1930), der 2-Hydroxyacetophenonoxim-Kupfer(11)-komplex aus Ber. 64, 1210 - 1215 (1931)) oder in an sich bekannter Weise durch Umsetzung von Verbindungen der Formel mit einem Kupfer-II-salz, insbesondere mit einem Salz einer Mineralsäure wie Kupfer(II)chlorid oder Kupfer(II)sulfat, oder Kupfer-II-oxid(hydroxid) in vorzugsweise alkoholischem, wäßrig alkoholischem oder wäßrigem Medium erhältlich. Bevorzugt werden 1 bis 2 Mol der Verbindung I pro Mol Kupferverbindung umgesetzt. Demzufolge handelt es sich bei den Umsetzungsprodukten um die entsprechenden 1:1- und 1:2-Kupfer-Komplexe bzw. (bei den Hydroxamsäure-derivaten) vermutlich um die entsprechenden sauren und neutralen Kupfersalze.The copper compounds to be used according to the invention are known (for example the salicylaldoxime-copper (11) complex from Ber. 63, 1928-30 (1930), the 2-hydroxyacetophenone oxime-copper (11) complex from Ber. 64, 1210-1215 (1931)) or in a manner known per se by reacting compounds of the formula with a copper (II) salt, in particular with a salt of a mineral acid such as copper (II) chloride or copper (II) sulfate, or copper (II) oxide ( hydroxide) is preferably obtainable in an alcoholic, aqueous alcoholic or aqueous medium. 1 to 2 moles of compound I are preferably reacted per mole of copper compound. Accordingly, the reaction products are the corresponding 1: 1 and 1: 2 copper complexes or (in the case of the hydroxamic acid derivatives) presumably the corresponding acidic and neutral copper salts.

Auch die Eignung von Übergangsmetallkomplexen der Verbindungen (I) als Lichtechtheitsverbesserungsmittel ist im Prinzip bekannt, jedoch wurden diese bislang stets für andere Substrate eingesetzt, wie z.B. Cellulosefasern, (vgl. GB 1 321 645 und 1 392 953), modifizierte Polyolefin- bzw. Polyacetalfasern (vgl. US 3 203 752) oder Ethylcellulose-Polymere (vgl. DE-A 2 625 386). Darüber hinaus wurden in diesen Patentschriften nicht die allenfalls am Rande erwähnten Kupferkomplexe sondern fast ausschließlich die Nickelkomplexe beispielhaft und als besonders bevorzugt beschrieben, woraus man den Schluß ziehen mußte, daß die Kuperkomplexe weniger gut geeignet sind.The suitability of transition metal complexes of the compounds (I) as light fastness improvers is also known in principle, but so far these have always been used for other substrates, such as e.g. Cellulose fibers (see GB 1 321 645 and 1 392 953), modified polyolefin and polyacetal fibers (see US 3 203 752) or ethyl cellulose polymers (see DE-A 2 625 386). In addition, these patents did not describe the copper complexes mentioned at most, but almost exclusively the nickel complexes as examples and as particularly preferred, from which it had to be concluded that the copper complexes are less suitable.

Es muß daher als ausgesprochen überraschend angesehen werden, daß bei der Lichtechtheitsverbesserung von Polyamidfärbungen allein die Kupferderivate von (1) den gewünschten Effekt ergeben, während die Nickelkomplexe eine wesentlich geringere bzw. keine Wirkung zeigen.It must therefore be regarded as extremely surprising that the improvement in the light-fastness of polyamide dyeings alone gives the copper derivatives of (1) the desired effect, while the nickel complexes have a substantially lower or no effect.

Unter "Polyamid" werden im übrigen vorzugsweise synthetische Polyamidfasern verstanden."Polyamide" is preferably understood to mean synthetic polyamide fibers.

Die Färbungen auf diesen Fasern können in herkömmlicher Weise sowohl mit Metallkomplexfarbstoffen als auch mit Säurefarbstoffen erzeugt werden. Bevorzugt sind die Metallkomplexfarbstoffe, insbesondere die 1:2 Chrom- oder 1:2 Kobalt-Komplexe von Mono- oder Diazoverbindungen, die in der Literatur in großer Zahl beschrieben und im Handel erhältlich sind. Diese Farbstoffe können auch 1-2 Sulfogruppen enthalten.The dyeings on these fibers can be produced in a conventional manner using both metal complex dyes and acid dyes. The metal complex dyes, in particular the 1: 2 chromium or 1: 2 cobalt complexes of mono- or diazo compounds, which are described in large numbers in the literature and are commercially available, are preferred. These dyes can also contain 1-2 sulfo groups.

Geeignete Säurefarbstoffe sind insbesondere solche Typen, die üblicherweise in Kombination mit den Metallkomplexfarbstoffen eingesetzt werden.Suitable acid dyes are, in particular, those types which are usually used in combination with the metal complex dyes.

Die Behandlung der Polyamidmaterialien mit den erfindungsgemäß zu verwendenden Kupferverbindungen kann vor, während oder nach, bevorzugt während der Färbung, erfolgen.The treatment of the polyamide materials with the copper compounds to be used according to the invention can take place before, during or after, preferably during the dyeing.

Die im Normalfall separat hergestellten Kupferverbindungen kommen, sofern sie nicht wasserlöslich sind, selbstverständlich in fein verteilter Form, wie sie durch Mahlung in Gegenwart üblicher Dispergiermittel erhalten wird, zum Einsatz.Provided that they are not water-soluble, the copper compounds normally produced separately are of course used in finely divided form, as is obtained by grinding in the presence of customary dispersants.

Gemäß einer speziellen Ausführungsform des erfindungsgemäßen Verfahrens wird dieses gewissermaßen im "Eintopf" durchgeführt, indem man die Fasermaterialien nicht direkt mit den in fester Form isolierten Kupferverbindungen behandelt, sondern - prinzipiell in beliebiger Reihenfolge - in situ aus den entsprechenden Ausgangsmaterialien auf der Faser erzeugt.According to a special embodiment of the method according to the invention, this is carried out, as it were, in a "one-pot", in that the fiber materials are not treated directly with the copper compounds isolated in solid form, but - in principle in any order - are produced in situ from the corresponding starting materials on the fiber.

Vorzugsweise werden bei dieser Variante die Fasern zunächst mit einer Färbeflotte, die außer dem Farbstoff und üblichen Färbereihilfsmitteln die metallfreien Verbindungen der Formel 1 enthalten, gefärbt und anschließend mit einer Kupfer-II-Salz-Lösung nachbehandelt.In this variant, the fibers are preferably first dyed with a dyeing liquor which, in addition to the dye and customary dyeing auxiliaries, contains the metal-free compounds of the formula 1 and is subsequently treated with a copper (II) salt solution.

HerstellungsbeispieleManufacturing examples Beispiel 1example 1 Salicylhydroxamsäure-Kupferverbindung (2:1)Salicylhydroxamic acid copper compound (2: 1)

76,5 g (0,5 Mol) käufliche Salicylhydroxamsäure werden in 500 ml Wasser vorgelegt, durch Zugabe von 40 g 50 %iger Natronlauge (0,5 Mol) in Lösung gebracht und dann 62,5 g (0,25 Mol) CuS04 x 5 H20 in Form einer gesättigten wäßrigen Lösung unter Rühren zugetropft. Es wird 10 Minuten nachgerührt, der grüne Niederschlag durch Filtration abgetrennt, mit Wasser aufgenommen, ausgerührt und erneut filtriert. Nach Trocknen bei 60° C im Vakuum (200 mbar) verbleiben 92,5 g (theoretisch 91,9 g) eines grüngrauen Pulvers. Der Kupfergehalt im Produkt wurde mit 18,1 % bestimmt.76.5 g (0.5 mol) of commercially available salicylhydroxamic acid are placed in 500 ml of water, dissolved by adding 40 g of 50% sodium hydroxide solution (0.5 mol) and then 62.5 g (0.25 mol) of CuS04 x 5 H 2 0 added dropwise in the form of a saturated aqueous solution with stirring. The mixture is stirred for 10 minutes, the green precipitate is separated off by filtration, taken up in water, stirred and filtered again. After drying at 60 ° C in a vacuum (200 mbar), 92.5 g (theoretically 91.9 g) of a green-gray powder remain. The copper content in the product was determined to be 18.1%.

Beispiel 2Example 2 Salicylhydroxamsäure-Kupferverbindung (1:1)Salicylhydroxamic acid copper compound (1: 1)

58 g (0,38 Mol) Salicylhydroxamsäure werden in 380 ml Wasser vorgelegt und 60,7 g 50 %ige Natronlauge (0,76 Mol) zugegeben. Bei 50° C tropft man unter Rühren 94,8 g (0,38 Mol) CuS04 x 5 H20 in Form einer gesättigten wäßrigen Lösung zu. Es wird 10 Minuten nachgerührt, der grüne Niederschlag durch Filtration abgetrennt, mit 300 ml Wasser aufgenommen, ausgerührt und erneut filtriert. Nach Trocknen bei 60°C im Vakuum (200 mbar) verbleiben 5 80,5 g (theoretisch 81,5 g) grüngraues Pulver.58 g (0.38 mol) of salicylhydroxamic acid are placed in 380 ml of water and 60.7 g of 50% sodium hydroxide solution (0.76 mol) are added. At 50 ° C., 94.8 g (0.38 mol) of CuSO4 x 5 H20 in the form of a saturated aqueous solution are added dropwise with stirring. The mixture is stirred for 10 minutes, the green precipitate is separated off by filtration, taken up in 300 ml of water, stirred and filtered again. After drying at 60 ° C in a vacuum (200 mbar), 5 80.5 g (theoretically 81.5 g) of green-gray powder remain.

Der Kupfergehalt im Produkt wurde mit 28,9 % bestimmt.The copper content in the product was determined to be 28.9%.

ApplikationsbeispieleApplication examples Beispiel 1 aExample 1 a

100 Teile Polyamid-6-Fasermaterial werden in 2000 Teile wäßrige Färbeflotte eingetragen, die 0,065 Teile des Kupferkomplexes

Figure imgb0002
und 0,15 Teile des Metallkomplex-Farbstoffes der Formel
Figure imgb0003
enthält. Durch Zugabe von Dinatriumphosphat und Mononatriumphosphat wird ein pH-Wert von 8 eingestellt. Dann wird die Flottentemperatur unter Bewegung des Färbegutes langsam auf 98 - 100°C erhöht und für 60 min bei dieser Temperatur belassen.100 parts of polyamide 6 fiber material are introduced into 2000 parts of aqueous dyeing liquor, the 0.065 parts of the copper complex
Figure imgb0002
 and 0.15 part of the metal complex dye of the formula
Figure imgb0003
 contains. A pH of 8 is set by adding disodium phosphate and monosodium phosphate. The liquor temperature is then slowly increased to 98-100 ° C. while the material to be dyed is kept and left at this temperature for 60 min.

Anschließend wird die Färbung dem Färbebad entnommen, gespült und getrocknet.

  • Die Färbung wird zusammen mit einer ohne (1) hergestellten Vergleichsfärbung gemäß Test der
  • Adam Opel AG
  • Rüsselsheim / BRD
  • GM (Engineering Standards Europe)
  • GME No 60 202 A/B
  • während 250 h im Xenontestgerät belichtet.
The dye is then removed from the dye bath, rinsed and dried.
  • The coloring is carried out together with a comparative coloring prepared without (1) according to the test of
  • Adam Opel AG
  • Ruesselsheim / FRG
  • GM (Engineering Standards Europe)
  • GME No 60 202 A / B
  • exposed for 250 h in the xenon tester.

Die mit (1) behandelte Färbung zeigt eine erheblich bessere Lichtechtheit als der Vergleich.The coloring treated with (1) shows a considerably better light fastness than the comparison.

Beispiel 1bExample 1b

Eine gleichgute Lichtechtheitsverbesserung erhält man, wenn die Flotte nicht auf pH 8, sondern mit Trinatriumphosphat auf pH 10 eingestellt wird.An equally good improvement in light fastness is obtained if the liquor is not adjusted to pH 8, but to pH 10 with trisodium phosphate.

Beispiel 1 cExample 1 c

Werden die nach 1a bzw. 1b hergestellten Färbungen abschließend während 30 s bei 180°C thermofixiert, so bleibt die Lichtechtheitsverbesserung voll erhalten.If the dyeings produced according to 1a or 1b are finally heat-set at 180 ° C. for 30 s, the improvement in light fastness is fully retained.

Beispiel 2Example 2

100 Teile Polyamid-6-Material werden in 2000 Teile wäßrige Färbeflotte eingetragen, die 0,1 Teile des In Beispiel 1 beschriebenen Kupferkomplexes (1) und 0,5 Teile des Farbstoffes der Formel

Figure imgb0004
enthalten.100 parts of polyamide 6 material are introduced into 2000 parts of aqueous dye liquor, the 0.1 part of the copper complex (1) described in Example 1 and 0.5 part of the dye of the formula
Figure imgb0004
 contain.

Die Färbeflotte wird mit einem Puffergemisch, bestehend aus Mononatriumphosphat und Essigsäure, auf pH 6 eingestellt. Man behandelt 1 Stunde bei 98 - 100° C, spült und trocknet.The dyeing liquor is adjusted to pH 6 with a buffer mixture consisting of monosodium phosphate and acetic acid. It is treated for 1 hour at 98-100 ° C., rinsed and dried.

Die so hergestellte Färbung zeigt eine deutlich bessere Lichtechtheit nach 250 h Belichtungszeit im Opel-Test als eine ohne (1) hergestellte.The dyeing produced in this way shows a significantly better light fastness after 250 h exposure time in the Opel test than one produced without (1).

Wird anstelle von pH 6 bei pH 4 gearbeitet, ist die Lichtechtheitsverbesserung ähnlich gut und erheblich besser als eine gemäß DE 3 041 153 A1 in Applikationsbeispiel 2a. hergestellte Färbung.If pH 4 is used instead of pH 6, the improvement in light fastness is similarly good and considerably better than that according to DE 3 041 153 A1 in application example 2a. produced coloring.

Beispiel 3aExample 3a

Wird wie in Beispiel 1 beschrieben gearbeitet, jedoch anstelle des Kupferkomplexes (1) 0,75 % (in Form einer 10 %igen wäßrigen Dispersion) der im Herstellungsbeispiel 1 beschriebenen Kupferverbindung der Salicylhydroxamsäure (bezogen auf das Fasergewicht) verwendet, erhält man sowohl bei pH 8 als auch bei pH 6 eine deutliche Verbesserung der Lichtechtheit.If the procedure is as described in Example 1, but instead of the copper complex (1) 0.75% (in the form of a 10% strength aqueous dispersion) of the copper compound of salicylhydroxamic acid described in Preparation Example 1 (based on the fiber weight) is used, it is obtained both at pH 8 as well as at pH 6 a clear improvement in light fastness.

Beispiel 3bExample 3b

Wird wie in Beispiel 3a beschrieben, jedoch die im Herstellungsbeispiel 2 beschriebene Kupferverbindung der Salicylhydroxamsäure verwendet, erhält man sowohl bei pH 8 als auch bei pH 6 eine deutliche Verbesserung der Lichtechtheit.If, as described in Example 3a, but the copper compound of salicylhydroxamic acid described in Preparation Example 2 is used, a clear improvement in the light-fastness is obtained both at pH 8 and at pH 6.

Bespiel 4Example 4

Es wird eine Polyamid-6-Färbung mit dem Farbstoff Acid Yellow 151 (C.I. 14 906) in bekannter Weise aus langer Flotte hergestellt und getrocknet.A polyamide 6 dyeing with the dye Acid Yellow 151 (C.I. 14 906) is prepared in a known manner from a long liquor and dried.

Diese Färbung wird mit 1 g/1 einer 10 %igen wäßrigen Dispersion des in Beispiel 1 beschriebenen Kupferkomplexes auf dem Foulard so imprägniert, daß die Naßgewichtszunahme 100 % beträgt.This dyeing is impregnated with 1 g / l of a 10% aqueous dispersion of the copper complex described in Example 1 on the padder in such a way that the increase in wet weight is 100%.

Nach dem Imprägniervorgang wird bei ca. 100°C getrocknet und anschließend während 30 s bei 180°C thermofixiert. Die so behandelte Gelbfärbung zeigt eine deutlich höhere Lichtechtheit als eine ohne Mitverwendung des beschriebenen Kupferkomplexes hergestellte Färbung.After the impregnation process, it is dried at approx. 100 ° C and then heat-set at 180 ° C for 30 s. The yellow coloring treated in this way shows a clearly higher light fastness than a coloring produced without the use of the copper complex described.

Beispiel 5aExample 5a

100 Teile Polyamid-6-Fasermaterial werden in 2000 Teile wäßrige Färbeflotte eingetragen, die 0,1 Teile des Kupferkomplexes

Figure imgb0005
sowie 0,15 Teile des Metallkomplex-Farbstoffes nach Beispiel 1a enthalten.100 parts of polyamide 6 fiber material are introduced into 2000 parts of an aqueous dyeing liquor containing 0.1 part of the copper complex
Figure imgb0005
 and 0.15 parts of the metal complex dye according to Example 1a.

Durch Zugabe von Dinatriumphosphat und Mononatriumphosphat wird ein pH-Wert von 8 eingestellt. Danach wird die Flottentemperatur unter Bewegung des Färbegutes langsam auf 98 - 100°C erhöht und während 1 Stunde bei dieser Temperatur belassen. Anschließend wird die Färbung gespült und getrocknet.A pH of 8 is set by adding disodium phosphate and monosodium phosphate. The liquor temperature is then slowly increased to 98-100 ° C. while moving the material to be dyed and left at this temperature for 1 hour. The dyeing is then rinsed and dried.

Die Färbung wird zusammen mit einer ohne (2) hergestellten Färbung belichtet.The coloring is exposed together with a coloring produced without (2).

Die mit (2) behandelte Färbung zeigt eine erheblich bessere Lichtechtheit.The coloring treated with (2) shows a considerably better light fastness.

Beispiel 5bExample 5b

Eine gleichgute Lichtechtheit erhält man, wenn die Färbeflotte nicht auf pH 8 sondern auf pH 6 eingestellt wird.An equally good lightfastness is obtained if the dye liquor is adjusted to pH 6 rather than pH 8.

Beispiel 5cExample 5c

Werden die nach 5a bzw. 5b hergestellten Färbungen anschließend während 30 s bei 180°C thermofixiert, so bleibt die Lichtechtheitsverbesserung voll erhalten.If the dyeings produced according to 5a or 5b are subsequently heat-set at 180 ° C. for 30 s, the improvement in light fastness is fully retained.

Beispiel 6Example 6 (Vergleichsbeispiel)(Comparative example)

Wird wie in Beispiel 1a beschrieben gefärbt, jedoch anstelle des Kupferkomplexes (1) der entsprechende Nickelkomplex mit 0,1 % bezogen auf das Fasergewicht verwendet, erhält man sowohl bei pH 6 als auch bei pH 8 keine Lichtechtheitsverbesserung. Die Färbung verhält sich bei der Belichtung so, als sei kein Lichtschutzmittel der Färbeflotte zugesetzt worden.If dyeing is carried out as described in Example 1a, but instead of the copper complex (1) the corresponding nickel complex is used at 0.1% based on the fiber weight, no improvement in light fastness is obtained either at pH 6 or at pH 8. When exposed to light, the coloring behaves as if no light stabilizer has been added to the dyeing liquor.

Beispiel 7aExample 7a

100 Teile Polyamid-6-Textilmaterial werden in 2000 Teile wäßrige Färbeflotte eingetragen, die 0,1 Teile Salicylaldoxim (1, R = H) sowie 0,2 Teile des Metallkomplex-Farbstoffes nach Beispiel 1 a enthalten.100 parts of polyamide 6 textile material are introduced into 2000 parts of an aqueous dyeing liquor containing 0.1 part of salicylaldoxime (1, R = H) and 0.2 part of the metal complex dye according to Example 1a.

Durch Zugabe von Dinatriumphosphat und Mononatriumphosphat wird in der Färbeflotte ein pH-Wert von 8 eingestellt. Unter ständiger Bewegung des Färbegutes wird die Temperatur der Färbeflotte allmählich auf 98 - 100°C gesteigert und für 60 Minuten bei dieser Temperatur belassen.By adding disodium phosphate and monosodium phosphate, a pH of 8 is set in the dye liquor. With constant movement of the material to be dyed, the temperature of the dyebath is gradually increased to 98-100 ° C and left at this temperature for 60 minutes.

Nach Abkühlen der Flotte wird das Polyamid-Material entnommen, kurz gespült und in 2000 Teile frische Färbeflotte, die 0,1 Teile CuS04.5H20 enthalten, gegeben. Nach allmählicher Erwärmung der Flotte auf 98 - 100° C wird diese für 30 Minuten bei dieser Endtemperatur behandelt. Während der gesamten Behandlungszeit wird das Färbegut gleichmäßig bewegt.After the liquor has cooled, the polyamide material is removed, rinsed briefly and added to 2000 parts of fresh dye liquor which contain 0.1 part of CuS0 4. 5H 20. After gradually warming the liquor to 98-100 ° C, it is treated for 30 minutes at this final temperature. The material to be dyed is moved evenly throughout the treatment.

Nach Abkühlen der Färbeflotte wird das Färbegut entnommen, gespült und getrocknet.After the dye liquor has cooled, the material to be dyed is removed, rinsed and dried.

Die Färbung wird gemeinsam mit einer ohne Salicylaldoxim/ Kupfersulfat-Nachbehandlung hergestellte Färbung nach "Opel-Test" belichtet. Die mit Salicylaldoxim/CuS04.5H20 zweibadig hergestellte Färbung zeigt eine wesentlich bessere Lichtechtheit.The dyeing is exposed together with a dye prepared without salicylaldoxime / copper sulfate aftertreatment according to the "Opel test". The dyeing produced with two baths with salicylaldoxime / CuS0 4 .5H 2 0 shows a much better light fastness.

Beispiel 7bExample 7b

Eine gleichgute Lichtechtheit erhält man, wenn die Salicylaldoxim enthaltende Färbeflotte nicht auf pH 8 sondern auf pH 6 eingestellt wird.An equally good light fastness is obtained if the dye liquor containing salicylaldoxime is adjusted not to pH 8 but to pH 6.

Beispiel 7cExample 7c

Werden die nach 7 a und 7 b hergestellten Färbungen einer in der Textilindustrie als Endbehandlung üblichen Thermofixierung während 30 s bei 180°C unterworfen, wird die Lichtechtheit nicht negativ beeinflußt.If the dyeings produced according to 7 a and 7 b are subjected to a heat-setting which is customary in the textile industry as a final treatment for 30 s at 180 ° C., the light fastness is not adversely affected.

Claims (9)

1. Process for improving the light fastness of polyamide dyeings using light fastness improvers based on copper compounds of phenols, characterised in that the phenols used are those compounds of the formula I
Figure imgb0008
in which
R denotes H, OH or C1-C4-alkyl.
2. Process according to Claim 1, characterised in that 0,01 - 2 % (based on weightof fibre) of the copper compounds are used.
3. Process according to Claim 1, characterised in that copper compounds of salicylaldoxime are used.
4. Process according to Claim 1, characterised in that copper compounds of salicylhydroxamic acid are used.
5. Process according to Claim 1, characterised in that the copper compounds are applied to thepolyamide fibres before, during or after dyeing.
6. Process according to Claim 1, characterised in that the copper compounds are added to the dyebath.
7. Process according to Claim 1, characterised in that the copper compounds are produced in situ on the fibre from the corresponding starting materials.
8. Process according to Claim 1, characterised in that polyamide dyeings obtained with metal complex dyestuffs are improved.
9. Process according to Claim 1, characterised im that dyeings on synthetic polyamides are improved.
EP83112324A 1982-12-20 1983-12-08 Process for improving the fastness to light of polyamide dyeings Expired EP0113856B1 (en)

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DE19823247051 DE3247051A1 (en) 1982-12-20 1982-12-20 METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS

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US5344467A (en) 1991-05-13 1994-09-06 The Lubrizol Corporation Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same
US5360459A (en) 1991-05-13 1994-11-01 The Lubrizol Corporation Copper-containing organometallic complexes and concentrates and diesel fuels containing same
US5376154A (en) 1991-05-13 1994-12-27 The Lubrizol Corporation Low-sulfur diesel fuels containing organometallic complexes
US5518510A (en) 1991-05-13 1996-05-21 The Lubrizol Corporation Low-sulfur diesel fuels containing organo-metallic complexes

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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
US4707161A (en) * 1983-07-23 1987-11-17 Basf Aktiengesellschaft Lightfastness of dyeings obtained with acid dyes or metal complex dyes on polyamides: treatment with copper hydroxamates
DE3577450D1 (en) * 1984-06-15 1990-06-07 Ciba Geigy Ag METHOD FOR COLORING HIGH MOLECULAR ORGANIC MATERIAL AND NEW METAL COMPLEXES.
EP0181836B1 (en) * 1984-11-09 1988-12-21 Ciba-Geigy Ag Process for improving the light fastness of dyed leathers
DE3565136D1 (en) * 1984-12-21 1988-10-27 Ciba Geigy Ag Process for the photochemical stabilisation of synthetic fibrous materials containing polyamide fibres
EP0200843B1 (en) * 1985-05-09 1988-06-22 Ciba-Geigy Ag Process for the photochemical stabilisation of undyed and dyed polyamide fibrous material and its mixtures
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
US4813970A (en) * 1988-02-10 1989-03-21 Crompton & Knowles Corporation Method for improving the lightfasteness of nylon dyeings using copper sulfonates
ES2059820T3 (en) * 1988-09-29 1994-11-16 Ciba Geigy Ag PROCEDURE FOR THE PHOTOCHEMICAL STABILIZATION OF MATERIAL OF DYED AND UNDYED POLYAMIDIC FIBERS, AND OF THEIR MIXTURES.
DE3925259A1 (en) * 1989-07-29 1991-01-31 Bayer Ag DRY PREPARATION OF LIGHT fastness improvers
DE3941295A1 (en) * 1989-12-14 1991-06-20 Basf Ag METHOD FOR COLORING POLYAMIDE SUBSTRATES
EP0511166A1 (en) * 1991-04-26 1992-10-28 Ciba-Geigy Ag Process for photochemical and thermic stabilization of polyamide fibre material with a fiberaffinitive copper complex and an oxalicacid diarylamide
TWI274070B (en) * 2002-10-15 2007-02-21 Sipix Imaging Inc Novel fluorinated dye stabilizers in fluorinated dielectric solvent

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DE3041153A1 (en) * 1980-10-31 1982-06-16 Bayer Ag, 5090 Leverkusen METHOD FOR IMPROVING THE LIGHT FASTNESS OF POLYAMIDE COLORS

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US5340369A (en) 1991-05-13 1994-08-23 The Lubrizol Corporation Diesel fuels containing organometallic complexes
US5344467A (en) 1991-05-13 1994-09-06 The Lubrizol Corporation Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same
US5360459A (en) 1991-05-13 1994-11-01 The Lubrizol Corporation Copper-containing organometallic complexes and concentrates and diesel fuels containing same
US5376154A (en) 1991-05-13 1994-12-27 The Lubrizol Corporation Low-sulfur diesel fuels containing organometallic complexes
US5518510A (en) 1991-05-13 1996-05-21 The Lubrizol Corporation Low-sulfur diesel fuels containing organo-metallic complexes
US5534039A (en) 1991-05-13 1996-07-09 The Lubrizol Corporation Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same
US5562742A (en) 1991-05-13 1996-10-08 The Lubrizol Corporation Copper-containing organometallic complexes and concentrates and diesel fuels containing same

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DE3247051A1 (en) 1984-06-20
US4544372A (en) 1985-10-01

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