EP0245204A1 - Process for the photochemical stabilization of undyed and dyed fibrous polyamide material and its mixture with other fibres - Google Patents

Abstract

A process is described 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 treated with a mixture of A) an organic copper complex, B) a light stabilizer and, if desired (C) an antioxidant , a means for carrying out the method and the fiber material treated with it.

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 organic copper complexes, 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.

EP-A 162 811 and Textilveredlung 20 (1985), No. 11, pages 346-357 disclose 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 organischen Kupferkomplex,
• 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) an organic copper complex,
• B) a light stabilizer and if desired
• C) an antioxidant

treated.

Non-coloring copper complexes of bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic aldehydes or ketones or oximes are suitable as component A). Such compounds have an excellent affinity for polyamide fiber material and if they have water-solubilizing groups they are also well water-soluble. They are therefore effective in extremely small amounts.

Bisazomethines of aromatic aldehydes or ketones are understood to mean Schiff bases of aliphatic or aromatic diamines, the aldehydes and ketones having an HO group in the o-position to the formyl or acyl 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. The ligands can contain one or more sulfo groups which are located in the aldehyde or ketone part and / or in the bisazomethine bridge.

worin R für Wasserstoff oder einen gegebenenfalls substituierten Alkyl- oder Arylrest steht, Q einen gegebenenfalls substituierten Alkylen-, Cycloalkylen- oder Arylenrest und n 0, 1, 2 oder 3 bedeutet.Copper complexes of the formula (1) are preferably used as component A)

where R is hydrogen or an optionally substituted alkyl or aryl radical, Q is an optionally substituted alkylene, cycloalkylene or arylene radical and n is 0, 1, 2 or 3.

The benzene rings A and B can also be substituted independently of one another.

If R denotes an optionally substituted alkyl radical, preference is given to a C ₁ -C ₈ -alkyl radical, in particular a C ₁ -C ₄ -alkyl radical, which can be branched or unbranched and optionally substituted by halogen, such as fluorine, chlorine or Bromine, C _I -C ₄ alkoxy, such as methoxy or ethoxy, by a phenyl or carboxyl radical, by C _I -C ₄ alkoxycarbonyl, 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 may also be substituted, for example by C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy.

If R 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 _I -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, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.

If Q is an alkylene radical, it is primarily a C ₂ -C ₄ alkylene radical, in particular a -CH ₂ -CH ₂ bridge. However, a C ₂ -C ₈ alkylene chain interrupted by oxygen or, in particular, nitrogen is also suitable, in particular the - (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ bridge.

If Q is an arylene radical, it is primarily a phenylene radical, in particular an o-phenylene radical. This can also be substituted by C _I -C ₄ alkyl or C _I -C ₄ alkoxy.

If Q is a cycloalkylene radical, it is a cycloaliphatic radical with 5-7 C atoms, such as cyclopentylene, cyclohexylene or cycloheptylene.

Possible substituents for the benzene rings A and B are: halogen, such as fluorine, chlorine or bromine, the cyano or nitro group, alkyl, alkoxy, hydroxy, hydroxyalkyl, alkoxyalkoxy, alkoxyalkoxyalkoxy, carboxymethoxy, alkylamino, dialkylamino, -SO ₂ NH ₂ , -SOzNHR or -SO ₂ N (R _o ) ₂ , where R is alkyl or alkoxyalkyl and where under Alkyl and alkoxy are each to be understood as residues with 1-4 C atoms, or a benzene residue formed from residues ortho to one another, together with the C atoms to which they are attached.

The sulfo group (s) which are located in the benzene rings A and / or B and / or in the bridge member Q, if this denotes an arylene radical, are preferably in the form of an alkali metal salt, in particular a sodium salt or else an amine salt.

In particular, the copper complexes of the formula (1) are used in the present process, in which R denotes hydrogen, Q denotes the ethylene or o-phenylene bridge and n = 0 or 2, the two sulfo groups being located in the benzene rings A and B and here especially the complexes in which the sulfo groups are arranged in p-position to the oxygen.

worin

• R' Wasserstoff oder C₁-C₃-Alkyl
• Ri, R₂, R₃ und R₄ je Wasserstoff, Halogen, Hydroxy, Hydroxyalkyl, Alkyl, Alkoxy, Alkoxyalkoxy, Alkoxyalkoxyalkoxy, Carboxymethoxy, Alkylamino, Dialkylamino, -SO₂NH₂, -SO₂NHR_o oder -SO₂N(R_o)₂ bedeuten, wobei R Alkyl oder Alkoxyalkyl ist und wobei unter Alkyl oder Alkoxy jeweils Gruppen mit 1-4 C-Atomen zu verstehen sind, oder
• R₁ und R₂ oder R₂ und R₃ oder R₃ und R₄ zusammen mit den C-Atomen, an die sie gebunden sind, einen Benzolrest bilden, und
• Qi einen C₂-C₄-Alkylenrest, einen durch Sauerstoff oder Stickstoff unterbrochenen C₂-C₈-Alkylenrest, einen Phenylenrest oder die Brücke
  
  - bedeuten, worin
• X und Y je C_I-C₄-Alkyl oder einen aromatischen Rest sind oder X und Y zusammen mit den C-Atomen, an die sie gebunden sind, einen cycloaliphatischen Rest mit 5-7 C-Atomen bilden.

The bisazomethine complexes of the formula (2) are of particular importance in the copper complexes of the formula (1)

wherein

• R 'is hydrogen or C ₁ -C ₃ alkyl
• Ri, R ₂ , R ₃ and R ₄ each represent hydrogen, halogen, hydroxy, hydroxyalkyl, alkyl, alkoxy, alkoxyalkoxy, alkoxyalkoxyalkoxy, carboxymethoxy, alkylamino, dialkylamino, -SO ₂ NH ₂ , -SO ₂ NHR _o or -SO ₂ N ( R _o ) ₂ , where R is alkyl or alkoxyalkyl and alkyl or alkoxy is to be understood in each case as meaning groups with 1-4 C atoms, or
• R ₁ and R ₂ or R ₂ and R ₃ or R ₃ and R ₄ together with the C atoms to which they are attached form a benzene radical, and
• Qi is a C ₂ -C ₄ alkylene radical, a C ₂ -C ₈ alkylene radical interrupted by oxygen or nitrogen, a phenylene radical or the bridge
  
  - mean what
• X and Y are each C _I -C ₄ alkyl or an aromatic radical or X and Y together with the C atoms to which they are attached form a cycloaliphatic radical with 5-7 C atoms.

The cycloaliphatic radicals formed by X and Y together with the C atoms to which they are attached are cyclopentylene, cyclohexylene or cycloheptylene radicals.

worin Ri und R₅ unabhängig voneinander für Wasserstoff oder einen gegebenenfalls substituierten Alkyl- oder Arylrest stehen, und bei Kupferkomplexen von Semicarbazonen bzw. Thiosemicarbazonen als Komponente A) handelt es sich in erster Linie um die Komplexe der Formel (3a)

worin R₁ die unter Formel (3) angegebene Bedeutung hat und Z₂ für Sauerstoff oder Schwefel steht.Copper complexes of acylhydrazones of aromatic aldehydes and ketones as component A) are primarily the complexes of the formula (3)

wherein R 1 and R ₅ independently of one another represent hydrogen or an optionally substituted alkyl or aryl radical, and copper complexes of semicarbazones or thiosemicarbazones as component A) are primarily the complexes of the formula (3a)

wherein R _{1 has} the meaning given under formula (3) and Z _{2 represents} oxygen or sulfur.

If R 1 and / or R ₅ in the formulas (3) and (3a) are an alkyl radical, this can be branched or unbranched and has a chain length of preferably 1 to 8, in particular 1 to 4, carbon atoms. Suitable substituents are halogen, such as fluorine, chlorine or bromine, C ₁ -C ₄ alkoxy, such as methoxy or ethoxy, also phenyl or carboxyl, C ₁ -C ₄ alkoxycarbonyl, such as acetyl or hydroxy, mono- or dialkylamino.

If R _i and / or R ₅ in the formulas (3) and (3a) are an optionally substituted aryl radical, a phenyl or naphthyl radical which can be substituted by C 1 -C ₄ -alkyl, such as methyl, ethyl, is particularly suitable , 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, propionylamino and butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.

Complexes of the formula (3) are preferably used in which R _{1 is} hydrogen and R _{5 is} hydrogen, methyl or, in particular, the phenyl radical, in particular the complexes in which the sulfo group is in turn in the p-position to the oxygen.

The complexes of formula (1), (3) and (3a) are preferably in neutral form, i.e. used as alkali salt, in particular sodium salt or amine salt.

worin R = H, OH, Alkyl oder Cycloalkyl bedeutet und in der der Ring A gegebenenfalls weiter substituiert sein kann, wie z.B. Kupferverbindungen des Salicylaldoxims und der Salicylhydroxamsäure.Copper complexes of oximes as component A) are mainly copper compounds of phenols of the formula (4)

wherein R = H, OH, alkyl or cycloalkyl and in which the ring A may optionally be further substituted, such as copper compounds of salicylaldoxime and salicylhydroxamic acid.

Suitable alkyl radicals are those with 1 to 4 carbon atoms. Suitable cycloalkyl radicals are cyclohexyl and methylcyclohexyl radicals. Suitable substituents in ring A are methyl, methoxy or chlorine. However, this ring is preferably unsubstituted.

worin

• R₆, R₇, R₈ und R₉ je Wasserstoff, Hydroxy, Chlor, Brom, Methyl, tert.Butyl, Methoxy, Methoxyethoxy, Ethoxyethoxyethoxy oder Diäthylamino, und R₇ zusätzlich auch Sulfo,
• 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.Preferred copper complexes of the formula (2) are those which correspond to the formula (5)

wherein

• R ₆ , R ₇ , R ₈ and R ₉ each represent hydrogen, hydroxy, chlorine, bromine, methyl, tert-butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino, and R ₇ additionally also sulfo,
• X _{1 is} hydrogen, methyl, ethyl or phenyl and
• Y _{1 is} hydrogen

or R ₆ and R ₇ together form a fused-on benzene radical or X ₁ and Y ₁ together form a cyclohexylene radical.

worin
R₁₀, R₁₁ und R₁₃ je Wasserstoff, Chlor, Brom, Methyl oder Methoxy und R₁₁ zusätzlich auch Sulfo bedeuten oder Rio 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
R ₁₀ , R ₁₁ and R ₁₃ each represent hydrogen, chlorine, bromine, methyl or methoxy and R ₁₁ additionally also mean sulfo or Rio and R ₁₁ together form a fused-on benzene ring, R _{12 is} hydrogen or hydroxy and X _{2 is} hydrogen, methyl, ethyl or Is phenyl.

Compounds of formula (6) of particular interest are those in which Rio, R ₁₁ , R ₁₂ , R ₁₃ and X _{2 are} hydrogen.

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.

• a) 2-Hydroxybenzophenone der Formel (7)
  
  worin
  • R₁ Wasserstoff, Hydroxy, C₁-C₁₄-Alkoxy oder Phenoxy,
  • R₂ Wasserstoff, Halogen, C₁-C₄-Alkyl oder Sulfo,
  • R₃ Wasserstoff, Hydroxy oder Ci-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'-di- methoxy-5-sulfo-, 4-Benzyloxy- und 5-Chlor-Derivat;
• b) 2-(2'-Hydroxyphenyl)-benzotriazole der Formel (8)
  
  worin
  • R₁ Wasserstoff, C₁-C₁₂-Alkyl, Chlor, C₅-C₆-Cycloalkyl, C₇-C₉-Phenylalkyl oder Sulfo
  • Rz Wasserstoff, C₁-C₄-Alkyl, G₁-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.

The following compounds can be used as component B):

• a) 2-hydroxybenzophenones of the formula (7)
  
  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 Ci-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 (8)
  
  wherein
  • R _{1 is} hydrogen, C ₁ -C ₁₂ alkyl, chlorine, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ phenylalkyl or sulfo
  • Rz is hydrogen, C ₁ -C ₄ -alkyl, G 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 or 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, 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 and the sodium salt of 2- (2'-hydroxy- 3'-tert-butyl-5'-methylphenyl) -5- (2H) -benzotriazolesulfonic acid and 3-tert.-butyl-4-hydroxy-5- (benzotriazole- (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)
  
  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. Before piperidine derivatives are included 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.

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-C_S Alkenoyl, Glycidyl oder eine Gruppe -CH₂CH(OH)-Z, worin Z Wasserstoff, Methyl oder Phenyl ist, bedeutet, wobei R¹ vorzugsweise Ci-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 (10)

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, C ₃ -C ₈ alkynyl, C ₇ -C ₁₂ aralkyl, C ₁ -C ₈ alkanoyl, C ₃ -C _S alkenoyl, glycidyl or a group -CH ₂ CH (OH) -Z, where Z is hydrogen, methyl or phenyl, where R ^{1 is} preferably Ci C12 is alkyl, allyl, benzyl, acetyl or acryloyl and R ² , if 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 carbon atoms, a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, an α, β-unsaturated carboxylic acid 3 to 5 carbon atoms or an aromatic carboxylic acid 7 to 15 carbon atoms, 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 one or two valuable 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 , 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 C ₁ -C ₁₂ 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 C ₁ -C ₁₈ alkyl, R ⁱ 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 -Cg alkenyl, it can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl act.

R ¹ as C ₃ -C ₈ alkynyl is preferably propargyl.

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

R ¹ is as C ₁ -C ₈ alkanoyl, 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 represents, for example, malonic, adipic, suberic, sebacic, maleic, phthalic, dibutylmalonic, dibenzylmalonic, butyl (3,5-di-tert.- butyl-4-hydroxybenzyl) malonic or bicycloheptenedicarboxylic acid residue.

If R ^{2 represents} 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) l-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-ß-(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) l-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetat
• 16) Trimellithsäure-tri-(2,2,6,6-tetramethylpiperidin-4-yl)-ester
• 17) l-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-I-n-butyl-2,2,6,6-tetramethylpiperidin)
• 23) Toluol-2',4'-bis-(4-carbamoyloxy-l-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-Lbis-(1,2,2,6,6-pentamethylpiperidin-4-yl)j-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-Cs Hydroxyalkyl, C₅-C₇ Cycloalkyl, C₇-C₈ Aralkyl, C₂-C₁₈ Alkanoyl, C₃-C_S 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, C₆-C₁₂ Arylen, Xylylen, eine -CH₂-CH(OH)-CH₂-Gruppe oder eine Gruppe -CH₂-CH(OH)-CH₂-0-D-0- 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.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) l-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-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-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-in-butyl-2,2,6,6-tetramethylpiperidine)
• 23) toluene-2 ', 4'-bis (4-carbamoyloxy-ln-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-Lbis- (1,2,2,6,6-pentamethylpiperidin-4-yl) j-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)

wherein n is the number 1 or 2, R and R ^{1 have} the meaning given under aa), R ^{3 is} hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -Cs hydroxyalkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₈ Aralkyl, C ₂ -C ₁₈ alkanoyl, C ₃ -C _S alkenoyl or benzoyl and R ⁴ when n is 1, 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, wherein Z is hydrogen, methyl or phenyl means; if n is 2, C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, xylylene, a -CH ₂ -CH (OH) -CH ₂ group or a group -CH ₂ -CH (OH) -CH ₂ - 0-D-0- 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 one Radical of 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 -Dicarboxylic acid can mean.

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 -C ₅ 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, 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^t-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'-dibutyl- adipamid
• 39) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2-hydroxypropylen-l,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, R_I Wasserstoff, C₁-C₄-Alkyl, C_I-C₄-Alkoxy oder Hydroxy, R₂ Wasserstoff oder Sulfo und R₃ und R₄ unabhängig voneinander C_I-C₄-Alkyl, C₁-C₄-Alkoxy, C₅-C₆-Cycloalkyl, Phenyl oder durch Ci-C_4-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-Alkyl- imino 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.

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 ^t- 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'-dibutyl adipamide
• 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, C ₁ -C ₄ alkyl or sulfo, R _{I is} hydrogen, C ₁ -C ₄ alkyl, C _I -C ₄ alkoxy or hydroxy, R _{2 is} hydrogen or sulfo and R ₃ and R _{4 are} independent one another are C _I -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₅ -C ₆ cycloalkyl, phenyl or substituted by C _4- alkyl and hydroxy phenyl, where 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 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 R ₁ , R ₂ and R _{3 is} a radical of the formula
  
  is where M is sodium, potassium, calcium, magnesium, ammonium or tetra-C ₁ -C ₄ -alkylammonium and m is 1 or 2, and the remaining substituent or substituents are, independently of one another, C ₁ -C ₁₂ -alkyl, phenyl , C ₁ -C ₁₂ alkyl or phenyl bonded to the triazinyl radical by oxygen, sulfur, imino or C ₁ -C ₄ alkylimino, such as, for example, the potassium salt of the compound of the formula (12a), in which R _{1 is} phenyl and R ₂ and R ₃ each represent the rest of the formula (12b) or the sodium salt of the compound of formula (12a), wherein R _{1 is} p-chlorophenyl and R ₂ and R ₃ each represent the rest of the formula (12b). Further compounds are described in EP-A-165608.

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, 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 Phenylalkylphsophonate der Formel (14)

worin R Hydroxy, Phenyl, Phenoxy, C₁-C₁₈-Alkylphenoxy, C₁-C₂₄-Alkyl- thio oder C₁-C₂₄-Alkoxy, R₁ Phenoxy, C₁-C₁₈-Alkylphenoxy, C₁-C₂₄-Alkylthio oder C_l-C₂₄-Alkoxy, R₂ und R₃ unabhängig voneinander C₁-C₁₈-, vorzugsweise C_I-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 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 O (CH ₂ ) ₂ O (CH ₂ ) ₂ O-, -HN- (CH ₂ ) _2-6- NH- or -O (CH ₂ ) ₂ -S- (CH ₂ ) ₂ O-or the remainder are - (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 and phenylalkylphosphonates of the formula (14)

wherein R is hydroxy, phenyl, phenoxy, C ₁ -C ₁₈ alkylphenoxy, C ₁ -C ₂₄ alkylthio or C ₁ -C ₂₄ alkoxy, R ₁ phenoxy, C ₁ -C ₁₈ alkylphenoxy, C ₁ -C _24- alkylthio or C ₁ -C ₂₄ -alkoxy, R ₂ and R ₃ independently of one another are C ₁ -C ₁₈ -, preferably C _I -C ₆ -alkyl and especially tert-butyl in the 3-position and 5-position, R ₄ Is hydrogen or C ₁ -C ₄ -alkyl and n is 0, 1, 2 or 3, preferably 0 or 1, such as, for example, di-n-octadecyl-3-tert-butyl-4-hydroxy-5-methylbenzylphosphonate, 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- (3rd ', 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 (1) to (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 processes known per se, as described, for example, in US Pat. Nos. 3,403,183 and 4,127,586, respectively. Compounds of the formula (8) in which R ₁ , Rz, R ₃ and / or R _{4 are} sulfo can be prepared by the process described in EP-A-112120.

Compounds of the formula (8) in which R 1, C ₁ -C ₁₂ -, preferably C ₁ -C ₄ alkyl and R ₃ sulfo - can also be prepared by adding the corresponding compound in which R _{3 is} C ₁ -C ₁₂ -, preferably C ₁ -C ₄ 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 e.g. in U.S.-A-3,640,928, 3,840,494 and 3,993,655.

The compounds of formula (12) can be prepared in a manner known per se, e.g. according to the methods 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 an organic copper complex, 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 up 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 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.

1:2-Co-Komplex (gelb) 0,25 %Four 10 g yarn strands 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). 05% dye 1

1: 2 co-complex (yellow) 0.25%

Dye 2

1:2-Co-Komplex (grün) 0,035 %

1: 2 co-complex (green) 0.035%

Dye 3

1:2-Cr-Komplex (schwarz)

1: 2 Cr complex (black)

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

Dyeing liquor 1: no further additives.

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

in feindisperser Form (Teilchengrösse <2 µm); gemahlen mit dem Kondensationsprodukt aus Naphthalinsulfonsäure und Formaldehyd als Dispergator im Gewichtsverhältnis 1:1.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 additives of dyeing liquors 2 and 3 combined.

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 Swiss standard SN-ISO I05-B02
• - Fractal light 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. Then the yarn is processed according to SNV (welding Certain standards association) -standard 197.461 tested for its 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%.

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

The dyeing is carried out as described in Example 1, with the difference that the following dye combination is used for dyeing 0.04%

Dye 4

1:2-Co-Komplex (gelb)

0,003 %

1: 2 co-complex (yellow)

0.003%

Dye 3 according to Example 1 (black)

The dyeings were tested as noted in Example I.

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).

Beispiel 3: Fotostabilisierung und Lichtechtheitsverbesserung einer "Mausgrau"-Färbung.The results are summarized in the following table:

Example 3: Photo stabilization and light fastness improvement of a "mouse gray" staining.

• (a) Es werden folgende Farbstoffe in den Färbeflotten 9-12 eingesetzt:
  • 0,05 %
  • Farbstoff 1 gemäss Beispiel 1 (gelb)
  • 0,015 %
  • Farbstoff 6
    
    1:2-Co-Komplex (bordeaux)
  • 0,14 % 81 Teile Farbstoff 3
  • Farbstoff 7 gemäss Beispiel 1 (schwarz) und 12 Teile des Farbstoffes
    
    1:2-Co-Komplex (schwarz)

The procedure and testing is carried out as described in Example 1 with the following differences:

• (a) The following dyes are used in dye liquors 9-12:
  • 0.05%
  • Dye 1 according to Example 1 (yellow)
  • 0.015%
  • Dye 6
    
    1: 2 co-complex (bordeaux)
  • 0.14% 81 parts of dye 3
  • Dye 7 according to Example 1 (black) and 12 parts of the dye
    
    1: 2 co-complex (black)

eingesetzt, während die Färbeflotten 11 und 12 noch 1 % des Lichtschutzmittels der Formel (101) enthalten.The dye liquor 9 contains no further additive. Fleets 10 and 12 also contain 0.075% of the copper complex of the formula

used, while the dye liquors 11 and 12 still contain 1% of the light stabilizer of the formula (101).

(b) 2% acetic acid (80%) is added to all dyeings 9-12 after the dye has been exhausted at 95 ° C.

The results are summarized in the following table:

Example 4: Improvement of the photo stability and the light fastness of a gray color.

Three 10 g skeins of polyamide 66 staple yarn are each dyed gray in a dyeing machine as described in Examples 1 and 3. After the dyeings have been rinsed, the skeins of yarn are each treated with one of the following liquors at 60 ° C. for 45 minutes at a liquor ratio of 1:20 with the addition of 2% acetic acid (80%).

Fleet 1: no addition

Fleet 2: addition of, based on the weight of the goods, 0.05% of the compound of the formula (200).

0,25 % der Verbindung der Formel

Fleet 3: addition of, based on the weight of the product, 0.05% of the compound of the formula (200) 0.25% of the compound of the formula

0.25% of the compound of the formula

The compounds of the formulas (400) and (401) are ground in aqueous solution of the condensation product of naphthalenesulfonic acid and formaldehyde as a dispersant in a weight ratio of 1: 1 to a particle size of <2 μm.

The lightfastness of the dyeings obtained with fleets 2 and 3 is the same, but is 0.5 points (xenon light) and 2 points (fractal light) better than dyeing 1. The photochemical resistance after a 1000-hour exposure in xenon light shows that with Fleet 3 treated skein has a 20% better tear strength than Fleet 2 treated skein, which still has 50% of the initial strength. The strand of yarn treated with the liquor 1 has only 20% of the initial strength.

• 0,042 % des Farbstoffes 4 gemäss Beispiel 2
• 0,016 % des Farbstoffes 6 gemäss Beispiel 3
• 0.008 % des Farbstoffes 7 gemäss Beispiel 3

zu einem Hellbeige gefärbt, wobei die Farbbäder noch folgende Zusätze enthalten:Example 5: 12 skeins of 10 g each of polyamide 66 staple yarn are made using the dye mixture

• 0.042% of dye 4 according to example 2
• 0.016% of dye 6 according to example 3
• 0.008% of dye 7 according to example 3

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

Flotte 4: Zusatz von 1 %, bezogen auf das Warengewicht, der Verbindung der Formel

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

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:

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 ½ 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 The solution is poured into a mixture of 600 g of ice and 400 ml of water with good stirring. The precipitated product is heated to 80 ° C. and, after cooling to room temperature, filtered off. The acid is squeezed out well and then slurried in one liter of water, then neutralized with stirring with 30% sodium hydroxide solution in 1½ hours (pH 7). The thick crystal sludge is then heated again to 80 ° C., resulting in a well-filable crystal form, and filtered off after cooling at room temperature. It is dried at 100 ° C. in vacuo. Yield: 83.5 g. The product can be recrystallized from ethanol / water in a ratio of 8: 2.

Example 6: 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)

(Herstellung der feindispersen Form wie für Verbindung (100)).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)).

(Herstellung der feindispersen Form wie bei Verbindung (100)).Fleet 4: addition of 0.06%, based on the weight of the product, of the compound of the formula

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

Fleet 5: addition of 0.06%, based on the weight of the product, of the compound of the formula

Fleet 6: addition of 0.06%, based on the weight of the product, of the compound of the formula

The lightfastnesses of the dyeings are determined according to DIN 75.202 prov. (Fakra). They are summarized in the following table:

gefärbt, indem man bei 50°C eingeht, 5 Minuten bei dieser Temperatur behandelt, sodann innerhalb von 20 Minuten auf 85°C aufheizt, noch 1 % Essigsäure (80 %) zusetzt, 30 Minuten färbt, abkühlt, die Färbung in kaltem Wasser spült und trocknet, wobei die Flotten noch folgende Zusätze enthaltenExample 7: 5 skeins of 10 g of a polyamide 6 carpet yarn are in a dyeing machine at a liquor ratio of 1:30 with 1% acetic acid (80%) and 1%, based on the weight of the goods, of dye 8 of the formula

dyed by entering at 50 ° C, treated for 5 minutes at this temperature, then heated to 85 ° C within 20 minutes, 1% acetic acid (80%) added, dyed for 30 minutes, cooled, the dyeing rinsed in cold water and dries, the liquors also contain the following additives

Fleet 1: no additives

Fleet 2: 0.04%, based on the weight of the product, of compound (600) in finely dispersed form.

Fleet 3: 1.5%, based on the weight of the goods, of the loosened connection (700),

Fleet 4: 1.5%, based on the weight of the compound (700), 0.04% based on the weight of the compound (600) in finely dispersed form.

The dyed yarn is tested for its light fastness (xenon light, fakra), exposed 100 h after fakra and 1000 h after xenon and tested for its tear strength and elongation.

The results are summarized in the table below:

• · Der Cu-Komplex - vor allem bei der Heissbelichtung - sehr deutlich den fotochemischen Faserabbau hemmt, während
• · das Antioxidant der Zerstörung des Farbstoffes entgegenwirkt; wie ersichtlich wird vor allem die Fakra-Lichtechtheit verbessert,
• · man mit der Kombination beider Stabilisatoren den Schutz von Farbstoff und Faser gegen den fotochemischen Abbau sehr deutlich erhöht.

The results show that

• · The Cu complex - especially in hot exposure - very clearly inhibits the photochemical fiber degradation, while
• · The antioxidant counteracts the destruction of the dye; as can be seen, especially the fakra light fastness is improved,
• · The combination of both stabilizers increases the protection of dye and fiber against photochemical degradation very significantly.

Claims (19)

1. A process for the photochemical stabilization of undyed and dyed polyamide fiber material or mixtures thereof with other fiber materials, characterized in that the fiber material is mixed with A) an organic copper complex, B) a light stabilizer and if desired C) an antioxidant
treated. 2. The method according to claim 1, characterized in that a non-coloring copper complex of bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic aldehydes or ketones or oximes is used as component A). 3. The method according to any one of claims 1 and 2, characterized in that a copper complex of the formula (I) is used as component A)

where R is hydrogen or an optionally substituted alkyl or aryl radical, Q is an optionally substituted alkylene, cycloalkylene or arylene radical and n is 0, 1, 2 or 3 and the benzene rings A and B can be substituted independently of one another. 4. The method according to any one of claims 1 to 3, characterized in that a bisazomethine complex of the formula (2) is used as component A)

wherein R 'is hydrogen or Ci-C3-alkyl Ri, R ₂ , R ₃ and R ₄ each represent hydrogen, halogen, hydroxy, hydroxyalkyl, alkyl, alkoxy, alkoxyalkoxy, alkoxyalkoxyalkoxy, carboxymethoxy, alkylamino, dialkylamino, -SO ₂ NH ₂ , -SO ₂ NHR _o or -SO ₂ N ( R _o ) ₂ , where R _{o is} alkyl or alkoxyalkyl and where alkyl or alkoxy are in each case to be understood as meaning groups with 1-4 C atoms, or R ₁ and R ₂ or R ₂ and R ₃ or R ₃ and R ₄ together with the C atoms to which they are attached form a benzene radical, and Q _{1 is} a C ₂ -C ₄ alkylene radical, a C ₂ -C ₈ alkylene radical interrupted by oxygen or nitrogen, a phenylene radical or the bridge

mean what X and Y are each C ₁ -C ₄ alkyl or an aromatic radical or X and Y together with the C atoms to which they are attached form a cycloaliphatic radical with 5-7 C atoms. 5. The method according to any one of claims 1 and 2, characterized in that an acylhydrazone of an aromatic aldehyde or ketone of the formula (3) is used as component A)

wherein R ₁ and R ₅ independently of one another represent hydrogen or an optionally substituted alkyl or aryl radical. 6. The method according to any one of claims 1 and 2, characterized in that a semicarbazone or thiosemicarbazone of the formula (3a) is used as component A)

wherein R _{1 is} hydrogen or an optionally substituted alkyl or aryl radical and Z _{2 is} oxygen or sulfur. 7. The method according to any one of claims 1 and 2, characterized in that as component A) copper compounds of phenols of the formula (4)

used, wherein R = H, OH, alkyl or cycloalkyl and in which the ring A may optionally be further substituted. 8. The method according to claim 4, characterized in that as component A) a bisazomethine complex of the formula (5)

used where R ₆ , R ₇ , R ₈ and R ₉ each represent hydrogen, hydroxy, chlorine, bromine, methyl, tert-butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino and R ₇ additionally also sulfo, X _{1 is} hydrogen, methyl, ethyl or phenyl and Y _{1 is} hydrogen
or R ₆ and R ₇ together form a benzene radical or X ₁ and Yi together form a cyclohexylene radical. 9. The method according to claim 8, characterized in that as component A) a bisazomethine complex of the formula (6)

used where
R ₁₀ , R ₁₁ and Ri _{3 are} each hydrogen, chlorine, bromine, methyl or methoxy and R _{11 is} also sulfo or Rio and R ₁₁ together form a benzene ring, R _{12 is} hydrogen or hydroxy and X _{2 is} hydrogen, methyl, ethyl or phenyl is. 10. The method according to any one of claims 1 to 9, characterized in that as component B) a 2-hydroxybenzophenone of the formula (7)

used where R _{1 is} hydrogen, hydroxy or C _I -C ₁₄ alkoxy, R _{2 is} hydrogen, C ₁ -C ₄ alkyl or sulfo, R _{3 is} hydrogen, hydroxy or C _i -C ₄ alkoxy and R _{4 is} hydrogen, hydroxy or carboxy
mean. 11. The method according to any one of claims 1 to 9, characterized in that as component B) a 2- (2'-hydroxyphenyl) benzotriazole or a salt thereof of the formula (8)

used where R _{1 is} hydrogen, C ₁ -C ₁₂ alkyl, chlorine, C ₅ -C ₆ cycloalkyl, C ₇ -C ₉ phenylalkyl or sulfo, Rz is hydrogen, C _I -C ₄ alkyl, C ₁ -C ₄ alkoxy, chlorine, hydroxy or sulfo, R ₃ C ₁ -C ₁₂ alkyl, C _I -C ₄ alkoxy, phenyl, (C ₁ -C ₈ alkyl) phenyl, C ₅ -C ₆ cycloalkyl, C ₂ -C ₉ alkoxycarbonyl, chlorine, Carboxyethyl or 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. 12. The method according to any one of claims 1 to 9, characterized in that a compound from the class of sterically hindered amines is used as component B). 13. The method according to claim 12, 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 (9) in its molecule

contains, wherein R is hydrogen or methyl. 14. The method according to any one of claims 1 to 9, characterized in that as component B) a 2- (2'-hydroxyphenyl) -S-triazine or a salt thereof of the formula (12)

used, wherein R is hydrogen, halogen, C ₁ -C ₄ alkyl or sulfo, Ri 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 _I -C ₄ alkoxy, C ₅ -C ₆ cycloalkyl, phenyl or phenyl substituted by Ci-C ₄ alkyl and hydroxy. 15. The method according to any one of claims 1 to 9, characterized in that an s-triazine compound of the formula is used as component B)

used, wherein at least one of the substituents R ₁ , R ₂ and R _{3 is} a radical of the formula

is where M is sodium, potassium, calcium, magnesium, ammonium or tetra-C ₁ -C ₄ -alkylammonium and m is 1 or 2, and the remaining substituent or substituents are, independently of one another, C ₁ -C ₁₂ -alkyl, phenyl , Ci-Ciz-alkyl or phenyl bonded to the triazinyl radical by oxygen, sulfur, imino or C ₁ -C ₄ -alkylimino. 16. The method according to any one of claims 1 to 15, characterized in that as component C) a hydroxyphenyl propionate of the formula (13)

used, where n is an integer from 1 to 4 and AC ₁ -C ₂₄ alkoxy, a bridge member -0 (CH ₂ ) ₆ 0-, -O (CH ₂ ) ₂ -O (CH ₂ ) ₂ O-, - 0 (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 O or the rest - (- CH ₂ O) ₄ -C mean. 17. The method according to any one of claims 1 to 15, characterized in that a phenylalkylphosphonate of the formula (14) as component C)

used, wherein R is hydroxy, phenyl, phenoxy, C ₁ -C ₁₈ alkylphenoxy, Ci-Cz4-alkylthio or C ₁ -C ₂₄ alkoxy, Ri phenoxy, C ₁ -C ₁₈ alkylphenoxy, C ₁ -C ₂₄ Alkylthio or C ₁ -C ₂₄ alkoxy, R ₂ and R ₃ independently of one another are C ₁ -C ₁₈ alkyl, R _{4 is} hydrogen or C ₁ -C ₄ alkyl and n is 0, 1, 2 or 3, 18. Agent for the photochemical stabilization of undyed and dyed polyamide fiber material or its mixtures with other fiber materials, characterized in that it A) 0.005 to 0.20% 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, if appropriate C) 0.05 to 3% by weight, preferably 0.1 to 1% by weight, of an antioxidant. 19. The polyamide fiber material treated by the method according to any one of claims 1 to 16 and mixtures thereof with other fiber materials.