EP0255481A1 - Process for the photochemical stabilisation of a fibrous polyamide material and its mixtures with other fibres - Google Patents

Abstract

A process for the photochemical stabilization of polyamide fiber material or its mixtures with other fiber materials is described, which is characterized in that the fiber material is mixed with a mixture of A) a water-soluble copper complex dye or a mixture of copper complex compounds, at least one component being a water-soluble copper complex dye, B ) treated with a light stabilizer and, if desired, C) an antioxidant, an agent for carrying out the process and the fiber material treated with it.

Description

The present invention relates to a process for the photochemical stabilization of polyamide fiber material and its blends with other fibers by treatment with organic copper complex dyes, light stabilizers and antioxidants.

The use of copper salts, e.g. 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 I.B. HANES in ADR 69 (1980), 3, pages 19 and 20. However, inorganic or organic copper salts often have the disadvantage that they are insufficiently and unevenly drawn onto the polyamide fiber and therefore have to be used in high concentrations in order to achieve the desired effect achieve. 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, such light fastness improvers 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.

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 and 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 dyes, light stabilizers and antioxidants allows a further improvement in the fastness properties and properties such as light fastness and tear resistance.

• oder einer Mischung von Kupferkomplexverbindungen, wobei mindestens eine Komponente ein wasserlöslicher Kupferkomplexfarbstoff ist.
  • B) einem Lichtschutzmittel und gewünschtenfalls
  • C) einem Antioxidant
  
  behandelt.
• Als Komponente (A) kommen vorzugsweise in Betracht:
  • a) wasserlösliche Kupferkomplexfarbstoffe, insbesondere wasserlösliche Kupferkomplexazofarbstoffe, oder bevorzugt
  • b) Mischungen von wasserlöslichen Kupferkomplexfarbstoffen mit sauren bzw. schwachsauren Farbstoffen für Polyamidfasern, oder
  • c) Mischungen enthaltend mindestens einen wasserlöslichen Kupferkomplexfarbstoff und mindestens eine wasserlösliche Kupferkomplexverbindung ohne Farbstoffcharakter, wobei die genananten Kupferkomplexverbindungen zweckmässigerweise in einer Menge eingesetzt werden, dass auf 1 g Polyamidfasermaterial 1 bis 4000, insbesondere 5 bis 800 und vorzugsweise 10 bis 200 jlg Kupfer, zukommt.

The present invention thus relates to a process for the photochemical stabilization of polyamide fiber material or its mixtures with other fiber materials, which is characterized in that the fiber material is mixed with a mixture of A) a water-soluble copper complex dye

• or a mixture of copper complex compounds, wherein at least one component is a water-soluble copper complex dye.
  • B) a light stabilizer and if desired
  • C) an antioxidant
  
  treated.
• The following are preferably considered as component (A):
  • a) water-soluble copper complex dyes, in particular water-soluble copper complex azo dyes, or preferably
  • b) mixtures of water-soluble copper complex dyes with acidic or weakly acidic dyes for polyamide fibers, or
  • c) Mixtures containing at least one water-soluble copper complex dye and at least one water-soluble copper complex compound without dye character, the aforementioned copper complex compounds being expediently used in an amount such that 1 to 4000, in particular 5 to 800 and preferably 10 to 200, ml of copper are added to 1 g of polyamide fiber material.

1) worin D ein Rest der Benzol- oder Naphthalinreihe, Y die HO-, CH₃0-oder HOOC-Gruppe und Y' die HO- oder eine Aminogruppe ist, und worin K den Rest einer Kupplungskomponente der Benzol-, Naphthalin-oder heterocyclischen Reihe oder den Rest einer Ketomethylenverbindung bedeutet.Copper complexes of azo dyes of the formula containing water-solubilizing groups are particularly preferred

1) wherein D is a residue of the benzene or naphthalene series, Y is the HO, CH ₃ 0 or HOOC group and Y 'is the HO or an amino group, and wherein K is the residue of a coupling component of the benzene, naphthalene or means heterocyclic series or the rest of a ketomethylene compound.

In the azomethine dyes of the formula (1), Y or Y 'is bonded to D or K in a position adjacent to the group -N = N-.

In the copper complex dyes, water-solubilizing groups include e.g. Sulfone, sulfonamide, N-mono- or N, N-dialkylsulfonamide groups, carboxyl groups or especially sulfonic acid groups.

Suitable sulfone groups are alkyl sulfone and in particular C ₁ -C ₄ alkyl sulfone groups.

Suitable N-mono- or N, N-dialkylsulfonamide groups are in particular those having one or two C 1 -C ₄ -alkyl radicals.

In particular, in the process according to the invention, component A) uses copper complex dyes with one or two water-solubilizing groups, in particular with a single water-solubilizing group.

verwendet, worin A ein gegebenenfalls substituierter Carboxyphenyl-oder Sulfophenylrest, R₁ Wasserstoff oder C₁-C₄-Alkyl und K der Rest einer Kupplungskomponente der Benzol-, Naphthalin-, Pyrazolon-, Aminopyrazol-, Acetoacetanilid-, 2,4-Dioxychinolin-, Pyridon- oder Pyridinreihe ist und der Ring B gegebenenfalls z.B. durch Chlor oder Nitro weitersubstituiert sein kann.An interesting embodiment of the method according to the invention is characterized in that component A) is a copper complex dye of the formula

used, in which A is an optionally substituted carboxyphenyl or sulfophenyl radical, R _{1 is} hydrogen or C ₁ -C ₄ alkyl and K is the rest of a coupling component of the benzene, naphthalene, pyrazolone, aminopyrazole, acetoacetanilide, 2,4-dioxyquinoline -, pyridone or pyridine series and the ring B can optionally be further substituted, for example by chlorine or nitro.

(3) diazotiert und auf eine Kupplungskomponente der Formel (4) kuppelt.Many metallizable azo dyes of the formula (1) have been described in the literature. The azo dyes of the formula (1) are prepared in a manner known per se by using an amine of the formula

(3) diazotized and coupled to a coupling component of formula (4).

The diazotization of the diazo component of the formula (3) is generally carried out by the action of nitrous acid in aqueous mineral acid solution at low temperature, the coupling to the coupling component of the formula (4) at acidic, neutral to alkaline pH values.

• 2-Amino-1-hydroxybenzol, 2-Amino-1-methoxybenzol, Anthranilsäure, 4-oder 5-Sulfonamido-anthranilsäure, 3- oder 5-Chloranthranilsäure, 4-Chlor- und 4,6-Dichlor-2-amino-1-hydroxybenzol, 4- oder 5- oder 6-Nitro-2-amino-1-hydroxybenzol, 4-Chlor- und 4-Methyl- und 4-Acetyiamino-6-nitro-2-amino-1-hydroxybenzoi, 6-Acetylamino- und 6-Chlor-4-nitro-2-amino-1-hydroxybenzol, 4-Cyan-2-amino-1-hydroxybenzol, 4-Methoxy-2-amino-1-hydroxybenzol, 2-Amino-1-hydroxybenzol-5-methyl-und -5-benzylsulfon, 2-Amino-1 -hydröxyben- zol-4-methyl-, -äthyl-, -chlormethyl- und -butylsulfon, 6-Chlor-, 5-Nitro- und 6-Nitro-2-amino-1-hydroxybenzol-4-methylsulfon, 2-Amino-1-hydroxybenzol-4-oder -5-sulfamid, -sulf-N-methyl- und -sulf-N-ß-hydroxyäthylamid, 2-Amino-1-methoxybenzol-4-sulfanilid, 4-Methoxy-5-chlor-2-amino-1-hydroxybenzol, 4-Methyl-2-amino-1-hydroxybenzol, 4-Chlor-5-nitro-2-amino-1-hydroxybenzol, 5-Nitro-4-methyl-2-amino-1-hydroxybenzol, 5-Nitro-4-methoxy-2-amino-1-hydroxybenzol, 3,4,6-Trichlor-2-amino-1-hydroxybenzol, 6-Acetylamino-4-chlor-2-amino-1-hydroxybenzol, 4,6-Dinitro-2-amino-1-hydroxybenzol, 4-Nitro-2-amino-1-hydroxybenzol-5- oder -6-sulfonsäureamid, 4- oder 5-Chloranisidin, 4- oder 5-Nitroanisidin, 2-Methoxy-5-methylanilin, 2,5-Dimethoxyanilin, 2-Anisidin-4- oder -5-ß-hydroxyäthylsulfon, 4-Methyl-6-sulfo-2-amino-1-hydroxybenzol, 2-Amino-4-sulfo-1-hydroxybenzol, 4-Chlor-6-sulfo-2-amino-1-hydroxybenzol, 6-Chlor-4-sulfo-2-amino-1-hydroxybenzol, 5-Nitro-4-sulfo-2-amino-1-hydroxybenzol, 4-Nitro-6-sulfo-2-amino-1-hydroxybenzol, 46-Nitro-4-sulfo-2-amino-1-hydroxybenzol, 4-Acetylamino-2-amino-1-hydroxybenzol, 4-Acetylamino-6-sulfo-2-amino-1-hydroxybenzol, 5-Acetylamino-2-amino-1-hydroxybenzol, 6-Acetylamino-4-sulfo-2-amino-1-hydroxybenzol, 4-Chlor-2-amino-4-hydroxybenzol-5-sulfamid, 2-Amino-1-hydroxybenzol-4-(N-2'-Carboxyphenyl)sulfamid, 1-Amino-2-hydroxy-4-sulfonaphthalin, 1-Amino-2- hydroxy-4-sulfo-6-nitronaphthalin, 1-Amino-2-hydroxy-4-sulfo-6-acetamido- naphthalin, 1-Amino-2-hydroxy-4,8-disulfonaphthalin, 1-Amino-2-hydroxy-6-sulfonaphthalin, 1-Amino-2-hydroxy-7-sulfonaphthalin, 1-Amino-2-hydroxy-8-sulfonaphthalin, 2-Amino-1-hydroxy-4-sulfonaphthalin, 2-Amino-1-hydroxy-6-sulfonaphthalin.

Examples of suitable amines of the formula (3) are:

• 2-amino-1-hydroxybenzene, 2-amino-1-methoxybenzene, anthranilic acid, 4- or 5-sulfonamido-anthranilic acid, 3- or 5-chloroanthranilic acid, 4-chloro and 4,6-dichloro-2-amino-1 -hydroxybenzene, 4- or 5- or 6-nitro-2-amino-1-hydroxybenzene, 4-chloro and 4-methyl and 4-acetyiamino-6-nitro-2-amino-1-hydroxybenzoi, 6-acetylamino - and 6-chloro-4-nitro-2-amino-1-hydroxybenzene, 4-cyano-2-amino-1-hydroxybenzene, 4-methoxy-2-amino-1-hydroxybenzene, 2-amino-1-hydroxybenzene- 5-methyl- and -5-benzylsulfone, 2-amino-1-hydroxoxybenzene-4-methyl-, -ethyl-, -chloromethyl- and -butyl-sulfone, 6-chloro-, 5-nitro- and 6-nitro- 2-amino-1-hydroxybenzene-4-methylsulfone, 2-amino-1-hydroxybenzene-4-or -5-sulfamide, -sulf-N-methyl- and -sulf-N-ß-hydroxyethylamide, 2-amino-1 -methoxybenzene-4-sulfanilide, 4-methoxy-5-chloro-2-amino-1-hydroxybenzene, 4-methyl-2-amino-1-hydroxybenzene, 4-chloro-5-nitro-2-amino-1-hydroxybenzene , 5-nitro-4-methyl-2-amino-1-hydroxybenzene, 5-nitro-4-methoxy-2-amino-1-hydroxybenzene, 3,4,6-trichloro-2-amino-1-hydr oxybenzene, 6-acetylamino-4-chloro-2-amino-1-hydroxybenzene, 4,6-dinitro-2-amino-1-hydroxybenzene, 4-nitro-2-amino-1-hydroxybenzene-5- or -6- sulfonic acid amide, 4- or 5-chloroanisidine, 4- or 5-nitroanisidine, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 2-anisidine-4- or -5-ß-hydroxyethylsulfone, 4-methyl-6- sulfo-2-amino-1-hydroxybenzene, 2-amino-4-sulfo-1-hydroxybenzene, 4-chloro-6-sulfo-2-amino-1-hydroxybenzene, 6-chloro-4-sulfo-2-amino- 1-hydroxybenzene, 5-nitro-4-sulfo-2-amino-1-hydroxybenzene, 4-nitro-6-sulfo-2-amino-1-hydroxybenzene, 46-nitro-4-sulfo-2-amino-1- hydroxybenzene, 4-acetylamino-2-amino-1-hydroxybenzene, 4-acetylamino-6-sulfo-2-amino-1-hydroxybenzene, 5-acetylamino-2-amino-1-hydroxybenzene, 6-acetylamino-4-sulfo- 2-amino-1-hydroxybenzene, 4-chloro-2-amino-4-hydroxybenzene-5-sulfamide, 2-amino-1-hydroxybenzene-4- (N-2'-carboxyphenyl) sulfamide, 1-amino-2- hydroxy-4-sulfonaphthalene, 1-amino-2-hydroxy-4-sulfo-6-nitronaphthalene, 1-amino-2-hydroxy-4-sulfo-6-acetamido naphthalene, 1-amino-2-hydroxy -4,8-disulfonaphthalene, 1-amino-2-hydroxy-6-sulfonaphthalene, 1-amino-2-hydroxy-7-sulfonaphthalene, 1-amino-2-hydroxy-8-sulfonaphthalene, 2-amino-1-hydroxy -4-sulfonaphthalene, 2-amino-1-hydroxy-6-sulfonaphthalene.

• - In o-Stellung zur OH-Gruppe kuppelnde Naphthole, die gegebenenfalls mit Chlor, Amino, Acylamino, Acyl, Ci-C₄-Alkyl, Ci-C₄-Alkoxy, Sulfonamido-, N-mono- oder N,N-disubstituierten Sulfonamldogruppen, Sulfo-und Sulfongruppen substituiert sind;
• - In o-Stellung zur Aminogruppe kuppelnde Naphthylamine, die gegebenenfalls mit Halogen, insbesondere Brom, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Sulfonamido-, mono- oder disubstituierten Sulfonamido-, Sulfo- oder Sulfongruppen substituiert sind;
• -5-Pyrazolone oder 5-Aminopyrazole, die in 1-Stellung einen gegebenenfalls mit Chlor, Nitro, C₁-C₄-Alkyl-und
• -Alkoxygruppen, Sulfonamido-, N-alkylierten Sulfonamidgruppen, Sulfogruppen, Sulfongruppen und insbesondere Aminogruppen substituierten Phenyl-oder Naphthylrest besitzen;
• - 2,6-Dihydro-3-cyano- oder -3-carbonamido-4-alkylpyridine und 6-Hydroxy-2-pyridone, die In 1-Stellung durch gegebenenfalls substituiertes C₁-C₄-Alkyl, z.B. Methyl, Isopropyl, ß-Hydroxyäthyl, ß-Aminoäthyl, y-Isopropoxypropyl oder durch -NH₂ oder eine substituierte Aminogruppe, wie z.B. Dimethylamlho oder Diäthylamino substituiert sind, in 3-Stellung eine Cyano- oder Carbonamidogruppe und in 4-Stellung eine C₁-C₄-Alkylgruppe, insbesondere Methyl, tragen;
• - Acetessigsäureanilide und Benzoylessigsäureanilide, die im Anilidkern gegebenenfalls mit C₁-C₄-Alkyl-,
• -Alkoxy-, -Alkylsulfonylgruppen, Ci-C₄-Hydroxyalkyl-, Alkoxyalkyl- oder Cyanalkylsulfonylgruppen, Sulfonamldo-, N-alkylierten Sulfonamidogruppen, Sulfo, Acetylamino und Halogen substituiert sein können;
• - Phenole, die mit niedrigmolekularen Acylaminogruppen und/oder mit 1 bis 5 Kohlenstoffatome enthaltenden Alkylgruppen substituiert sind und in o-Stellung kuppeln.

The coupling components of the formula (4) can be derived, for example, from the following groups of coupling components:

• - Naphthols coupling in the o-position to the OH group, which are optionally substituted with chlorine, amino, acylamino, acyl, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, sulfonamido, N-mono- or N, N-disubstituted Sulfonamido groups, sulfo and sulfone groups are substituted;
• - Naphthylamines coupling in the o-position to the amino group, which are optionally substituted with halogen, in particular bromine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfonamido, mono- or disubstituted sulfonamido, sulfo or sulfone groups ;
• -5-pyrazolones or 5-aminopyrazoles, which are in the 1-position, optionally with chlorine, nitro, C ₁ -C ₄ -alkyl and
• Alkoxy groups, sulfonamido, N-alkylated sulfonamide groups, sulfo groups, sulfone groups and in particular amino groups have substituted phenyl or naphthyl radicals;
• 2,6-dihydro-3-cyano- or -3-carbonamido-4-alkylpyridines and 6-hydroxy-2-pyridones, which are in the 1-position by optionally substituted C ₁ -C ₄ -alkyl, for example methyl, isopropyl, ß-hydroxyethyl, ß-aminoethyl, y-isopropoxypropyl or substituted by -NH ₂ or a substituted amino group, such as dimethylamlho or diethylamino, in the 3-position a cyano or carbonamido group and in the 4-position a C ₁ -C ₄ - Alkyl group, especially methyl;
• Acetoacetic acid anilides and benzoylacetic acid anilides, which are optionally in the anilide core with C ₁ -C ₄ alkyl,
• Alkoxy, alkylsulfonyl groups, C 1 -C ₄ -hydroxyalkyl, alkoxyalkyl or cyanoalkylsulfonyl groups, sulfonamldo, N-alkylated sulfonamido groups, sulfo, acetylamino and halogen can be substituted;
• - Phenols which are substituted with low molecular weight acylamino groups and / or with alkyl groups containing 1 to 5 carbon atoms and couple in the o-position.

• 2-Naphthol, 1-Naphthol, 1-Hydroxynaphthalin-4- oder 5-sulfonsäure, 1,3- oder 1,5-Dihydroxynaphthalin, 1-Hydroxy-7-aminonaphthalin-3-sulfonsäure, 2-Naphthol-6-sulfonamid, 1-Hydroxy-7-N-methyl- oder N-acetylaminonaphthalin-3-sulfonsäure, 2-Naphthol-6-ß-hydroxyäthylsulfon, 1-Hydroxy-6-amino- oder -6-N-Methyl-oder -6-N-Acetylaminonaphthalin-3-sulfonsäure, 1-Hydroxy-7-aminonaphthalin-3,6-disulfonsäure, 1-Hydroxy-6-aminonaphthalin-3,5-disulfonsäure, 1-Acetylamino-7-naphthol, 1-Hydroxy-6-N-(4'-aminophenyi)aminoapht- halin-3-sulfonsäure, 1-Hydroxy-5-aminonaphthalin-3-sulfonsäure, 1-Propionylamino-7-naphthol, 2-Hydroxy-6-aminonaphthalin-4-sulfonsäure, 1-Carbomethoxyamino-7-naphthol, 1-Hydroxy-8-aminonaphthalin-5-sulfonsäure, 1-Carboäthoxy-amino-7-naphthol, 1-Hydroxy-8-aminonaphthalin-5,7-disulfonsäure, 1-Carbopropoxy- amino-7-naphthol, 1-Hydroxy-8-aminonaphthalin-3-sulfonsäure, 1-Dimethylaminosulfonyl-amino-7-naphthol, 6-Acetylamino-2-naphthol, 1-Hydroxy-8-amino-naphthalin- 3,5- oder -3,6-disulfonsäure, 4-Acetylamino-2-naphthol, 2-Hydroxy-5-aminonaphthalin-4,7-disulfonsäure, 4-Methoxy-l-naphthol, 4-Acetylamino-1-naphthol, 1-Naphthol-3-, -4- oder -5-sulfonamid, 2-Naphthol-3-, -4-, -5-, -6-, -7- oder -8-sulfonamid, 5,8-Dichlor-1-naphthol, 5-Chlor-1-naphthol, 2-Naphthylamin, 2-Naphthylamin-1-sulfonsäure, 2-Aminonaphthalin-5-, -6-oder -7-sulfonamid, 2-Aminonaphthalin-6(-sulfonsäure-)N-methyl-, -äthyl-, -isopropyl-, -ß-oxyäthyl- oder -y-methoxypropylamid, 2-Aminonaphthalin-6-sulfanilid, 2-Aminonaphthalin-6-sulfonsäure-N-methylanilid, 1-Aminonaphthalin-3-, -4- oder -5-sulfonamid, 1-Aminonaphthalin-5-methyl- oder -äthylsulfon, 5,8-Dichlor-1-amino naphthalin, 2-Phenylaminonaphthalin, 2-N-Methylaminonaphthalin, 2-N-Aethylaminonaphthalin, 2-Phenylaminonaphthalin-5-, -6- oder -7-sulfonamid, 2-(3'-Chlorphenylamino)-naphthalin-5-, -6- oder -7-sulfonamid, 6-Methyl-2-aminonaphthalin, 6-Brom-2-amino-naphthalin, 6-Methoxy-2-aminonaphthalin, 1,3-DimefhyIpyrazolon, 3-Methyl-5-pyrazolon, 1-Phenyl-3-methyl-5-pyrazolon, 1-Phenyl-3-carbonamido-5-pyrazolon, 1-(2'-, 3'- oder 4'-Methylphenyl)-3-methyl-5-pyrazolon, 1-[3'- oder 4'-(ß-Hydroxyäthylsulfonyl)-phenyl]-3-methyl-5-pyrazolon, 1-(2'-Methoxyphenyl)-3-methyl-5-pyrazolon, 1-(2'-, 3'- oder 4'-Chlorphenyl)-3-methyl-5-pyrazolon, 1-(2'-, 3'-oder 4'-Nitrophenyl)-3-methyl-5-pyrazolon, 1-(2', 5'- oder 3', 4'-Dichlorphenyl)-3-methyl-5-pyrazolon, 1-(2'-, 3'- oder 4'-Sulfamoylphenyl)-3-methyl-5-pyrazolon, 1-(2'-, 3'- oder 4-Methylsulfonylphe- nyl)-3-methyl-5-pyrazolon, 2,6-Dihydro-3-cyano-4-methylpyridin, 1-Methyl-3-cyano-4-äthyl-6-hydroxypyridon-(2), 1-Amino-3-cyano-4-methyl-6-hydroxypyridon-(2), 1-Phenyl-3-carbonamido-4-methyl-6-hydroxypyridon-(2), Acetoacetanilid, Acetoacet-o-, -m- oder -p-sulfoanilid, Acetoacet-4-(ß-hydroxyäthylsulfonyl)-anilid, Acetoacet-o-anisidid, Acetoacetnaphthylamid, Acetoacet-o-toluidid, Acetoacet-o-chloranilid, Acetoacet-m-oder -p-chloranilid, Acetoacetanilid-3- oder -4-sulfonamid, Acetoacet-3- oder -4-aminoanilid, Acetoacet-m-xylidid, Benzoylessigsäureanilid, 4-Methylphenol, 3-Dialkylaminophenoi, besonders 3-Dimethylamino- und 3-Diäthylaminophenol, 4-t-Butylphenol, 4-t-Amylphenol, 2- oder 3-Acetylamino-4-methylphenol, 2-Methox- ycarbonylamino-4-methylphenol, 2-Aethoxycarbonylamino-4-methylphenol, 3,4-Dimethylphenol und 2,4-Dimethylphenol, 1-(4'-Aminophenyl)-3-methyl-5-pyrazolon, 1-(2'-, 3'- oder 4'-Sulfophenyl)-3-methyl-5-pyrazo-Ion, 1-(2'-Chlor-4'- oder 5'-sulfophenyl)-3-methyl-5-pyrazolon, 1-(2'-Methyl-6'-chlorphenyl)-3-methyl-5-pyrazolon, 1-(2'-Methyl-4'-sulfophenyl)-3-methyl-5-pyrazolon, 1-(2'-, 3'- oder 4'-Chlor- oder Methyl- oder Sulfophenyl)-3-carboxy-5-pyrazolon, 1-[5'-sulfonaphthyl(2')]-3-methyl-5-pyrazolon, 1-[4"-Amino-2',2"-disul- fostilben-(4')]-3-methyl-5-pyrazolon, 1-Aethyl-3-cyano-4-methyl-6-hydroxypyridon-(2), 1-Aethyl-3-sulfomethyl-4-methyl-6-hydroxypyridon-(2), 2,6-Dihydroxy-3-cyano-4-sulfomethylpyridin, 2,4,6-Trihydroxypyrimidin, 2,3-Dihydroxypyridin, 5-Brom-(chlor)-2,3-dihydroxypyridin, 2-Amino-3-hydroxypyridin, 5-Brom-2-amino-3-hy- droxypyridin, 5-Ethylmercapto-2,3-dihydroxypyridin, 5-Phenylsulfonyl-2,3-dihydropyridin, 2,3-Dihydroxy-pyridin-5-sulfonsäure und 2-Amino-3-hydroxypyridin-5-sulfonsäure.

Examples of such coupling components are:

• 2-naphthol, 1-naphthol, 1-hydroxynaphthalene-4- or 5-sulfonic acid, 1,3- or 1,5-dihydroxynaphthalene, 1-hydroxy-7-aminonaphthalene-3-sulfonic acid, 2-naphthol-6-sulfonamide, 1-hydroxy-7-N-methyl- or N-acetylaminonaphthalene-3-sulfonic acid, 2-naphthol-6-ß-hydroxyethylsulfone, 1-hydroxy-6-amino- or -6-N-methyl-or -6-N -Acetylaminonaphthalene-3-sulfonic acid, 1-hydroxy-7-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-6-aminonaphthalene-3,5-disulfonic acid, 1-acetylamino-7-naphthol, 1-hydroxy-6-N - (4'-Aminophenyi) aminoaphthalene-3-sulfonic acid, 1-hydroxy-5-aminonaphthalene-3-sulfonic acid, 1-propionylamino-7-naphthol, 2-hydroxy-6-aminonaphthalene-4-sulfonic acid, 1-carbomethoxyamino -7-naphthol, 1-hydroxy-8-aminonaphthalene-5-sulfonic acid, 1-carboethoxy-amino-7-naphthol, 1-hydroxy-8-aminonaphthalene-5,7-disulfonic acid, 1-carbopropoxy-amino-7-naphthol , 1-Hydroxy-8-aminonaphthalene-3-sulfonic acid, 1-dimethylaminosulfonylamino-7-naphthol, 6-acetylamino-2-naphthol, 1-hydroxy-8-amino-naphthalene 3,5- or -3,6 -disul fonic acid, 4-acetylamino-2-naphthol, 2-hydroxy-5-aminonaphthalene-4,7-disulfonic acid, 4-methoxy-l-naphthol, 4-acetylamino-1-naphthol, 1-naphthol-3-, -4- or -5-sulfonamide, 2-naphthol-3-, -4-, -5-, -6-, -7- or -8-sulfonamide, 5,8-dichloro-1-naphthol, 5-chloro-1- naphthol, 2-naphthylamine, 2-naphthylamine-1-sulfonic acid, 2-aminonaphthalene-5-, -6-or -7-sulfonamide, 2-aminonaphthalene-6 (-sulfonic acid-) N-methyl-, -ethyl-, - isopropyl-, -ß-oxyethyl- or -y-methoxypropylamide, 2-aminonaphthalene-6-sulfanilide, 2-aminonaphthalene-6-sulfonic acid-N-methylanilide, 1-aminonaphthalene-3-, -4- or -5-sulfonamide, 1-aminonaphthalene-5-methyl or ethyl sulfone, 5,8-dichloro-1-amino naphthalene, 2-phenylaminonaphthalene, 2-N-methylaminonaphthalene, 2-N-ethylaminonaphthalene, 2-phenylaminonaphthalene-5-, -6- or -7-sulfonamide, 2- (3'-chlorophenylamino) -naphthalene-5-, -6- or -7-sulfonamide, 6-methyl-2-aminonaphthalene, 6-bromo-2-amino-naphthalene, 6-methoxy- 2-amino naphthalene, 1,3-dimethyl pyrazolone, 3-methyl-5-pyrazolone, 1-phen yl-3-methyl-5-pyrazolone, 1-phenyl-3-carbonamido-5-pyrazolone, 1- (2'-, 3'- or 4'-methylphenyl) -3-methyl-5-pyrazolone, 1- [ 3'- or 4 '- (ß-Hydroxyethylsulfonyl) phenyl] -3-methyl-5-pyrazolone, 1- (2'-methoxyphenyl) -3-methyl-5-pyrazolone, 1- (2'-, 3' - or 4'-chlorophenyl) -3-methyl-5-pyrazolone, 1- (2'-, 3'- or 4'-nitrophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'- or 3 ', 4'-dichlorophenyl) -3-methyl-5-pyrazolone, 1- (2'-, 3'- or 4'-sulfamoylphenyl) -3-methyl-5-pyrazolone, 1- (2'-, 3'- or 4-methylsulfonylphenyl) -3-methyl-5-pyrazolone, 2,6-dihydro-3-cyano-4-methylpyridine, 1-methyl-3-cyano-4-ethyl-6-hydroxypyridone- ( 2), 1-amino-3-cyano-4-methyl-6-hydroxypyridone- (2), 1-phenyl-3-carbonamido-4-methyl-6-hydroxypyridone- (2), acetoacetanilide, acetoacet-o-, -m- or -p-sulfoanilide, acetoacet-4- (β-hydroxyethylsulfonyl) anilide, acetoacet-o-anisidide, acetoacetnaphthylamide, acetoacet-o-toluidide, acetoacet-o-chloroanilide, acetoacet-m-or -p-chloroanilide , Acetoacetanilide-3- or -4-sulfonamide, acetoacet-3- or -4-aminoa nilide, acetoacet-m-xylidide, benzoylacetic acid anilide, 4-methylphenol, 3-dialkylaminophenoi, especially 3-dimethylamino- and 3-diethylaminophenol, 4-t-butylphenol, 4-t-amylphenol, 2- or 3-acetylamino-4-methylphenol , 2-methoxycarbonylamino-4-methylphenol, 2-ethoxycarbonylamino-4-methylphenol, 3,4-dimethylphenol and 2,4-dimethylphenol, 1- (4'-aminophenyl) -3-methyl-5-pyrazolone, 1- (2'-, 3'- or 4'-sulfophenyl) -3-methyl-5-pyrazo ion, 1- (2'-chloro-4'- or 5'-sulfophenyl) -3-methyl-5-pyrazolone , 1- (2'-Methyl-6'-chlorophenyl) -3-methyl-5-pyrazolone, 1- (2'-Methyl-4'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (2 ' -, 3'- or 4'-chloro- or methyl- or sulfophenyl) -3-carboxy-5-pyrazolone, 1- [5'-sulfonaphthyl (2 ')] - 3-methyl-5-pyrazolone, 1- [ 4 "-amino-2 ', 2" -disulfostilbene- (4')] - 3-methyl-5-pyrazolone, 1-ethyl-3-cyano-4-methyl-6-hydroxypyridone- (2), 1 -Aethyl-3-sulfomethyl-4-methyl-6-hydroxypyridone- (2), 2,6-dihydroxy-3-cyano-4-sulfomethylpyridine, 2,4,6-trihydroxypyrimidine, 2,3-dihydroxypyridine, 5-bromo - (chlorine) -2.3 -dihydroxypyridine, 2-amino-3-hydroxypyridine, 5-bromo-2-amino-3-hydroxypyridine, 5-ethylmercapto-2,3-dihydroxypyridine, 5-phenylsulfonyl-2,3-dihydropyridine, 2,3-dihydroxy -pyridine-5-sulfonic acid and 2-amino-3-hydroxypyridine-5-sulfonic acid.

The metal complexes are prepared by methods known per se in an aqueous or organic medium. Copper salts, such as e.g. Copper sulfate and copper nitrate. The freshly precipitated hydroxides can also be used. The reaction is carried out in the weakly acidic to alkaline range. One works, for example, with copper sulfate in an aqueous medium in the presence of sodium acetate or ammonia or with copper nitrate in the presence of soda in an organic medium such as methyl cellosolve.

Generally the reaction is carried out with heating, e.g. slightly below the boiling point of the solvent used.

A further embodiment of the process according to the invention is characterized in that component A) is a mixture comprising at least one water-soluble copper complex dye and a fiber-affine, water-soluble copper complex of an organic compound which is not a dye, i.e. which has no chromophoric groups.

Copper complexes of bisazomethines, acylhydrazones, semicarbazones and thiosemicarbazones of aromatic aldehydes or ketones which are preferably used as the non-coloring component are preferably sulfonic acid groups. Such compounds are readily water-soluble and also have an excellent affinity for polyamide fiber. Such complexes are therefore effective even in small amounts. In addition, it has been shown that they not only increase the light fastness of the dyed polyamide material, but also generally protect the polyamide fiber against photochemical degradation and thus largely maintain its mechanical properties, such as tear resistance and elasticity.

Bisazomethines of aromatic aldehydes and ketones are understood here as Schiff bases of aliphatic or cycloaliphatic diamines, the aldehydes and ketones in the o-position to the formyl or. Acyl residue have an OH group. The bond with the copper atom takes place via these two OH groups and the two nitrogen atoms in the bisazomethine part. Accordingly, these are tidentate ligands containing one or more sulfo groups which are located in the aldehyde or ketone part and / or in the bisazomethine bridge.

verwendet, worin R₂ Wasserstoff oder einen gegebenenfalls substituierten Alkyl- oder Arylrest, Z einen gegebenenfalls substituierten Alkylen- oder Cycloalkylenrest und n 1, 2 oder 3 bedeuten und die Ringe M und N unabhängig voneinander substituiert sein können; oder

• b) der Formel
  
  verwendet, worin R₃ und R₄ unabhängig voneinander dieselbe Bedeutung wie für R₂ angegeben haben; oder
• c) der Formel
  
  verwendet, worin R₅ Wasserstoff oder einen gegebenenfalls substituierten Alkyl- oder Arylrest und V ein Sauerstoff- oder Schwefelatom bedeuten.

Preferred embodiments of the processes according to the invention are characterized in that component A) is a mixture comprising a copper complex dye and a copper complex without color character a) of the formula

used in which R _{2 is} hydrogen or an optionally substituted alkyl or aryl radical, Z is an optionally substituted alkylene or cycloalkylene radical and n is 1, 2 or 3 and the rings M and N can be substituted independently of one another; or

• b) the formula
  
  used, wherein R ₃ and R ₄ independently of one another have the same meaning as given for R ₂ ; or
• c) the formula
  
  used, wherein R _{5 is} hydrogen or an optionally substituted alkyl or aryl radical and V is an oxygen or sulfur atom.

If R ₂ , R ₃ or Rs denotes an optionally substituted alkyl radical, preference is given to a C ₁ to Cs alkyl radical, in particular a C ₁ to C ₄ alkyl radical, which can be branched or unbranched and optionally substituted by halogen, such as fluorine, chlorine or bromine, C ₁ to C ₄ alkoxy, such as methoxy or ethoxy, by a phenyl or carboxyl radical, by Ci to C ₄ alkylcarbonyl, such as the acetyl radical or by hydroxy or a mono- or dialkylated amino group . In addition, the cyclohexyl radical can also be used, which can also be substituted, for example by C ₁ to C ₄ alkyl or C ₁ to C ₄ alkoxy.

If R ₂ , R ₃ or Rs is an optionally substituted aryl radical, a phenyl or naphthyl radical is particularly suitable, which can be substituted by C ₁ -C ₄ alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, C ₁ -C ₄ alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as fluorine, chlorine and Bromine, C ₂ -C ₅ alkanoylamino, such as acetylamino, proponylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.

If Z is an alkylene radical, it is primarily a C ₂ to C ₄ alkylene radical, in particular a -CH ₂ -CH ₂ bridge. However, a C ₂ to Cs alkylene chain interrupted by oxygen or, in particular, nitrogen is also suitable, and in particular the - (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ bridge.

If Z is a cycloalkylene radical, this is preferably cyclohexylene and can have one or two methyl groups.

Examples of suitable substituents for the benzene rings M and N are: Ci to C ₄ alkyl, C ₁ to C ₄ alkoxy, halogen, such as fluorine, chlorine or bromine, and also the cyano or nitro groups.

The sulfo groups which are located in the benzene rings M and / or N are preferably present as an alkali metal salt, in particular as a sodium salt or also as an amine salt.

In particular, the copper complexes of the formula (5) are used in the present process, in which R ₂ denotes hydrogen, Z denotes the ethylene or cyclohexylene bridge and n = 2, the two sulfo groups being in the benzene rings M and N, and above all here the complexes in which the sulfo groups are each arranged in p-position to the oxygen. Z is preferably -CH ₂ -CH ₂ -.

If R _{4 is} an alkylene radical, this can be branched or unbranched and has a chain length of preferably 1 to 8, in particular 1 to 4, carbon atoms. Halogen, such as fluorine, are suitable as substituents. Chlorine or bromine, C ₁ to C ₄ alkoxy, such as methoxy or ethoxy, also phenyl or carboxyl, C ₁ to C ₄ alkylcarbonyl, such as acetyl or hydroxy, mono- or dialkylamino.

If R _{4 is} an optionally substituted aryl radical, a phenyl or naphthyl radical which can be substituted by C ₁ -C ₄ -alkyl, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, is particularly suitable and tert-butyl, Ci-C ₄ -alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as fluorine, chlorine and bromine, C ₂ -Cs Alkanoylamino such as acetylamino, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.

The complexes of formula (6) are also preferred in neutral form, i.e. used as alkali salt, in particular sodium salt or amine salt.

Complexes of the formula (6) are preferably used in which R _{3 is} hydrogen and R _{4 is} hydrogen, methyl or in particular the phenyl radical, especially the complexes in which the sulfo group is in turn in the p-position to the oxygen.

In addition to the copper complexes of the formulas (6) and (7), the ligands of which are derived from the sulfosalicylaldehydes or the corresponding phenylketones, e.g. also those in which instead of mononuclear, multinuclear aromatic aldehydes and ketones, such as the 2-hydroxy-1-naphthaldehyde sulfonic acid can be used to build up the ligand. It is also pointed out that the fourth coordination point of the metal atom in the complexes of formulas (6) and (7) is occupied by water as the neutral ligand.

In the process according to the invention, the ratio of copper complex dye: fiber-affine, water-soluble copper complex of an organic compound which itself has no dye character is preferably 99: 1 to 10:90.

The mixing ratio depends on the number of copper complex dyes used and the desired depth of color of the dyeings and is selected such that the copper content of the polyamide fiber material is over 5 ppm, preferably over 10 ppm.

The copper complexes of the formulas (5), (6) and (7) given and their alkali metal salts, such as potassium and lithium salts, and in particular their sodium salts, are obtained by known methods.

The metal complexes of the formula (5) are accessible, for example, in two different ways. So you can first metallize the aldehyde or ketone and then react with the corresponding diamine to the finished complex of formula (5). However, one can also first synthesize the ligand from aldehyde or ketone and diamine and then carry out the metallization.

The acylhydrazones, the ligands of the complexes (6), are obtained, for example, by reacting the aldehyde or ketone with the corresponding monoacylhydrazine and subsequent metallization. The complexes of the formula (7) can also be prepared quite analogously. At least one of the starting products for the preparation of the compounds of the formula (5), (6) and (7) must contain a sulfonic acid group.

The component (A) used is preferably the copper complexes of the formulas (5) to (7), in particular the copper complexes of the formulas (5) and (6).

und innerhalb der Gruppe der Metallkomplexe mit Acylhydrazonligand die Kupferkomplexe der Formeln

The copper complexes of the formulas are very particularly preferred within the group of metal complexes with bisazomethine ligand

and within the group of metal complexes with acylhydrazone ligand, the copper complexes of the formulas

The fourth coordination point of the copper in the complexes of formulas (10), (11) and (12) is occupied by water without this being explicitly stated in the structural formulas.

A further preferred embodiment of the method according to the invention is characterized in that at least one copper complex dye is used as component A) together with acid dyes, in particular in the same dye bath.

Examples of suitable acid dyes are metal-free mono- or polyazo dyes, 1: 2 chrpm or 1: 2 cobalt complex azo dyes, anthraquinone, dioxazine, phthalocyanine, nitroaryl or stilbene dyes which contain at least one acid group, such as a carboxyl , Sulfo-, Ci-C4-alkylsulfonyl, sulfamoyl or di-C ₁ -C ₄ alkylsulfamoyl- preferably have a sulfonic acid group.

An interesting embodiment of the method according to the invention is e.g. characterized in that a mixture of at least one red dye, at least one yellow or orange dye and at least one blue dye is used for trichromatic dyeing, the mixture containing at least one copper complex dye.

As component B) all those compounds can be mentioned which are also known as UV absorbers and e.g. in Kirk-Othmer 23, 615-627; A.F. 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.

The copper complex dyes can optionally be used in combination with conventional dyes for polyamide fiber material.

• a) 2-Hydroxybenzophenone der Formel (13)
  
  worin
  • R₁ Wasserstoff, Hydroxy, C₁-C₁₄-Alkoxy oder Phenoxy,
  • R₂ Wasserstoff, Halogen, 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-, 2'-Hydroxy-4,4'-dimethoxy-5-sulfo-, 4-Benzyloxy- und 5-Chlor-Derivat;
• b) 2-(2'-Hydroxyphenyl)-benzotriazole der Formel (14)
  
  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-Cylcoalkyl, C₂-C₉-Alkoxycarbonyl, Chlor, Carboxyethyl, C₇-C₉-Phenylalkyl, oder Sulfo
  • R₄ Wasserstoff, Chlor, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₂-C₉-Alkoxycarbonyl, Carboxy oder Sulfo und
  • Rs 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 (14) 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-(a,a-dimethylbenzyl)-Derivat sowie das Natriumsalz der 2-(2'-Hydroxy-3'-tert.butyl-5'-methylphenyl)-5-(2H)-benzotriazolsulfonsäure, der 3-tert.-Butyl-4-hydroxy-5-[benzotriazol-(2)-yl]-benzolsulfonsäure, der 3-tert.- Butyl-4-hydroxy-5-[5-chlor-benzotriazol-(2)-yl]-benzolsulfonsäure und der 3-sec.-Butyl-4-hydroxy-5-[benzotriazol-(2)-yl]-benzolsulfonsäure; oder
• 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 (15)
  
  enthält, worin R Wasserstoff oder Methyl bedeutet.

The following compounds can be used as component B):

• a) 2-hydroxybenzophenones of the formula (13)
  
  wherein
  • R _{1 is} hydrogen, hydroxy, C ₁ -C ₁₄ alkoxy or phenoxy,
  • R _{2 is} hydrogen, halogen, C ₁ -C ₄ alkyl or sulfo,
  • R _{3 is} hydrogen, hydroxy or C ₁ -C ₄ alkoxy and
  • R _{4 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, 2'-hydroxy-4,4'-dimethoxy-5-sulfo, 4-benzyloxy and 5-chloro derivatives;
• b) 2- (2'-hydroxyphenyl) benzotriazoles of the formula (14)
  
  wherein
  • R _{1 is} hydrogen, C ₁ -C ₁₂ alkyl, chlorine, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ phenylalkyl or sulfo
  • R _{2 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, chlorine, hydroxy or sulfo
  • R _{3 is} C ₁ -C ₁₂ alkyl, C ₁ -C ₄ alkoxy, phenyl, (C ₁ -C ₈ alkyl) phenyl, C ₅ -C ₆ cycloalkyl, C ₂ -C ₉ alkoxycarbonyl, chlorine, Carboxyethyl, C ₇ -C ₉ phenylalkyl, or sulfo
  • R _{4 is} hydrogen, chlorine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₉ alkoxycarbonyl, carboxy or sulfo and
  • Rs is 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 (14) 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 (a, a-dimethylbenzyl) derivative as well as the sodium salt of 2- (2'-hydroxy- 3'-tert-butyl-5'-methylphenyl) -5- (2H) -benzotriazolesulfonic acid, the 3-tert.-butyl-4-hydroxy-5- [benzotriazol- (2) -yl] -benzenesulfonic acid, the 3- tert-butyl-4-hydroxy-5- [5-chloro-benzotriazole- (2) -yl] -benzenesulfonic acid and 3-sec-butyl-4-hydroxy-5- [benzotriazole- (2) -yl] -benzenesulfonic acid; or
• 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 (15) in its molecule
  
  contains, wherein R is hydrogen or methyl.

The light stabilizer can contain one or more such groups of the formula (15), for example it can be a mono-, bis-, tris-, tetra- or oligo-piperidine compound. Preference is given to piperidine derivatives which contain one or more groups of the formula (15) in which R is hydrogen, and those whose ring nitrogen has no 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.

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, Cs_-Cs-Alkinyl, C₇-C₁₂-Aralkyl, C₁-C₈-Alkanoyl, C₃-Cs-Alkenoyl, Glycidyl oder eine Gruppe -CH₂-CH(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,ß-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 aromatischen 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.aa) compounds of the formula (16)

wherein n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, R ^{1 is} hydrogen, oxyl, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, Cs _- Cs-alkynyl, C ₇ -C ₁₂ aralkyl, C ₁ -C ₈ alkanoyl, C ₃ -Cs alkenoyl, glycidyl or a group -CH ₂ -CH (OH) -Z, where Z is hydrogen, methyl or phenyl, where R ^{1 is} preferably C ₁ -C ₁₂ alkyl, allyl, benzyl, acetyl or acryloyl and R ² , when n is 1, is hydrogen, C ₁ -C ₁₈ alkyl, cyanoethyl, benzyl, glycidyl optionally interrupted by one or more oxygen atoms, 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 a radical of an aliphatic carboxylic acid having 2 to 18 C atoms, a cycloaliphatic carboxylic acid having 7 to 15 C atoms, an α, ß-unsaturated carboxylic acid with 3 to 5 carbon atoms or an aromatic carbons acid with 7 to 15 carbon atoms means, when n is 2, C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing Acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, if n is 3, is 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, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

If any substituents are C ₁ -C ₁₂ -alkyl, they are, 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 C ₁ -C ₁₈ alkyl, R ¹ or R ^{2 can represent,} for example, the groups mentioned above and, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

If R ^{1 is} C ₃ -C ₈ -alkenyl, it can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2 -butenyl act.

As Cs-Ca-alkynyl, R ¹ is preferably propargyl.

As C ₇ -C ₁₂ aralkyl, R ^{1 is} in particular phenethyl or especially benzyl.

As C ₁ -C ₈ alkanoyl, R ¹ is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and as C ₃ -C ₅ alkenoyl, in particular acryloyl.

If R ^{2 is} a monovalent radical of a carboxylic acid, it represents, for example, acetic, caproic, stearic, acrylic, methacrylic, benzoic or β- (3,5-di-tert-butyl-4-hydroxy) phenyl) propionic acid residue.

If R ^{2 is} a divalent radical of a dicarboxylic acid, it is, for example, a malonic acid, adipic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl (3,5-di-tert.- butyl-4-hydroxybenzyl) malonic or bicycloheptenedicarboxylic acid residue. If R ^{2 is} a trivalent carboxylic acid residue, it means, for example, a trimellitic acid or a nitrilotriacetic acid residue.

If R ^{2 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 R ^{2 is} a divalent radical of a dicarbamic acid, it is, for example, a hexamethylene dicarbamic acid or a 2,4-tolylene dicarbamic acid radical.

• 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-tetramethyipiperidin
• 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-diethyl-piperidin-4-yl(sebacat
• 13) Di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalat
• 14) 1-Propargyl-4-ß-cyanoethyloxy-2,2,6,6-tetramethylpiperidin
• 15) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-ylacetat
• 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) Toluol-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-tetramethylpiperdin
• 32) 4-Hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidin
• 33) 1-Glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidin

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-tetramethyipiperidine
• 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-diethyl-piperidin-4-yl (sebacate
• 13) Di- (1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate
• 14) 1-Propargyl-4-ß-cyanoethyloxy-2,2,6,6-tetramethylpiperidine
• 15) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-ylacetate
• 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) toluene-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-tetramethylpiperdine
• 32) 4-Hydroxy-N- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine
• 33) 1-Glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

worin n die Zahl 1 oder 2 bedeutet, R und R¹ die unter a) angegebene Bedeutung haben, R³ Wasserstoff, Ci-C₁2-Alkyl, C₂-Cs-Hydroxyalkyl, C₅-C₇-Cycloalkyl, C₇-C₈-Aralkyl, C₂-C₁₈-Alkanoyl, C₃-Cs-Alkenoyl oder Benzoyl ist und R₄ wenn n 1 ist, Wasserstoff, C₁-C₁₈-Alkyl, C₃-Cs-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, Cs-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.bb) compounds of the formula (17)

in which n denotes the number 1 or 2, R and R ^{1 have} the meaning given under a), R ^{3 is} hydrogen, Ci-C ₁ 2-alkyl, C ₂ -Cs-hydroxyalkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₈ aralkyl, C ₂ -C ₁₈ alkanoyl, C ₃ -Cs alkenoyl or benzoyl and R ₄ when n is 1 is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -Cs alkenyl, C ₅ -C ₇ cycloalkyl, with a hydroxy, cyano, alkoxycarbonyl or carbamide group substituted C ₁ -C ₄ alkyl, glycidyl, a group of the formula -CH ₂ -CH (OH) -Z or the formula-CONH-Z is; wherein Z is hydrogen, methyl or phenyl; if n is 2, C ₂ -C ₁₂ alkylene, Cs-C12 arylene, xylylene, a -CH ₂ -CH (OH) -CH ₂ group or a group -CH ₂ -CH (OH) -CH ₂ - ODO- means where DC is ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene, C ₆ -C ₁₂ cycloalkylene, or provided that R _{3 is} not alkanoyl, alkenoyl or benzoyl, R ^{4 is} also a divalent radical an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or also the group -CO-, or R ³ and R ⁴ together, if n is 1, the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3- Can mean dicarboxylic acid.

If any substituents are C ₁ -C ₁₂ or C ₁ -C ₁₈ alkyl, they have the meaning already given under aa).

If any substituents are C ₅ -C ₇ -cycloalkyl, they are in particular cyclohexyl.

As C ₇ -C ₈ aralkyl, R ^{3 is} in particular phenylethyl or especially benzyl. As C ₂ -C ₅ hydroxyalkyl, R ^{3 is} in particular 2-hydroxyethyl or 2-hydroxypropyl.

R ³ is as C ₂ -C ₁₈ alkanoyl, for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and as C ₃ -Cs alkenoyl, in particular acryloyl.

If R ^{4 is} C ₂ -C ₈ alkenyl, then it is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

R ⁴ as a C ₁ -C ₄ alkyl substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- ( Be dimethylaminocarbonyl) ethyl.

Any C ₂ -C ₁₂ alkylene substituents are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene. Any C ₆ -C ₁₅ arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

As C ₆ -C ₁₂ cycloalkylene, D is in particular cyclohexylene.

• 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;

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;

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 (18) sind z.B. 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 oder 2-(2'-Hydroxy-4'-methoxy-5'-sulfophenyl)-4,6-diphenyl-s-triazin; (vergl. z.B. WO-A-86/03528.d) 2- (2'-hydroxyphenyl) -s-triazines of the formula (18)

wherein R is hydrogen, halogen, C ₁ -C ₄ alkyl or sulfo, R _{1 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or hydroxy R _{2 is} hydrogen or sulfo and R ₃ and R _{4 are} independently of one another C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₅ -C ₆ cycloalkyl, phenyl or phenyl substituted by C ₁ -C ₄ alkyl and hydroxy, the sulfo groups in free form or in salt form, For example, alkali metal, alkaline earth metal, ammonium or amine salts may be present. Examples of compounds of the formula (18) are, for example, 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 or 2- (2'-hydroxy-4'-methoxy-5'-sulfophenyl) -4,6-diphenyl-s-triazine; (see, for example, WO-A-86/03528.

Compounds C) which, e.g. In Kirk-Othmer (3.), 3, pages 132-135 or in R. Gächter and H. Müller, Taschenbuch der Kunststoff-Additive, Carl Hanser Verlag, Manchen, pages 4-78 (1983).

• a) sterisch gehinderte Phenole z.B. Hydroxiphenylpropionate der Formel (19)
  
  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)₂0(CH₂)₂0(CH₂)₂0-, -HN-(CH₂)₂-₆-NH- oder O(CH₂)₂-S-(CH₂)₂0-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-, Trlmethylen- oder Hexamethylendiamin:
• b) Thioether der Formel (20)
  • (20) ROOC-(CH₂)₂-S-(CH₂)₂-COOR
  • worin R einen C_a-C₂₄-Alkylrest bedeutet, wie z.B. das Dilaurylthiodipropionsäure- und Distearylthiodipropionsäurederivat und
• c) Phosphite der Formel (21)
  
  worin R_i Phenyl, 2,4-Di-tert.butylphenyl oder p-Nonylphenyl und R₂ n-Decyl, 2,4-Di-tert.butyl-phenyl oder p-Nonylphenyl bedeuten, wie z.B. das Tris-(p-nonylphenyl)-phosphit, Tris-(2,4-di-tert.butylphenyl)-phosphit und Diphenyl-n-decyl-phosphit sowie
• d) ein Gemisch aus einem Hydroxyphenylpropionat der oben angegebenen Formel (19) mit einem Phosphit der oben angegebenen Formel (21) in einem Molverhältnis (19):(21) von 1:1 bis 1:4.
• e) Phosponate der Formel
  
  worin R₁ und R₂ unabhängig voneinander C₁-C₂₄-Alkoxy und n die Zahl 0, 1,2 oder 3 bedeuten.

The following compounds can be used as component C):

• a) sterically hindered phenols, for example hydroxiphenylpropionates of the formula (19)
  
  wherein n is an integer from 1 to 4 and AC ₁ -C ₂₄ alkoxy, a bridge member -O (CH ₂ ) ₆ O-, -O (CH ₂ ) ₂ O (CH ₂ ) ₂ O-, -O (CH ₂ ) ₂ 0 (CH ₂ ) ₂ 0 (CH ₂ ) ₂ 0-, -HN- (CH ₂ ) ₂ - ₆ -NH- or O (CH ₂ ) ₂ -S- (CH ₂ ) ₂ 0 -or den Rest - (CH ₂ O) 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:
• b) thioethers of the formula (20)
  • (20) ROOC- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -COOR
  • wherein R is a C _a -C ₂₄ alkyl radical, such as the dilaurylthiodipropionic acid and distearylthiodipropionic acid derivative and
• c) phosphites of the formula (21)
  
  in which R _{i is} phenyl, 2,4-di-tert-butylphenyl or p-nonylphenyl and R _{2 is} n-decyl, 2,4-di-tert-butyl-phenyl or p-nonylphenyl, such as, for example, tris (p- nonylphenyl) phosphite, tris (2,4-di-tert.butylphenyl) phosphite and diphenyl-n-decyl phosphite as well
• d) a mixture of a hydroxyphenyl propionate of the above formula (19) with a phosphite of the above formula (21) in a molar ratio (19) :( 21) of 1: 1 to 1: 4.
• e) Phosphonates of the formula
  
  wherein R ₁ and R ₂ independently of one another are C ₁ -C ₂₄ alkoxy and n is the number 0, 1, 2 or 3.

• Di-n-octadecyl-1-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)ethanphosphonat,
• Di-ethyl-3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonat,
• Di-n-butyl-3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonat oder
• Di-n-dodecyl-3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonat.

Examples of compounds of the formula are, for example

• Di-n-octadecyl-1- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) ethane phosphonate,
• Di-ethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
• Di-n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate or
• Di-n-dodecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate.

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 (7) to (12) are e.g. known from EP-A 51 188,113 856 and 162811 and can be prepared by known processes.

The compounds of the formulas (13) and (14) 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.

The preparation of the compounds from the class of the sterically hindered amines of the formulas (15) to (17) is e.g. in U.S.-A-3,640,928, 3,840,494 and 3,993,655.

The compounds of formula (18) can be prepared in a manner known per se, e.g. according to the methods described in Helv. 55, 1566-1595 (1972).

Compounds of formula (19) can be prepared in a manner known per se, e.g. in GB-A-1 103 144.

Compounds of formula (20) can be prepared in a manner known per se, e.g. according to the method described in US-A-2,468,725.

The phosphites of formula (21) can also be prepared by methods known per se, e.g. according to the method published in US-A-4 187 212.

The phosphonates of formula (22) can be prepared in a manner known per se, e.g. according to the method disclosed in US-A-3,270,091.

The agents according to the invention are expediently applied from an aqueous bath, these being used advantageously in an amount such that 5 to 800 μg, in particular 10 to 200 μg, of copper metal are added to 1 g of polyamide. Si therefore contain a) 0.005 to 0.8% by weight of an organic copper complex with 10% copper content, 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 for stabilizing colored 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 (particle size <5 μm) which are obtained by grinding in the presence of customary dispersants.

Synthetic polyamide, e.g. Polyamide-6, polyamide-6,6 or also polyamide-12 understood. In addition to the pure polyamide fibers, fiber mixtures made of polyurethane and polyamide are also considered, e.g. Jersey material made of polyamide / polyurethane in a mixing ratio of 70:30. In principle, the pure or mixed polyamide material can be in a wide variety of processing forms, e.g. 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 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.

• Farbstoff der Formel
  
• Farbstoff der Formel
  
• Farbstoff der Formel
  
• Farbstoff der Formel
  
• Farbstoff der Formel
  
• Lichtschutzmittel der Formel
  
  in feindisperser Form (Teilchengrösse <4 µm); gemahlen mit dem Kondensationsprodukt aus Naphthalinsulfonsäure und Formaldehyd, als Dispergator, im Gewichtsverhältnis 1:1.

Example 1: Four 10 g skeins of polyamide 66 staple yarn and four polyamide 66 auto upholstery pieces of 10 g are treated in a dyeing machine (eg AHIBA ^® machine) with liquors (liquor ratio 1:20), which are generally 1 g / I contain ammonium sulfate (pH 6.5) and the following dyes and additives (calculated on the fiber material):

• Dye of the formula
  
• Dye of the formula
  
• Dye of the formula
  
• Dye of the formula
  
• Dye of the formula
  
• Light stabilizers of the formula
  
  in finely dispersed form (particle size <4 µm); ground with the condensation product of naphthalenesulfonic acid and formaldehyde, as a dispersant, in a weight ratio of 1: 1.

• 0,08 % des Farbstoffes der Formel (101)
• 0,035 % des Farbstoffes der Formel (102)
• (Oliv-Färbung)
• Färbeflotte 2: 0,08 % des Farbstoffes der Formel (101)
• 0,035 % des Farbstoffes der Formel (102)
• 0,055 % des Farbstoffes der Formel (103)
• 0,008 % des Farbstoffes der Formel (104)
• (Oliv-Färbung)

Dyeing liquor 1: 0.05% of the dye of the formula (100)

• 0.08% of the dye of the formula (101)
• 0.035% of the dye of the formula (102)
• (Olive color)
• Dyeing liquor 2: 0.08% of the dye of the formula (101)
• 0.035% of the dye of the formula (102)
• 0.055% of the dye of the formula (103)
• 0.008% of the dye of the formula (104)
• (Olive color)

Dyeing liquor 3: like dyeing liquor 2 plus 1% of the light stabilizer of the formula

Dyeing liquor 4: like dyeing liquor 2 but aftertreatment of the dyeing with 0.65% of the light stabilizer

Formula (105) and 1.00% acetic acid (80%) diluted with water for 45 minutes at 60 ° C. The finished dyeings are rinsed and dried and tested as follows:

(a) light fastness:

• - Xenonlicht gemäss der Schweizerischen Norm SN-ISO 105-B02
• - Fakralicht gemäss der DIN 75.202 (Heissbelichtung)

The jersey material is tested:

• - Xenon light according to the Swiss standard SN-ISO 105-B02
• - Fractal light according to DIN 75.202 (hot exposure)

(b) Photo stability:

The polyamide staple yarn is wound onto cardboard and exposed for 150 hours under conditions of light. The yarn is then tested for tensile strength and elongation in accordance with SNV (Swiss Association for Standardization) - standard 197.461. The following results are obtained, the tensile strength and elongation of unexposed and untreated polyamide 68 staple yarn being set equal to 100%.

• a) die Färbung aus der Färbeflotte 1, wie die Werte der Reissfestigkeit und Dehnung veranschaulichen, nach einer 150-stündigen Heissbelichtung nach Fakra eine äusserst ungenügende photochemische Stabilität aufweist,
• b) die Mitverwendung der Cu-Komplexfarbstoffe der Formeln (103) und (104) einen deutlichen Anstieg der photochemischen Stabilität bewirkt,
• c) diese durch die Mitverwendung des Lichtschutzmittels der Formel (106) oder (105) verbessert wird und
• d) die Lichtechtheiten, besonders jene nach Fakra, durch die Verbindung der Formel (106) oder (105) verbessert werden.

These results show that

• a) the dyeing from dyeing liquor 1, as the values of the tensile strength and elongation illustrate, has extremely poor photochemical stability after a 150-hour hot exposure according to Fakra,
• b) the co-use of the Cu complex dyes of the formulas (103) and (104) brings about a significant increase in the photochemical stability,
• c) this is improved by the use of the light stabilizer of the formula (106) or (105) and
• d) the light fastness properties, especially those according to Fakra, are improved by the compound of the formula (106) or (105).

Example 2: The dyeing of the polyamide 66 yarns or the tricot material is carried out as described in Example 1 with the following differences

Dyeing liquor 5: 0.05% of the dye of the formula

Dyeing liquor 6: 0.05% of the dye of the formula (200)

1.0% of the light stabilizer of the formula

Dyeing liquor 7: 0.05% of the dye of the formula (200) 1.0% of the light stabilizer of the formula

(als 10%-iges sandgemahlenes Produkt).Dyeing liquor 8: 0.05% of the dye of the formula (200) 0.4% of the compound of the formula

(as a 10% sand-ground product).

Dyeing liquor 9: 0.05% of the dye of the formula (200) 0.4% of the compound of the formula (203)

1.0% of the light stabilizer of the formula (202)

Dyeing liquor 10: 0.25% of the dye of the formula (200) Dyeing liquor 11: 0.25% of the dye of the formula (200)

1.0% of the light stabilizer of the formula (201)

Dyeing liquor 12: 0.25% of the dye of the formula (200)

1.0% of the light stabilizer of the formula (202)

The finished dyeings are rinsed and dried and tested as described in Example 1.

The results are summarized in the table below:

The results show that the light stabilizers improve the lightfastness of the dyeings. If the amount of copper in the fiber is increased, the photochemical degradation can also be delayed (dyeing liquors 8 and 9).

und

• 1,0 % Essigsäure (80%)
• enthält.

Example 3: The dyeings are made on polyamide 66 tricot as described in Example 2 with 0.1% and 0.25% of the dye of the formula (200). The colors are then halved. While halves 1 and 3 remain unchanged, halves 2 and 4, on the other hand, are treated in a liquor ratio 1:25 at 65 ° C. for 30 minutes with a liquor which
1.5% of the compound of the formula

and

• 1.0% acetic acid (80%)
• contains.

All 4 dyeings are tested for their light fastness after rinsing and drying.

The results are shown in Table 3 below.

Example 4: The dyeings are carried out as described in Example 1, but with the following differences: dye liquor 13: 0.025% of the dye of the formula (101) 0.050% of the dye of the formula (103) (hue light green) dye liquor 14: 0.025% of the dye of the formula (101) 0.050% of the dye of the formula (103) (hue light green) 1.0% of the light stabilizer of the formula

Dyeing liquor 15: 0.025% of the dye of the formula (101) 0.050% of the dye of the formula (103) (hue light green) 1.0% of the light stabilizer of the formula (400) 0.075% of the compound of the formula

Dyeing liquor 16: 0.025% of the dye of the formula (101) 0.050% of the dye of the formula (103) (hue light green) 1.0% of the light stabilizer of the formula (400) 0.05% of the compound of the formula

Dyeing liquor 17: 0.025% of the dye of the formula (101) 0.050% of the dye of the formula (103) (hue light green) 1.0% of the light stabilizer of the formula (400) 0.5% of the compound of the formula

The finished dyeings are rinsed and dried and tested as in Example 1.

The results are summarized in the table below.

The results show that the light stabilizers improve the lightfastness of the dyeings and that the increase in the amount of copper in the fiber delays the photochemical degradation (dyeing liquors 15-17).

Claims (27)

1. A process for the photochemical stabilization of polyamide fiber material _a l or mixtures thereof with other fiber materials, characterized in that the fiber material is made with a mixture of A) a water-soluble copper complex dye or a mixture of copper complex compounds, at least one component being a water-soluble copper complex dye, B) a light stabilizer and if desired C) an antioxidant
treated. 2. The method according to claim 1, characterized in that one uses at least one water-soluble copper complex azo dye. 3. The method according to claim 2, characterized in that water-soluble copper complexes of azo dyes of the formula

wherein D is a radical of the benzene or naphthalene series, Y is the HO-, CH ₃ 0 or HOOC group and Y 'is the HO- group or amino group, and wherein K is the radical of a coupling component of the benzene, naphthalene or heterocyclic series or the rest of a ketomethylene compound. 4. The method according to claim 3, characterized in that a copper complex dye of the formula

used, in which A is an optionally substituted carboxyphenyl or sulfophenyl radical, R _{1 is} hydrogen or C ₁ -C ₄ alkyl and K is the rest of a coupling component of the benzene, naphthalene, pyrazolone, aminopyrazole, acetoacetanilide, 2,4-dioxyquinoline -, pyridone or pyridine series and the ring B can optionally be further substituted, for example by chlorine or nitro. 5. The method according to claim 1, characterized in that the mixture contains a copper complex dye and a fiber-affine, water-soluble copper complex of an organic compound which is not a dye. 6. The method according to claim 5, characterized in that the mixture comprises a copper complex dye and a fiber-affine, water-soluble copper complex of bisazomethines, acylhydrazones, Contains semicarbazones or thiosemicarbazones of aromatic aldehydes or ketones. 7. The method according to claim 5, characterized in that one of the formula as fiber-affine water-soluble copper complex

used, wherein R _{2 is} hydrogen or an optionally substituted alkyl or aryl radical, Z is an optionally substituted alkylene or cycloalkylene radical and n is 1, 2 or 3 and the rings M and N can be substituted independently of one another. 8. The method according to claim 5, characterized in that the fiber-affine, water-soluble copper complex is one of the formula

used, wherein R ₃ and R ₄ independently of one another have the same meaning as for R ₂ in claim 7. 9. The method according to claim 5, characterized in that the fiber-affine, water-soluble copper complex is one of the formula

used, wherein R _{5 is} hydrogen or an optionally substituted alkyl or aryl radical and V is an oxygen or sulfur atom. 10. The method according to claim 5, characterized in that a mixture is used in which the ratio of copper complex dye to the fiber-affine water-soluble copper complex compound, which itself has no dye character, is 99: 1 to 10:90. 11. The method according to claim 1, characterized in that copper complex dyes or mixtures of the copper complex compounds are used in an amount such that 2 to 4000 μg of copper are added to 1 g of polyamide material, in particular that 10 to 200 μg of copper are added to 1 g of polyamide. 12. The method according to claim 1, characterized in that one uses at least one copper complex dye or mixture of the copper complex compounds, each together with acid dyes. 13. The method according to claim 12, characterized in that one uses at least one copper complex dye or the mixture of the copper complex compounds together with acid dyes or weakly acid dyes in the same dye bath. 14. The method according to claim 12 or 13, characterized in that metal-free monoazo or polyazo dyes, 1: 2-chromium or 1: 2-cobalt complex azo dyes, anthraquinone, dioxazine, phthalocyanine, nitroaryl or stilbene dyes are used as acid dyes, which have at least one carboxyl, sulfo, C _i -C ₄ alkylsulfonyl, sulfamoyl or C ₁ -C ₄ dialkylsulfamoyl group. 15. The method according to claim 12, characterized in that for the trichromatic dyeing a mixture of at least one red dye, at least one yellow or orange dye and at least one blue dye is used, the mixture containing at least one copper complex dye. 16. The method according to any one of claims 1 to 15, characterized in that as component B) a 2-hydroxybenzophenone of the formula

used where R _{1 is} hydrogen, hydroxy, C ₁ -C ₁₄ alkoxy or phenoxy, R _{2 is} hydrogen, halogen, C ₁ -C ₄ alkyl or sulfo, R _{3 is} hydrogen, hydroxy or C ₁ -C ₄ alkoxy and R _{4 is} hydrogen, hydroxy or carboxy
mean. 17. The method according to any one of claims 1 to 15, characterized in that as component B) a 2- (2'-hydroxyphenyl) benzotriazole of the formula

wherein R _{1 is} hydrogen, C ₁ -C ₁₂ alkyl, chlorine, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ phenylalkyl or sulfo R _{2 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, chlorine, hydroxy or sulfo R _{3 is} C ₁ -C ₁₂ alkyl, C ₁ -C ₄ alkoxy, phenyl, (C ₁ -C ₈ alkyl) phenyl, C ₅ -C ₆ cycloalkyl, C ₂ -C ₉ alkoxycarbonyl, chlorine, Carboxyethyl, C ₇ -C ₉ phenylalkyl, or sulfo R _{4 is} hydrogen, chlorine, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₉ alkoxycarbonyl, carboxy or sulfo and R _{5 is} hydrogen or chlorine
mean. 18. The method according to any one of claims 1 to 15, characterized in that a compound from the class of sterically hindered amines is used as component B). 19. The method according to claim 18, characterized in that a 2,2,6,6-tetraalkylpiperidine derivative is used as the sterically hindered amine, which has at least one group of the formula in its molecule

contains, wherein R is hydrogen or methyl. 20. The method according to any one of claims 1 to 15, characterized in that as component B) a 2- (2'-hydroxyphenyl) -s-triazine of the formula

used, wherein R is hydrogen, halogen, C _i -C ₄ alkyl or sulfo, R _{1 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or hydroxy, R _{2 is} hydrogen or sulfo and R ₃ and R ₄ independently of one another are C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₅ -C ₆ cycloalkyl, phenyl or phenyl substituted by C ₁ -C ₄ alkyl, and hydroxy. 21. The method according to any one of claims 1 to 19, characterized in that as Component (C) a hydroxyphenyl propionate of the formula

used, where n is an integer from 1 to 4 and AC ₁ -C ₂₄ alkoxy, a bridge member -O (CH ₂ ) ₆ O-, -0 (CH2) 20 (CH2) 20-, -0 (CH ₂ ) ₂ 0 (CH ₂ ) ₂ 0 (CH ₂ ) ₂ 0-, -HN- (CH ₂ ) ₂ - ₆ -NH- or -0 (CH ₂ ) ₂ -S- (CH ₂ ) ₂ 0 -or the rest - (CH ₂ O) ₄ -C mean. 22. The method according to any one of claims 1 to 19, characterized in that component C) is a thioether of the formula
ROOC-CH ₂ CH ₂ -S-CH ₂ CH ₂ COOR
used, wherein R is a C ₈ -C ₂₄ alkyl radical. 23. The method according to any one of claims 1 to 19, characterized in that as component C) a phosphite of the formula

used, wherein R _{1 is} phenyl, 2,4-di-tert-butylphenyl or nonylphenyl and R _{2 is} n-decyl, 2,4-di-tert.butylphenyl or nonylphenyl. 24. The method according to any one of claims 1 to 19, characterized in that as component C) a mixture of a hydroxyphenyl propionate of the formula

with a phosphite of the formula

in the molar ratio hydroxyphenyl propionate: phosphite of 1: 1 to 1: 4, where n is an integer from 1 to 4 and AC ₁ -C ₂₄ alkoxy, a bridge member -O (CH ₂ ) ₆ O-, -NH- (CH ₂ ) ₂ -s-NH-, -OCH ₂ CH ₂ -NH-OC-CO-NH-CH ₂ CH ₂ 0-, -OCH ₂ CH ₂ 0CH ₂ CH ₂ 0-, -OCH ₂ CH ₂ 0CH ₂ CH ₂ 0CH ₂ CH ₂ 0- or -0 (CH ₂ ) ₂ -S- (CH ₂ ) ₂ 0 -or the rest - (CH ₂ 0) ₄ -C, R ₁ phenyl, 2,4-di-tert. phenyl or nonylphenyl and R _{2 is} n-decyl, 2,4-di-tert-butylphenyl or nonylphenyl. 25. The method according to any one of claims 1 to 19, characterized in that a component c) is a phosphonate of the formula

used, wherein R ₁ and R ₂ independently of one another are C ₁ -C ₂₄ alkoxy and n is the number 0, 1, 2 or 3. 26. Agent for the photochemical stabilization of undyed and dyed polyamide fiber material or mixtures thereof with other fiber materials, characterized in that it a) 0.005 to 0.8% by weight of an organic copper complex, b) 0.05 to 3% by weight, preferably 0.1 to 1% by weight of a light stabilizer and optionally c) 0.05 to 3% by weight, preferably 0.1 to 1% by weight, of an antioxidant. 27. The treated with the method according to any one of claims 1 to 25 polyamide fiber material and its mixtures with other fiber materials.