EP0245204B1 - Process for the photochemical stabilization of undyed and dyed fibrous polyamide material and its mixture with other fibres - Google Patents

Description

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 treatment with non-coloring organic copper complexes, light stabilizers and antioxidants.

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 69 (1980), 3, pages 19 and 20. However, inorganic or organic copper salts often have the disadvantage that they absorb insufficiently and unevenly onto the polyamide fiber and are therefore used in high concentrations to achieve the desired effect. Usually they can only be used as post-treatment and in discontinuous procedures.

EP-A 51 188 recommends treating the polyamide material before, during or after the dyeing with a mixture of copper complexes of bisazomethines and light stabilizers to improve the lightfastness of polyamide dyeings. However, these copper complexes have an undesirable inherent color and an inadequate hydrolysis and acid stability, as is correctly stated in EP-A 113 856 by the same applicant.

EP-A 113 856 discloses less colored copper complexes of salicylaldoxime and salicylhydroxamic acid, which are used solely to improve the light fastness of polyamide dyeings.

From EP-A 162 811 and Textilveredlung 20 (1985), No. 11, pages 346-357, the use of non-coloring, dye bath-stable, fiber-affine copper complex compounds for light or light-heat stabilization of dyeings on polyamide fibers is known. The improvements in authenticity and properties thus achieved currently satisfy e.g. claims made by the auto industry.

It has now been found that a mixture of copper complex compounds, light stabilizers and antioxidants allows a further improvement in the fastness properties and properties such as light fastness and tear resistance.

• A) einem nicht färbenden Bisazomethin-Kupferkomplex der Formel (5)
  
  worin
  R₆, R₇, R₈ und R₉ je Wasserstoff, Hydroxy, Chlor, Brom, Methyl, tert.Butyl, Methoxy, Methoxyethoxy, Ethoxyethoxyethoxy oder Diäthylamino,
  X₁ Wasserstoff, Methyl, Ethyl oder Phenyl und
  Y₁ Wasserstoff bedeuten
  oder R₆ und R₇ zusammen einen ankondensierten Benzolrest oder X₁ und Y₁ zusammen einen Cyclohexylenrest bilden,
• B) einem Lichtschutzmittel und gewünschtenfalls
• C) einem Antioxidant

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 fiber materials, which is characterized in that the fiber material is mixed with a mixture

• A) a non-coloring bisazomethine copper complex of the formula (5)
  
  wherein
  R₆, R₇, R₈ and R₉ each represent hydrogen, hydroxy, chlorine, bromine, methyl, tert-butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino,
  X₁ is hydrogen, methyl, ethyl or phenyl and
  Y₁ is hydrogen
  or R₆ and R₇ together form a fused-on benzene radical or X₁ and Y₁ together form a cyclohexylene radical,
• B) a light stabilizer and if desired
• C) an antioxidant

treated.

The compounds which can be used as component A) have an excellent affinity for the polyamide fiber material. They are therefore effective in extremely small amounts.

Bisazomethines of aromatic aldehydes are understood to mean Schiff bases of aliphatic diamines, the aldehydes having an HO group in the o-position to the formyl radical. The bond with the metal atom takes place via these two HO groups and the two nitrogen atoms in the bisazomethine part. Accordingly, these are tidentate ligands.

worin
R₁₀, R₁₁ und R₁₃ je Wasserstoff, Chlor, Brom, Methyl oder Methoxy bedeuten oder R₁₀ und R₁₁ zusammen einen ankondensierten Benzolring bilden, R₁₂ Wasserstoff oder Hydroxy und X₂ Wasserstoff, Methyl, Ethyl oder Phenyl ist.Copper complexes of the formula (6) are of particular interest

wherein
R₁₀, R₁₁ and R₁₃ each represent hydrogen, chlorine, bromine, methyl or methoxy or R₁₀ and R₁₁ together form a fused benzene ring, R₁₂ is hydrogen or hydroxy and X₂ is hydrogen, methyl, ethyl or phenyl.

Of particular interest are those compounds of formula (6) in which R₁₀, R₁₁, R₁₂, R₁₃ and X₂ are hydrogen.

All those compounds which are also known as UV absorbers and are described, for example, in Kirk-Othmer 23 , 615-627; AF Strobel, ADR, 50 , (1961), 583-588; 51 (1962) 99-104 R. Gächter and H. Müller, Taschenbuch der Kunststoff-Additive, Carl Hanser Verlag, Munich pp. 101-198 (1983) and in US-A-4,511,596.

• a) 2-Hydroxybenzophenone der Formel (7)
  
  worin
  R₁ Wasserstoff, Hydroxy oder C₁-C₁₄-Alkoxy,
  R₂ Wasserstoff, C₁-C₄-Alkyl oder Sulfo,
  R₃ Wasserstoff, Hydroxy oder C₁-C₄-Alkoxy und
  R₄ Wasserstoff, Hydroxy oder Carboxy
  bedeuten,
  wie z.B. das 4-Hydroxy-, 4-Methoxy-, 4-Octyloxy-, 4-Decyloxy-, 4-Dodecyloxy-, 4-Methoxy-2'-carboxy-, 4,2',4'-Trihydroxy-, 4,4'-Dimethoxy-2'-hydroxy-, 4-Methoxy-5-sulfo- und 2'-Hydroxy-4,4'-dimethoxy-5-sulfo-, -Derivat;
• b) 2-(2'-Hydroxyphenyl)-benzotriazole der Formel (8)
  
  worin

  R₁

  Wasserstoff, C₁-C₁₂-Alkyl, Chlor, C₅-C₆-Cycloalkyl, C₇-C₉-Phenylalkyl oder Sulfo

  R₂

  Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Chlor, Hydroxy oder Sulfo,

  R₃

  C₁-C₁₂-Alkyl, C₁-C₄-Alkoxy, Phenyl, (C₁-C₈-Alkyl)-phenyl, C₅-C₆-Cycloalkyl, C₂-C₉-Alkoxycarbonyl, Chlor, Carboxyethyl oder C₇-C₉-Phenylalkyl oder Sulfo,

  R₄

  Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₉-Alkoxycarbonyl, Carboxy oder Sulfo und

  R₅

  Wasserstoff oder Chlor

  bedeuten, wobei die Carboxy- und Sulforeste auch als Salze, z.B. Alkalimetall-, Erdalkalimetall-, Ammonium- oder Aminsalze vorliegen können. Beispiele von Verbindungen der Formel (8) sind das 5'-Methyl-, 3',5'-Di-tert.butyl-, 5'-tert.Butyl-, 5'-(1,1,3,3-Tetramethylbutyl)-, 5-Chlor-3',5'-di-tert.butyl-, 5-Chlor-3'-tert.butyl-5'-methyl-, 3'-sec.Butyl-5'-tert.butyl-, 4'-Octyloxy-, 3',5'-Di-tert.amyl- und 3',5'-Bis-(α,α-dimethylbenzyl)-Derivat sowie das Natriumsalz der 2-(2'-Hydroxy-3'-tert.butyl-5'-methylphenyl)-5-(2H)-benzotriazolsulfonsäure und der 3-tert.-Butyl-4-hydroxy-5-[benzotriazol-(2)-yl]-benzolsulfonsäure.
• c) Verbindungen aus der Klasse der sterisch gehinderten Amine wie z.B. ein 2,2,6,6-Tetraalkylpiperidinderivat, welches in seinem Molekül mindestens eine Gruppe der Formel (9)
  
  enthält, worin R Wasserstoff oder Methyl bedeutet.
  Das Lichtschutzmittel kann eine oder mehrere solcher Gruppen der Formel (9) enthalten, beispielsweise kann es sich um eine Mono-, Bis-, Tris-, Tetra- oder Oligo-piperidinverbindung handeln. Bevorzugt sind Piperidinderivate, die eine oder mehrere Gruppen der Formel (9) enthalten, worin R Wasserstoff ist, sowie solche, deren Ringstickstoff kein Wasserstoffatom trägt.
  Die meisten dieser Piperidin-Lichtschutzmittel tragen polare Substituenten in der 4-Stellung des Piperidinringes.
  Von Bedeutung sind insbesondere die folgenden Klassen von Piperidinverbindungen.
  • aa) Verbindungen der Formel (10)
    
    worin n eine Zahl von 1 bis 4, vorzugsweise 1 oder 2 bedeutet, R Wasserstoff oder Methyl bedeutet, R¹ Wasserstoff, Oxyl, C₁-C₁₈ Alkyl, C₃-C₈ Alkenyl, C₃-C₈ Alkinyl, C₇-C₁₂ Aralkyl, C₁-C₈ Alkanoyl, C₃-C₅ Alkenoyl, Glycidyl oder eine Gruppe -CH₂CH(OH)-Z, worin Z Wasserstoff, Methyl oder Phenyl ist, bedeutet, wobei R¹ vorzugsweise C₁-C₁₂ Alkyl, Allyl, Benzyl, Acetyl oder Acryloyl ist und R², wenn n 1 ist, Wasserstoff, gegebenenfalls durch ein oder mehrere Sauerstoffatome unterbrochenes C₁-C₁₈ Alkyl, Cyanethyl, Benzyl, Glycidyl, einen einwertigen Rest einer aliphatischen, cycloaliphatischen, araliphatischen, ungesättigten oder aromatischen Carbonsäure, Carbaminsäure oder Phosphor enthaltenden Säure oder einen einwertigen Silylrest, vorzugsweise einen Rest einer aliphatischen Carbonsäure mit 2 bis 18 C-Atomen, einer cycloaliphatischen Carbonsäure mit 7 bis 15 C-Atomen, einer α,β-ungesättigten Carbonsäure mit 3 bis 5 C-Atomen oder einer aromatischen Carbonsäure mit 7 bis 15 C-Atomen bedeutet, wenn n 2 ist, C₁-C₁₂ Alkylen, C₄-C₁₂ Alkenylen, Xylylen, einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen, araliphatischen oder aramatischen Dicarbonsäure, Dicarbaminsäure oder Phosphor enthaltenden Säure oder einen zweiwertigen Silylrest, vorzugsweise einen Rest einer aliphatischen Dicarbonsäure mit 2 bis 36 C-Atomen, einer cycloaliphatischen oder aromatischen Dicarbonsäure mit 8 - 14 C-Atomen oder einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbaminsäure mit 8 - 14 C-Atomen bedeutet, wenn n 3 ist, einen dreiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tricarbonsäure, einer aromatischen Tricarbaminsäure oder einer Phosphor enthaltenden Säure oder einen dreiwertigen Silylrest bedeutet und wenn n 4 ist, einen vierwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Tetracarbonsäure bedeutet.
    Bedeuten etwaige Substituenten C₁-C₁₂ Alkyl, so stellen sie z.B. Methyl, Ethyl, n-Propyl, n-Butyl, sek.-Butyl, tert.-Butyl, n-Hexyl, n-Octyl, 2-Ethyl-hexyl, n-Nonyl, n-Decyl, n-Undecyl oder n-Dodecyl dar.
    In der Bedeutung von C₁-C₁₈ Alkyl können R¹ oder R² z.B. die oben angeführten Gruppen und dazu noch beispielsweise n-Tridecyl, n-Tetradecyl, n-Hexadecyl oder n-Octadecyl darstellen.
    Wenn R¹ C₃-C₈ Alkenyl bedeutet, so kann es sich z.B. um 1-Propenyl, Allyl, Methallyl, 2-Butenyl, 2-Pentenyl, 2-Hexenyl, 2-Octenyl, 4-tert.-Butyl-2-butenyl handeln.
    R¹ ist als C₃-C₈ Alkinyl bevorzugt Propargyl.
    Als C₇-C₁₂ Aralkyl ist R¹ insbesondere Phenethyl oder vor allem Benzyl.
    R¹ ist als C₁-C₈ Alkanoyl beispielsweise Formyl, Propionyl, Butyryl, Octanoyl, aber bevorzugt Acetyl und als C₃-C₅ Alkenoyl insbesondere Acryloyl.
    Bedeutet R² einen einwertigen Rest einer Carbonsäure, so stellt es beispielsweise einen Essigsäure-, Capronsäure-, Stearinsäure-, Acrylsäure-, Methacrylsäure-, Benzoe- oder β-(3,5-Di-tert.-butyl-4-hydroxy-phenyl)-propionsäurerest dar.
    Bedeutet R² einen zweiwertigen Rest einer Dicarbonsäure, so stellt es beispielsweise einen Malonsäure-, Adipinsäure-, Korksäure-, Sebacinsäure-, Maleinsäure-, Phthalsäure-, Dibutylmalonsäure-, Dibenzylmalonsäure-, Butyl-(3,5-di-tert.-butyl-4-hydroxybenzyl)malonsäure- oder Bicycloheptendicarbonsäurerest dar.
    Stellt R² einen dreiwertigen Rest einer Tricarbonsäure dar, so bedeutet es z.B. einen Trimellitsäure- oder einen Nitrilotriessigsäurerest.
    Stellt R² einen vierwertigen Rest einer Tetracarbonsäure dar, so bedeutet es z.B. den vierwertigen Rest von Butan-1,2,3,4-tetracarbonsäure oder von Pyromellitsäure.
    Bedeutet R² einen zweiwertigen Rest einer Dicarbaminsäure, so stellt es beispielsweise einen Hexamethylendicarbaminsäure- oder einen 2,4-Toluylen-dicarbaminsäurerest dar.
    Beispiele für Tetraalkylpiperidin-Verbindungen dieser Klasse sind folgende Verbindungen:
    • 1) 4-Hydroxy-2,2,6,6-tetramethylpiperidin
    • 2) 1-Allyl-4-hydroxy-2,2,6,6-tetramethylpiperidin
    • 3) 1-Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidin
    • 4) 1-(4-tert.-Butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidin
    • 5) 4-Stearoyloxy-2,2,6,6-tetramethylpiperidin
    • 6) 1-Ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidin
    • 7) 4-Methacryloyloxy-1,2,2,6,6-pentamethylpiperidin
    • 8) 1,2,2,6,6-Pentamethylpiperidin-4-yl-β-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionat
    • 9) Di-(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)-maleinat
    • 10) Di-(2,2,6,6-tetramethylpiperidin-4-yl)-adipat
    • 11) Di-(2,2,6,6-tetramethylpiperidin-4-yl)-sebacat
    • 12) Di-(1,2,3,6-tetramethyl-2,6-diethylpiperidin-4-yl)-sebacat
    • 13) Di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl)-phthalat
    • 14) 1-Propargyl-4-β-cyanoethyloxy-2,6,6,6-tetramethylpiperidin
    • 15) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetat
    • 16) Trimellithsäure-tri-(2,2,6,6-tetramethylpiperidin-4-yl)-ester
    • 17) 1-Acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidin
    • 18) Dibutyl-malonsäure-di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-ester
    • 19) Butyl-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonsäure-di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-ester
    • 20) Dibenzyl-malonsäure-di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-ester
    • 21) Dibenzyl-malonsäure-di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)ester
    • 22) Hexan-1',6'-bis-(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidin)
    • 23) Tuluol-2',4'-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidin)
    • 24) Dimethyl-bis-(2,2,6,6-tetramethylpiperidin-4-oxy)-silan
    • 25) Phenyl-tris-(2,2,6,6-tetramethylpiperidin-4-oxy)-silan
    • 26) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)-phosphit
    • 27) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)phosphat
    • 28) Phenyl-[bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)]-phosphonat
    • 29) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-sebacat
    • 30) 4-Hydroxy-1,2,2,6,6-pentamethylpiperidin
    • 31) 4-Hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidin
    • 32) 4-Hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidin
    • 33) 1-Glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidin
  • bb) Verbindungen der Formel (11)
    
    worin n die Zahl 1 oder 2 bedeutet, R und R¹ die unter aa) angegebene Bedeutung haben, R³ Wasserstoff, C₁-C₁₂ Alkyl, C₂-C₅ Hydroxyalkyl, C₅-C₇ Cycloalkyl, C₇-C₈ Aralkyl, C₂-C₁₈ Alkanoyl, C₃-C₅ Alkenoyl oder Benzoyl ist und R⁴ wenn n 1 ist, Wasserstoff, C₁-C₁₈ Alkyl, C₃-C₈ Alkenyl, C₅-C₇ Cycloalkyl, mit einer Hydroxy-, Cyano-, Alkoxycarbonyl- oder Carbamidgruppe substituiertes C₁-C₄ Alkyl, Glycidyl, eine Gruppe der Formel -CH₂-CH(OH)-Z oder der Formel -CONH-Z ist, worin Z Wasserstoff, Methyl oder Phenyl bedeutet; wenn n 2 ist, C₂-C₁₂ Alkylen, C₆-C₁₂ Arylen, Xylylen, eine -CH₂-CH(OH)-CH₂-Gruppe oder eine Gruppe -CH₂-CH(OH)-CH₂-O-D-O-bedeutet, worin D C₂-C₁₀ Alkylen, C₆-C₁₅ Arylen, C₆-C₁₂ Cycloalkylen ist, oder vorausgesetzt, dass R³ nicht Alkanoyl, Alkenoyl oder Benzoyl bedeutet, R⁴ auch einen zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbonsäure oder Dicarbaminsäure oder auch die Gruppe -CO- bedeuten kann, oder R³ und R⁴ zusammen, wenn n 1 ist, den zweiwertigen Rest einer aliphatischen, cycloaliphatischen oder aromatischen 1,2- oder 1,3-Dicarbonsäure bedeuten können.
  
  Stellen etwaige Substituenten C₁-C₁₂- oder C₁-C₁₈Alkyl dar, so haben sie die bereits unter aa) angegebene Bedeutung.
  Bedeuten etwaige Substituenten C₅-C₇ Cycloalkyl, so stellen sie insbesondere Cyclohexyl dar.
  Als C₇-C₈ Aralkyl ist R³ insbesondere Phenylethyl oder vor allem Benzyl. Als C₂-C₅Hydroxyalkyl ist R³ insbesondere 2-Hydroxyethyl oder 2-Hydroxypropyl.
  R³ ist als C₂-C₁₈ Alkanoyl beispielsweise Propionyl, Butyryl, Octanoyl, Dodecanoyl, Hexadecanoyl, Octadecanoyl, aber bevorzugt Acetyl und als C₃-C₅ Alkenoyl insbesondere Acryloyl.
  Bedeutet R⁴ C₂-C₈ Alkenyl, dann handelt es sich z.B. um Allyl, Methallyl, 2-Butenyl, 2-Pentenyl, 2-Hexenyl oder 2-Octenyl.
  R⁴ als mit einer Hydroxy-, Cyano-, Alkoxycarbonyl- oder Carbamidgruppe substituiertes C₁-C₄-Alkyl kann z.B. 2-Hydroxyethyl, 2-Hydroxypropyl, 2-Cyanethyl, Methoxycarbonylmethyl, 2-Ethoxycarbonylethyl, 2-Aminocarbonylpropyl oder 2-(Dimethylaminocarbonyl)-ethyl sein.
  Stellen etwaige Substituenten C₂-C₁₂ Alkylen dar, so handelt es sich z.B. um Ethylen, Propylen, 2,2-Dimethylpropylen, Tetramethylen, Hexamethylen, Octamethylen, Decamethylen oder Dodecamethylen.
  Bedeuten etwaige Substituenten C₆-C₁₅-Arylen, so stellen sie z.B. o-, m- oder p-Phenylen, 1,4-Naphthylen oder 4,4'-Diphenylen dar.
  Als C₆-C₁₂ Cycloalkylen ist D insbesondere Cyclohexylen.
  Beispiele für Tetraalkylpiperidin-Verbindungen dieser Klasse sind folgende Verbindungen:
  • 34) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylen-1,6-diamin
  • 35) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylen-1,6-diacetamid
  • 36) 1-Acetyl-4-(N-cyclohexylacetamido)-2,2,6,6-tetramethylpiperidin
  • 37) 4-Benzoylamino-2,2,6,6-tetramethylpiperidin
  • 38) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyladipamid
  • 39) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2-hydroxypropylen-1,3-diamin
  • 40) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylen-diamin
  • 41) Die Verbindung der Formel
    
  • 42) 4-(Bis-2-hydroxyethyl-amino)-1,2,2,6,6-pentamethylpiperidin
  • 43) 4-(3-Methyl-4-hydroxy-5-tert.-butyl-benzoesäureamido)-2,2,6,6-tetramethylpiperidin und
  • 44) 4-Methacrylamido-1,2,2,6,6-pentamethylpiperidin;
• d) 2-(2'-Hydroxyphenyl)-s-triazine der Formel (12)
  
  worin R Wasserstoff, Halogen, C₁-C₄-Alkyl oder Sulfo, R₁ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Hydroxy, R₂ Wasserstoff oder Sulfo und R₃ und R₄ unabhängig voneinander C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₅-C₆-Cycloalkyl, Phenyl oder durch C₁-C₄-Alkyl und Hydroxy substituiertes Phenyl bedeuten, wobei die Sulfogruppen in freier Form oder in Salzform, z.B. Alkalimetall-, Erdalkalimetall-, Ammonium- oder Aminsalze vorliegen können. Beispiele von Verbindungen der Formel (12) sind das 2-(2',4'-Dihydroxyphenyl)-4,6-diphenyl-s-triazin, 2-(2'-Hydroxy-4'-methoxyphenyl)-4,6-diphenyl-s-triazin, 2-(2'-Hydroxy-5'-methylphenyl)-4,6-diphenyl-s-triazin, 2,4-Bis-(2'-hydroxy-3'-methylphenyl)-6-ethyl-s-triazin, 2,4-Bis-(2'-hydroxyphenyl)-6-methoxy-s-triazin, 2,4-Bis-cyclohexyl-6-(2'-hydroxy-4'-methoxyphenyl)-s-triazin und 2-(2'-Hydroxy-4'-methoxy-5'-sulfophenyl)-4,6-diphenyl-s-triazin; (vergl. z.B. WO-A-86/03528)
• e) s-Triazinverbindungen der Formel
  
  worin mindestens einer der Substituenten R₁, R₂ und R₃ ein Rest der Formel
  
  ist, worin M Natrium, Kalium, Calcium, Magnesium, Ammonium oder Tetra-C₁-C₄-alkylammonium und m 1 oder 2 ist, und der übrige Substituent bzw. die übrigen Substituenten unabhängig voneinander C₁-C₁₂-Alkyl, Phenyl, durch Sauerstoff, Schwefel, Imino oder C₁-C₄-Alkylimino an den Triazinylrest gebundenes C₁-C₁₂-Alkyl oder Phenyl ist, wie z.B. das Kaliumsalz der Verbindung der Formel (12a), worin R₁ Phenyl und R₂ und R₃ je der Rest der Formel (12b) bedeuten oder das Natriumsalz der Verbindung der Formel (12a), worin R₁ p-Chlorphenyl und R₂ und R₃ je den Rest der Formel (12b) bedeuten. Weitere Verbindungen sind in EP-A-165608 beschrieben.

The following compounds can be used as component B):

• a) 2-hydroxybenzophenones of the formula (7)
  
  wherein
  R₁ is hydrogen, hydroxy or C₁-C₁₄ alkoxy,
  R₂ is hydrogen, C₁-C₄ alkyl or sulfo,
  R₃ is hydrogen, hydroxy or C₁-C₄ alkoxy and
  R₄ is hydrogen, hydroxy or carboxy
  mean,
  such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-methoxy-2'-carboxy, 4,2 ', 4'-trihydroxy-, 4 , 4'-dimethoxy-2'-hydroxy, 4-methoxy-5-sulfo and 2'-hydroxy-4,4'-dimethoxy-5-sulfo, derivative;
• b) 2- (2'-hydroxyphenyl) benzotriazoles of the formula (8)
  
  wherein

  R₁

  Hydrogen, C₁-C₁₂-alkyl, chlorine, C₅-C₆-cycloalkyl, C₇-C₉-phenylalkyl or sulfo

  R₂

  Hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, chlorine, hydroxy or sulfo,

  R₃

  C₁-C₁₂-alkyl, C₁-C₄-alkoxy, phenyl, (C₁-C₈-alkyl) -phenyl, C₅-C₆-cycloalkyl, C₂-C₉-alkoxycarbonyl, chlorine, carboxyethyl or C₇-C₉-phenylalkyl or sulfo,

  R₄

  Hydrogen, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₉-alkoxycarbonyl, carboxy or sulfo and

  R₅

  Hydrogen or chlorine

  mean, the carboxy and sulo radicals can also be present as salts, for example alkali metal, alkaline earth metal, ammonium or amine salts. Examples of compounds of formula (8) are 5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5' - (1,1,3,3-tetramethylbutyl ) -, 5-Chloro-3 ', 5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl -, 4'-octyloxy, 3 ', 5'-di-tert.amyl and 3', 5'-bis (α, α-dimethylbenzyl) derivative as well as the sodium salt of 2- (2'-hydroxy- 3'-tert-butyl-5'-methylphenyl) -5- (2H) -benzotriazolesulfonic acid and 3-tert.-butyl-4-hydroxy-5- [benzotriazol- (2) -yl] -benzenesulfonic acid.
• c) compounds from the class of sterically hindered amines, such as, for example, a 2,2,6,6-tetraalkylpiperidine derivative, which has at least one group of the formula (9) in its molecule
  
  contains, wherein R is hydrogen or methyl.
  The light stabilizer can contain one or more such groups of the formula (9), for example it can be a mono-, bis-, tris-, tetra- or oligo-piperidine compound. Prefers are piperidine derivatives which contain one or more groups of the formula (9) in which R is hydrogen, and those whose ring nitrogen does not bear a hydrogen atom.
  Most of these piperidine light stabilizers have polar substituents in the 4-position of the piperidine ring.
  The following classes of piperidine compounds are of particular importance.
  • aa) compounds of the formula (10)
    
    wherein n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, R¹ is hydrogen, oxyl, C₁-C₁₈ alkyl, C₃-C₈ alkenyl, C₃-C₈ alkynyl, C₇-C₁₂ aralkyl, C₁-C₈ alkanoyl , C₃-C₅ alkenoyl, glycidyl or a group -CH₂CH (OH) -Z, where Z is hydrogen, methyl or phenyl, where R¹ is preferably C₁-C₁₂ alkyl, allyl, benzyl, acetyl or acryloyl and R² if n 1 is hydrogen, optionally interrupted by one or more oxygen atoms C₁-C₁₈ alkyl, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably one The rest of an aliphatic carboxylic acid with 2 to 18 C atoms, a cycloaliphatic carboxylic acid with 7 to 15 C atoms, an α, β-unsaturated carboxylic acid with 3 to 5 C atoms or one Aromatic carboxylic acid having 7 to 15 carbon atoms means when n is 2, C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aramatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent acid Silyl radical, preferably a radical of an aliphatic dicarboxylic acid with 2 to 36 C atoms, a cycloaliphatic or aromatic dicarboxylic acid with 8-14 C atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid with 8 - 14 C atoms, if n is 3, represents a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphorus-containing acid or a trivalent silyl radical and, when n is 4, means a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
    If any substituents are C₁-C₁₂ alkyl, they represent, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n- Nonyl, n-decyl, n-undecyl or n-dodecyl.
    In the meaning of C₁-C₁₈ alkyl, R¹ or R² can represent, for example, the groups mentioned above and, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
    If R¹ is C₃-C₈ alkenyl, it can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.
    R¹ as C₃-C₈ alkynyl is preferably propargyl.
    As C₇-C₁₂ aralkyl, R¹ is in particular phenethyl or especially benzyl.
    R¹ is as C₁-C₈ alkanoyl, for example formyl, propionyl, butyryl, octanoyl, but preferably acetyl and as C₃-C₅ alkenoyl in particular acryloyl.
    If R² is a monovalent radical of a carboxylic acid, it is, for example, acetic, caproic, stearic, acrylic, methacrylic, benzoic or β- (3,5-di-tert-butyl-4-hydroxy-phenyl) ) -propionic acid residue.
    If R² is a divalent radical of a dicarboxylic acid, it is, for example, a malonic, adipic, suberic, sebacic, maleic, phthalic, dibutylmalonic, dibenzylmalonic, butyl (3,5-di-tert-butyl) -4-hydroxybenzyl) malonic or bicycloheptenedicarboxylic acid residue.
    If R² represents a trivalent carboxylic acid residue, it means, for example, a trimellitic acid or a nitrilotriacetic acid residue.
    If R² represents a tetravalent residue of a tetracarboxylic acid, it means, for example, the tetravalent residue of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
    If R² is a divalent radical of a dicarbamic acid, it is, for example, a hexamethylene dicarbamic acid or a 2,4-tolylene dicarbamic acid radical.
    Examples of tetraalkylpiperidine compounds of this class are the following compounds:
    • 1) 4-Hydroxy-2,2,6,6-tetramethylpiperidine
    • 2) 1-Allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
    • 3) 1-Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
    • 4) 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine
    • 5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine
    • 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine
    • 7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine
    • 8) 1,2,2,6,6-pentamethylpiperidin-4-yl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
    • 9) Di- (1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleate
    • 10) Di- (2,2,6,6-tetramethylpiperidin-4-yl) adipate
    • 11) Di- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate
    • 12) Di- (1,2,3,6-tetramethyl-2,6-diethylpiperidin-4-yl) sebacate
    • 13) Di- (1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate
    • 14) 1-Propargyl-4-β-cyanoethyloxy-2,6,6,6-tetramethylpiperidine
    • 15) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate
    • 16) Trimellitic acid tri (2,2,6,6-tetramethylpiperidin-4-yl) ester
    • 17) 1-Acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine
    • 18) Dibutyl malonic acid di (1,2,2,6,6-pentamethylpiperidin-4-yl) ester
    • 19) Butyl- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid di- (1,2,2,6,6-pentamethylpiperidin-4-yl) ester
    • 20) Dibenzylmalonic acid di (1,2,2,6,6-pentamethylpiperidin-4-yl) ester
    • 21) Dibenzyl-malonic acid di- (1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) ester
    • 22) Hexane-1 ', 6'-bis (4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine)
    • 23) Tuluol-2 ', 4'-bis (4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine)
    • 24) Dimethyl bis (2,2,6,6-tetramethylpiperidine-4-oxy) silane
    • 25) Phenyl-tris (2,2,6,6-tetramethylpiperidine-4-oxy) silane
    • 26) Tris- (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite
    • 27) Tris- (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate
    • 28) Phenyl- [bis- (1,2,2,6,6-pentamethylpiperidin-4-yl)] phosphonate
    • 29) Di- (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate
    • 30) 4-Hydroxy-1,2,2,6,6-pentamethylpiperidine
    • 31) 4-Hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine
    • 32) 4-Hydroxy-N- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine
    • 33) 1-Glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
  • bb) compounds of the formula (11)
    
    in which n is the number 1 or 2, R and R¹ have the meaning given under aa), R³ is hydrogen, C₁-C₁₂ alkyl, C₂-C₅ hydroxyalkyl, C₅-C₇ cycloalkyl, C₇-C₈ aralkyl, C₂-C₁₈ alkanoyl, C₃- C₅ is alkenoyl or benzoyl and R⁴ when n is 1, hydrogen, C₁-C₁₈ alkyl, C₃-C₈ alkenyl, C₅-C₇ cycloalkyl, C₁-C₄ alkyl, glycidyl substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group, one Group of the formula -CH₂-CH (OH) -Z or the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; when n is 2, C₂-C₁₂ alkylene, C₆-C₁₂ arylene, xylylene, a -CH₂-CH (OH) -CH₂ group or a group -CH₂-CH (OH) -CH₂-ODO-, where D is C₂- C₁₀ alkylene, C₆-C₁₅ arylene, C₆-C₁₂ cycloalkylene, or provided that R³ is not alkanoyl, alkenoyl or benzoyl, R⁴ can also mean a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or the group -CO- , or R³ and R⁴ together, if n is 1, can mean the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.
  
  If any substituents are C₁-C₁₂- or C₁-C₁₈alkyl, they have the meaning already given under aa).
  Any substituents C₅-C₇ cycloalkyl, they represent in particular cyclohexyl.
  As C₇-C₈ aralkyl, R³ is especially phenylethyl or especially benzyl. As C₂-C₅Hydroxyalkyl R³ is in particular 2-hydroxyethyl or 2-hydroxypropyl.
  R³ is as C₂-C₁₈ alkanoyl, for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl and as C₃-C₅ alkenoyl in particular acryloyl.
  R⁴ C₂-C₈ means alkenyl, then it is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
  R⁴ as a C₁-C₄-alkyl substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) - be ethyl.
  Represent any substituents C₂-C₁₂ alkylene, it is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  If any substituents are C₆-C₁₅ arylene, they are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
  As C₆-C₁₂ cycloalkylene, D is especially cyclohexylene.
  Examples of tetraalkylpiperidine compounds of this class are the following compounds:
  • 34) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diamine
  • 35) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diacetamide
  • 36) 1-Acetyl-4- (N-cyclohexylacetamido) -2,2,6,6-tetramethylpiperidine
  • 37) 4-Benzoylamino-2,2,6,6-tetramethylpiperidine
  • 38) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dibutyladipamide
  • 39) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dicyclohexyl-2-hydroxypropylene-1,3-diamine
  • 40) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylene diamine
  • 41) The compound of the formula
    
  • 42) 4- (bis-2-hydroxyethylamino) -1,2,2,6,6-pentamethylpiperidine
  • 43) 4- (3-methyl-4-hydroxy-5-tert-butyl-benzoic acid amido) -2,2,6,6-tetramethylpiperidine and
  • 44) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine;
• d) 2- (2'-hydroxyphenyl) -s-triazines of the formula (12)
  
  wherein R is hydrogen, halogen, C₁-C₄-alkyl or sulfo, R₁ hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or hydroxy, R₂ hydrogen or sulfo and R₃ and R₄ independently of one another C₁-C₄-alkyl, C₁-C₄ -Alkoxy, C₅-C₆-cycloalkyl, phenyl or phenyl substituted by C₁-C₄-alkyl and hydroxy, where the sulfo groups can be present in free form or in salt form, for example alkali metal, alkaline earth metal, ammonium or amine salts. Examples of compounds of formula (12) are 2- (2 ', 4'-dihydroxyphenyl) -4,6-diphenyl-s-triazine, 2- (2'-hydroxy-4'-methoxyphenyl) -4,6- diphenyl-s-triazine, 2- (2'-hydroxy-5'-methylphenyl) -4,6-diphenyl-s-triazine, 2,4-bis (2'-hydroxy-3'-methylphenyl) -6- ethyl-s-triazine, 2,4-bis (2'-hydroxyphenyl) -6-methoxy-s-triazine, 2,4-bis-cyclohexyl-6- (2'-hydroxy-4'-methoxyphenyl) -s -triazine and 2- (2'-hydroxy-4'-methoxy-5'-sulfophenyl) -4,6-diphenyl-s-triazine; (see for example WO-A-86/03528)
• e) s-triazine compounds of the formula
  
  wherein at least one of the substituents R₁, R₂ and R₃ is a radical of the formula
  
  is where M is sodium, potassium, calcium, magnesium, ammonium or tetra-C₁-C₄-alkylammonium and m is 1 or 2, and the remaining substituent or substituents are independently of one another C₁-C₁₂-alkyl, phenyl, by oxygen, Sulfur, imino or C₁-C₄-alkylimino is C₁-C₁₂-alkyl or phenyl bonded to the triazinyl radical, such as, for example, the potassium salt of the compound of the formula (12a), in which R₁ is phenyl and R₂ and R₃ are each the rest of the formula (12b) or the sodium salt of the compound of formula (12a), wherein R₁ p-chlorophenyl and R₂ and R₃ each represent the rest of formula (12b). Further compounds are described in EP-A-165608.

Compounds C) which can be used are those described, for example, in Kirk-Othmer (3rd), 3 , pages 132-135 or in R. Gächter and H. Müller, Taschenbuch der Kunststoff-Additive, Carl Hanser Verlag, Munich, pages 4-78 (1983).

worin n eine ganze Zahl von 1 bis 4 und A C₁-C₂₄-Alkoxy, ein Brückenglied -O(CH₂)₆O-, -O(CH₂)₂O(CH₂)₂O-, -O(CH₂)₂O(CH₂)₂O(CH₂)₂O-, -HN-(CH₂)₂₋₆-NH- oder -O(CH₂)₂-S-(CH₂)₂O-oder den Rest (̵CH₂O)₄-C bedeuten, wie z.B. die Ester der 3-(3',5'-Di-tert.butyl-4-hydroxyphenyl)-propionsäure mit Methanol, Octadecanol, 1,6-Hexandiol, Diethylenglycol, Triethylenglycol oder Pentaerythrit oder die Diamide der 3-(3',5'-Di-tert.butyl-4-hydroxyphenyl)-propionsäure mit Ethylen-, Trimethylen- oder Hexamethylendiamin und Verbindüngen der Formel (14)

worin R Hydroxy, Phenyl, Phenoxy, C₁-C₁₈-Alkylphenoxy, C₁-C₂₄-Alkylthio oder C₁-C₂₄-Alkoxy, R₁ Phenoxy, C₁-C₁₈-Alkylphenoxy, C₁-C₂₄-Alkylthio oder C₁-C₂₄-Alkoxy, R₂ und R₃ unabhängig voneinander C₁-C₁₈-, vorzugsweise C₁-C₆-Alkyl und besonders tert.-Butyl in 3-und 5-Stellung, R₄ Wasserstoff oder C₁-C₄-Alkyl und n 0, 1, 2 oder 3, vorzugsweise 0 oder 1 bedeuten, wie z.B. Di-n-octadecyl-3-tert.-butyl-4-hydroxy-5-methylbenzyl-phosphonat, Di-n-octadecyl-1-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-ethan-phosphonat, Di-n-octadecyl-3,5-di-tert.-butyl-2-hydroxybenzyl-phosphonat, Di-n-dodecyl-2-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-ethan-phosphonat, Diethyl-3,5-di-tert.-butyl-4-hydroxybenzylphosphonat, Dimethyl-3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonat, Di-p-tert.-octylphenyl-3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonat, O-n-Butyl-3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonsäure, Di-n-butyl-3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonat und O-Ethyl-3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonsäure.Suitable component C) are sterically hindered phenols, for example hydroxiphenylpropionates of the formula (13)

wherein n is an integer from 1 to 4 and A is C₁-C₂₄-alkoxy, a bridge member -O (CH₂) ₆O-, -O (CH₂) ₂O (CH₂) ₂O-, -O (CH₂) ₂O (CH₂) ₂O ( CH₂) ₂O-, -HN- (CH₂) ₂₋₆-NH- or -O (CH₂) ₂-S- (CH₂) ₂O- or the rest ((CH₂O) ₄-C, such as the esters of 3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionic acid with methanol, octadecanol, 1,6-hexanediol, diethylene glycol, triethylene glycol or pentaerythritol or the diamides of 3- (3', 5'-di- tert-butyl-4-hydroxyphenyl) propionic acid with ethylene, trimethylene or hexamethylene diamine and compounds of the formula (14)

wherein R is hydroxy, phenyl, phenoxy, C₁-C₁₈-alkylphenoxy, C₁-C₂ Alkyl-alkylthio or C₁-C₂₄-alkoxy, R₁ phenoxy, C₁-C₁₈-alkylphenoxy, C₁-C₂₄-alkylthio or C₁-C₂₄-alkoxy, R₂ and R₃ independently of one another C₁-C₁₈-, preferably C₁-C₆-alkyl and especially tert-butyl in the 3-and 5-position, R₄ is hydrogen or C₁-C₄-alkyl and n is 0, 1, 2 or 3, preferably 0 or 1 such as di-n-octadecyl-3-tert-butyl-4-hydroxy-5-methylbenzyl-phosphonate, di-n-octadecyl-1- (3 ', 5'-di-tert-butyl-4' -hydroxyphenyl) -ethane-phosphonate, Di-n-octadecyl-3,5-di-tert-butyl-2-hydroxybenzyl-phosphonate, di-n-dodecyl-2- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -ethane-phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dimethyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, di-p-tert-octylphenyl- 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, on-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid, di-n-butyl-3,5-di- tert-butyl-4-hydroxybenzyl-phosphonate and O-ethyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid.

The compounds specified above as components A), B) and C) are known and can be prepared by processes known per se.

The compounds of formulas (5) and (6) are e.g. known from EP-A 51 188, 113 856 and 162 811 and can be prepared by known methods.

The compounds of the formulas (7) and (8) can be prepared by methods known per se, such as e.g. in US-A-3,403,183 and US-A-4,127,586, respectively. Compounds of the formula (8) in which R₁, R₂, R₃ and / or R₄ are sulfo can be prepared by the process described in FP-A-112120.

Compounds of formula (8) in which R₁, C₁-C₁₂-, preferably C₁-C₄-alkyl and R₃ are sulfo, can also be prepared by the corresponding compound in which R₃ is C₁-C₁₂-, preferably C₁-C₄ -Alkyl, with oleum, preferably 25% oleum, sulfonated at temperatures between 10 and 30 ° C and the product obtained neutralized to pH 7.

The preparation of the compounds from the class of the sterically hindered amines of the formulas (9) to (11) is described, for example, in US Pat. Nos. 3,640,928, 3,840,494 and 3,993,655.

The compounds of the formula (12) can be prepared in a manner known per se, for example by the processes described in Helv. 55 , 1566-1595 (1972) and in WO 86/03528.

Compounds of formula (13) can be prepared in a manner known per se, e.g. in GB-A-1 103 144.

The compounds of formula (14) can be prepared in a manner known per se, e.g. following the procedures described in US-A-3,268,630.

The agents according to the invention 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, of copper metal are added to 1 g of polyamide. They therefore contain a) 0.005 to 0.2% by weight of a bisazomethine complex of the formula (5, b) 0.05 to 3, preferably 0.1 to 1% by weight of a light stabilizer and optionally c) 0.05 to 3, preferably 0.1 to 1% by weight of an antioxidant.

The agents according to the invention, which are also the subject of the present invention, are used to stabilize dyed material before, during or after dyeing. The agent is expediently added directly to the dyebath. The coloring is carried out continuously or discontinuously.

Unless water-soluble, the agents according to the invention are expediently used as finely divided dispersions which are obtained by grinding in the presence of customary dispersants.

Polyamide material is understood to mean synthetic polyamide, such as polyamide-6, polyamide-6,6 or also polyamide-12. In addition to the pure polyamide fibers, fiber mixtures made of polyurethane and polyamide are also considered, for example tricot material made of polyamide / polyurethane in a mixing ratio of 70:30. Basically the pure or mixed polyamide material can be in a wide variety of processing forms, such as fiber, yarn, woven or knitted fabric.

Mainly polyamide material that is exposed to light and heat, e.g. As a car upholstery fabric or carpets, it is particularly suitable for being treated by the present method.

The coloring takes place in the usual way e.g. with metal complex, anthraquinone or azo dyes. The known types, in particular the 1: 2 chromium or 1: 2 cobalt complexes of mono- or 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.

The following examples serve to illustrate the invention. Parts mean parts by weight and percentages percent by weight. The percentages regarding the additions of the individual treatment or. Unless otherwise noted, dye baths refer to the fiber material.

Example 1: Improvement of the photo stability and the light fastness of an olive color.

Die Verbindungen werden dem Färbebad in gelöster Form zugesetzt.

Färbeflotte 1:

keine weiteren Zusätze.

Färbeflotte 2:

0,04 % des Kupferkomplexes der Formel

in feindisperser Form (Teilchengrösse <2 µm); gemahlen mit dem Kondensationsprodukt aus Naphthalinsulfonsäure und Formaldehyd als Dispergator im Gewichtsverhältnis 1:1; wässrige Dispersion

Färbeflotte 3:

1 % des Lichtschutzmittels der Formel

in feindisperser Form (Teilchengrösse <2 µm); gemahlen mit dem Kondensationsprodukt aus Naphthalinsulfonsäure und Formaldehyd als Dispergator im Gewichtsverhältnis 1:1.

Färbeflotte 4:

die Zusätze der Färbeflotten 2 und 3 kombiniert.

Four strands of 10 g each of polyamide 66 staple yarn are treated in a dyeing machine with liquors (liquor ratio 1:20), which generally contain 1 g / l ammonium sulfate (pH 6.5) and the following dyes (calculated on the yarn)

The compounds are added to the dye bath in dissolved form.

Dyeing liquor 1:

no other additives.

Dyeing liquor 2:

0.04% of the copper complex of the formula

in finely dispersed form (particle size <2 µm); ground with the condensation product of naphthalenesulfonic acid and formaldehyde as a dispersant in a weight ratio of 1: 1; aqueous dispersion

Dyeing liquor 3:

1% of the light stabilizer of the formula

in finely dispersed form (particle size <2 µm); ground with the condensation product of naphthalenesulfonic acid and formaldehyde as a dispersant in a weight ratio of 1: 1.

Dyeing liquor 4:

the additions of dye liquors 2 and 3 combined.

• (a) Lichtechtheiten:
  • Xenonlicht gemäss der Schweizerischen Norm SN-ISO 105-B02
  • Fakralicht gemäss der DIN 75.202 (Heissbelichtung)
• (b) Fotostabilität:
  Das Polyamid-Stapelgarn wird auf Karton aufgewickelt und während 750 Stunden unter Xenonlicht bzw. 120 Stunden unter Fakralichtbedingungen belichtet. Danach wird das Garn gemäss SNV (Schweizerische Normen-Vereinigung)-Norm 197.461 auf seine Reissfestigkeit und Dehnung geprüft. Es werden folgende Ergebnisse erhalten, wobei die Reissfestigkeit und Dehnung von unbelichtetem und unbehandeltem Polyamid-66-Stapelgarn gleich 100 % gesetzt werden.

Tabelle 1 Färbeflotte Lichtechtheit Reissfestigkeit/Dehnung in % Xenon Fakra Belichtung 120h nach Fakralicht Belichtung 750h nach Xenonlicht 1 6-7 5 32,6 / 36 49,7 / 51,2 2 6-7 6 73,4 / 67,1 69,4 / 64,2 3 -7 5 31,6 / 38,9 64,5 / 56,7 4 7 7 79,4 / 68,1 71,2 / 61,3 The dyeing materials are added to the liquors prepared as described, treated at 40 ° C for 5 minutes and heated at a rate of 1.5 ° C / min. to 95 ° C. The mixture is left at this temperature for 60 minutes, the dye bath is then cooled to 70 ° C., the dyeings are rinsed in cold water, centrifuged and dried at 80 ° C. in a forced air oven.
The dyeings are then tested as follows:

• (a) light fastness:
  • Xenon light according to the S chweizerischen N orm SN-ISO 105-B02
  • Fakralicht according to DIN 75.202 (hot exposure)
• (b) Photo stability:
  The polyamide staple yarn is wound up on cardboard and exposed for 750 hours under xenon light or 120 hours under fractal light conditions. Thereafter, the yarn according to SNV (S chweizerische N ormen- V ociation) standard 197,461 tested for tensile strength and elongation. The following results are obtained, the tensile strength and elongation of unexposed and untreated polyamide 66 staple yarn being set equal to 100%.

Table 1 Dyeing liquor Lightfastness Tensile strength / elongation in % xenon Fakra Exposure 120h after light Exposure 750h after xenon light 1 6-7 5 32.6 / 36 49.7 / 51.2 2nd 6-7 6 73.4 / 67.1 69.4 / 64.2 3rd -7 5 31.6 / 38.9 64.5 / 56.7 4th 7 7 79.4 / 68.1 71.2 / 61.3

• a) der Kupferkomplex die Lichtechtheit und Fotostabilität bei der Heissbelichtung verbessert,
• b) das Lichtschutzmittel eine Verbesserung der Lichtechtheit und Fotostabilität bei der Xenonbelichtung erbringt und
• c) die Kombination beider Verbindungen die Lichtechtheit und Fotostabilität sowohl bei der Heiss- als auch bei der Xenonbelichtung verbessert.

The results show that

• a) the copper complex improves the light fastness and photo stability during the hot exposure,
• b) the light stabilizer improves the light fastness and photo stability in the xenon exposure and
• c) the combination of both compounds improves the light fastness and photo stability in both the hot and the xenon exposure.

Example 2: Improvement of the photo stability and the light fastness of a beige color.

Die Testung der Färbungen wurde wie im Beispiel 1 vermerkt vorgenommen.

Färbeflotte 5:

nur Farbstoffe 3, 4 und 5

Färbeflotte 6:

zusätzlich Kupferkomplex der Formel (100)

Färbeflotte 7:

zusätzlich Lichtschutzmittel der Formel (101)

Färbeflotte 8:

zusätzlich Kombination der Verbindungen der Formeln (100) und (101).

The dyeing is carried out as described in Example 1, with the difference that the following dye combination is used for dyeing

The dyeings were tested as noted in Example 1.

Dyeing liquor 5:

only dyes 3, 4 and 5

Dyeing liquor 6:

additionally copper complex of the formula (100)

Dyeing liquor 7:

additionally light stabilizers of the formula (101)

Dyeing liquor 8:

additionally a combination of the compounds of the formulas (100) and (101).

The results are summarized in the following table: Table 2 Dyeing liquor Lightfastness Tensile strength / elongation in % xenon Fakra Exposure 120h after light Exposure 750h after xenon light 5 6 5 24.9 / 26.6 45.8 / 44.5 6 6 6 54.4 / 57.5 54.3 / 55.2 7 6-7 5-6 33.9 / 36.1 58.5 / 53.2 8th 7 6-7 65.1 / 65.5 70.8 / 63.7

Example 3: 12 skeins of 10 g each of polyamide 66 staple yarn are made using the dye mixture

0.008 % des Farbstoffes 7 :
81 Teile Farbstoff 3
gemäss Beispiel 1 (schwarz)
und
12 Teile des Farbstoffes

zu einem Hellbeige gefärbt, wobei die Farbbäder noch folgende Zusätze enthalten:

Flotte 1:

kein Zusatz

Flotte 2:

Zusatz von 0,04 %, bezogen auf das Warengewicht, der Verbindung der Formel (100).

Flotte 3:

Zusatz von 1 %, bezogen auf das Warengewicht, der Verbindung der Formel

Flotte 4:

Zusatz von 1 %, bezogen auf das Warengewicht, der Verbindung der Formel

Flotte 5:

Zusatz von 1 %, bezogen auf das Warengewicht, der Verbindung der Formel

Flotte 6:

Zusatz von 1 %, bezogen auf das Warengewicht, der Verbindung der Formel

Flotte 7:

Zusatz von 1 %, bezogen auf das Warengewicht, der Verbindung der Formel

Flotte Nr. Zusatzmenge* in % Verbindung Nr. 8 0,04 (100) 1,00 (500) 9 0,04 (100) 1,00 (501) 10 0,04 (100) 1,00 (502) 11 0,04 (100) 1,00 (503) 12 0,04 (100) 1,00 (504) * der Wirksubstanzen bezogen auf das Warengewicht 0.042% of dye 4 according to example 2
0.016% of dye 6:

0.008% of dye 7:
81 parts of dye 3
according to example 1 (black)
and
12 parts of the dye

colored to a light beige, the color baths also contain the following additives:

Fleet 1:

no addition

Fleet 2:

Addition of 0.04%, based on the weight of the product, of the compound of the formula (100).

Fleet 3:

Addition of 1%, based on the weight of the product, of the compound of the formula

Fleet 4:

Addition of 1%, based on the weight of the product, of the compound of the formula

Fleet 5:

Addition of 1%, based on the weight of the product, of the compound of the formula

Fleet 6:

Addition of 1%, based on the weight of the product, of the compound of the formula

Fleet 7:

Addition of 1%, based on the weight of the product, of the compound of the formula

Fleet number Additional quantity * in% Connection no. 8th 0.04 (100) 1.00 (500) 9 0.04 (100) 1.00 (501) 10th 0.04 (100) 1.00 (502) 11 0.04 (100) 1.00 (503) 12th 0.04 (100) 1.00 (504) * of the active substances based on the weight of the goods

The 12 yarn strands are dyed as described in Example 1, with the difference that 2% acetic acid (80%) is added to the dyebath at 95 ° C. after a dyeing time of 20 minutes.

The dyeings are then tested for light fastness according to SN-ISO 105-B02 (= xenon light), DIN 75.202 prov. (Fakra) and FORD EU-BO 50-2 (= Ford), as well as for light stability. To determine the latter, the yarn is exposed to Fakra for 150 hours and then examined for tensile strength and elongation in accordance with SNV 197.461.

The results are summarized in the following table: Table 4 Coloring from fleet Lightfastness Tear strength / elongation [%] after exposure to 150 h Fakra XENON FAKRA FORD 1 5 <4 2-3 h 17.4 / 17.1 2nd 5-6 6 -3-4 H 70.6 / 59.6 3rd 6-7 4+ 4-5 27.4 / 27.5 4th 6-7 4-5 4+ 35.7 / 29.5 5 6-7 4-5 4-5 36.4 / 33.4 6 6 4-5 3-4 30.2 / 29.8 7 6-7 5 4-5 40.0 / 39.6 8th 6-7 6-7 -5 73.9 / 69.6 9 6-7 7 4-5 78.6 / 69.8 10th 7 7 -5 79.9 / 69.4 11 6-7 6-7 4th 72.8 / 69.2 12th 7 7 4-5 71.6 / 65.9

From the table it can be seen that the Cu complex primarily improves fiber stability and fakra light fastness, while the UV absorber helps to improve light fastness according to xenon and especially Ford (high UV radiation).

80,9 g 2-(2'-Hydroxy-3',5'-di-tert.butylphenyl)-benzotriazol werden innerhalb von einer Stunde bei 15-20°C in 150 ml 25%igem Oleum eingetragen. Es entsteht eine Lösung, die noch 16 Stunden bei Raumtemperatur gerührt wird. Anschliessend lässt man die Lösung in ein Gemisch aus 600 g Eis und 400 ml Wasser unter gutem Rühren einfliessen. Das ausgefallene Produkt wird auf 80°C erhitzt und nach dem Abkühlen auf Raumtemperatur abfiltriert. Die Säure wird gut abgepresst und dann in einem Liter Wasser aufgeschlämmt. Danach wird unter Rühren mit 30%iger Natronlauge in 1 ¹/₂ Stunden neutralisiert (pH 7). Der dick ausgefallene Kristallbrei wird nun erneut auf 80°C erhitzt, wobei eine gut filtriebare Kristallform entsteht, und nach dem Abkühlen bei Raumtemperatur abfiltriert. Er wird bei 100°C im Vakuum getrocknet. Ausbeute: 83,5 g. Das Produkt kann aus Ethanol/Wasser im Verhältnis 8:2 umkristallisiert werden.Preparation of the compound of formula (502)

80.9 g of 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole are introduced into 150 ml of 25% oleum in one hour at 15-20 ° C. A solution is formed which is stirred for 16 hours at room temperature. The solution is then allowed to flow into a mixture of 600 g of ice and 400 ml of water with thorough stirring. The precipitated product is heated to 80 ° C and filtered off after cooling to room temperature. The acid is squeezed out well and then slurried in one liter of water. Then it is neutralized with stirring with 30% sodium hydroxide solution in 1½ hours (pH 7). The thick crystal sludge is then heated again to 80 ° C., whereby a crystal-clear crystal form is formed and, after cooling, is filtered off at room temperature. It is dried at 100 ° C in a vacuum. Yield: 83.5 g. The product can be recrystallized from ethanol / water in a ratio of 8: 2.

Example 4: 10 pieces of 10 g of a highly matted polyamide 6 tricot material are dyed with the olive dye mixture of Example 1 as indicated there, the dyebaths containing the following additives and at 95 ° C. after 20 minutes of dyeing time 2% acetic acid (80%) be added.

Fleet 1:

no addition

Fleet 2:

Additions of 1%, based on the weight of the product, of the compound (500)

Fleet 3:

Additions of 0.03%, based on the weight of the product, of the compound of the formula

(Preparation of the finely dispersed form as for compound (100)).

The lightfastnesses of the dyeings are determined according to DIN 75.202 prov. (Fakra). They are summarized in the following table: Table 5 Coloring from fleet FAKRA light fastness 1 <4 2nd 4-5 3rd 6

Claims (11)

1. A process for the photochemichal stabilization of undyed and dyed polyamide fibre material or blends thereof with other fibre materials, which comprises treating the fibre material with a mixture of

   A) a non-dyeing bisazomethine copper complex of the formula (5)

   

   in which R₆, R₇, R₈ and R₉ are each hydrogen, hydroxyl, chlorine, bromine, methyl, tert-butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino,
   X₁ is hydrogen, methyl, ethyl or phenyl and
   Y₁ is hydrogen,
   or R₆ and R₇ together form a fused benzene radical or X₁ and Y₁ together form a cyclohexylene radical.

   B) a light stabilizer and, if desired,

   C) an antioxidant.
2. A process according to claim 1, wherein the component A) used is a bisazomethine complex of the formula (6)

   

   in which
   R₁₀, R₁₁ and R₁₃ are each hydrogen, chlorine, bromine, methyl or methoxy or R₁₀ and R₁₁ together form a benzene ring, R₁₂ is hydrogen or hydroxyl and X₂ is hydrogen, methyl, ethyl or phenyl.
3. A process according to claim 1 or 2, wherein the component B) used is a 2-hydroxybenzophenone of the formula (7)

   

   in which
   R₁ is hydrogen, hydroxyl or C₁-C₁₄alkoxy
   R₂ is hydrogen, C₁-C₄alkyl or sulfo,
   R₃ is hydrogen, hydroxyl or C₁-C₄alkoxy and
   R₄ is hydrogen, hydroxyl or carboxyl.
4. A process according to claim 1 or 2, wherein the component B) used is a 2-(2'-hydroxyphenyl)-benzotriazole or a salt thereof, of the formula (8)

   

   in which

   R₁   is hydrogen, C₁-C₁₂alkyl, chlorine, C₅-C₆cycloalkyl, C₇-C₉phenylalkyl or sulfo,

   R₂   is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, chlorine, hydroxyl or sulfo,

   R₃   is C₁-C₁₂alkyl, C₁-C₄alkoxy, phenyl, (C₁-C₈alkyl)-phenyl, C₅-C₆cycloalkyl, C₂-C₉alkoxycarbonyl, chlorine, carboxyethyl, C₇-C₉phenylalkyl or sulfo,

   R₄   is hydrogen, chlorine, C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₉alkoxycarbonyl, carboxyl or sulfo and
   R₅ is hydrogen or chlorine.
5. A process according to claim 1 or 2, wherein the component B) used is a compound from the class of sterically hindered amines.
6. A process according to claim 5, wherein the sterically hindered amine used is a 2,2,6,6-tetraalkylpiperidine derivative which, in its molecule, contains at least one group of the formula (9)

   

   in which R is hydrogen or methyl.
7. A process according to claim 1 or 2, wherein the component B) used is a 2-(2'-hydroxyphenyl)-s-triazine or a salt thereof, of the formula (12)

   

   in which R is hydrogen, halogen, C₁-C₄alkyl or sulfo, R₁ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or hydroxyl, R₂ is hydrogen or sulfo and R₃ and R₄ independently of one another are C₁-C₄alkyl, C₁-C₄alkoxy, C₅-C₆cycloalkyl phenyl or phenyl substituted by C₁-C₄alkyl and hydroxyl.
8. A process according to claim 1 or 2, wherein the component B) used is an s-triazine compound of the formula

   

   in which at least one of the substituents R₁, R₂ and R₃ is a radical of the formula

   

   in which M is sodium, potassium, calcium, magnesium, ammonium or tetra-C₁-C₄alkylammonium and m is 1 or 2, and the remaining substituent or substituents independently of one another are C₁-C₁₂alkyl, phenyl, or C₁-C₁₂alkyl or phenyl which are bonded to the triazinyl radical via oxygen, sulfur, imino or C₁-C₄alkylimino.
9. A process according to any one of claims 1 to 8, wherein the component C) used is a hydroxyphenylpropionate of the formula (13)

   

   in which n is an integer from 1 to 4 and A is C₁-C₂₄alkoxy, a bridge member -O(CH₂)₆O-, -O(CH₂)₂O(CH₂)₂O-, -O(CH₂)₂O(CH₂)₂O(CH₂)₂O-, -HN-(CH₂)₂₋₆-NH- or -O(CH₂)₂-S-(CH₂)₂O- or is the radical --(----CH₂O)₄-C.
10. A process according to any one of claims 1 to 8, wherein the component C) used is a phenylalkylphosphonate of the formula (14)

    

    in which R is hydroxyl, phenyl, phenoxy, C₁-C₁₈alkylphenoxy, C₁-C₂₄alkylthio or C₁-C₂₄alkoxy, R₁ is phenoxy, C₁-C₁₈alkylphenoxy, C₁-C₂₄alkylthio or C₁-C₂₄alkoxy, R₂ and R₃ independently of one another are C₁-C₁₈alkyl, R₄ is hydrogen or C₁-C₄alkyl and n is 0, 1, 2 or 3.
11. An agent for the photochemical stabilization of undyed and dyed polyamide fibre material or blends thereof with other fibre materials, which comprises

    A) 0.005 to 0.20 % by weight of a bisazomethine complex of the formula (5),

    B) 0.05 to 3 % by weight of a light stabilizer and, if desired,

    C) 0.05 to 3 % by weight of an antioxidant.