EP0185611A1 - Process for the photochemical stabilisation of synthetic fibrous materials containing polyamide fibres - Google Patents

Abstract

Process for the photochemical stabilization of fiber materials made of synthetic polyamides, in which the fiber materials with at least one water-soluble copper complex dye or with a mixture of copper complex compounds containing at least one water-soluble copper complex dye or at least one water-soluble copper complex dye in combination with a water-soluble 1: 2-Co-, 1: 2 -Cr metal complex, azo, anthraquinone, nitroaryl or dioxazine dye are treated. The fiber materials treated (or dyed) by the process according to the invention are distinguished by very high tensile strength and elongation values after exposure or hot exposure.

Description

The present invention relates to a method for the photochemical stabilization of synthetic polyamide fiber materials with water-soluble copper complex dyes.

Dyed synthetic polyamide fiber material is damaged when exposed to light, especially when exposed to heat; therefore synthetic polyamide fibers are used in some areas of application, e.g. viewed as car upholstery or sail fabrics, as problem fibers.

In line with today's requirements, the aim is to improve the photochemical stability of synthetic polyamide fiber materials.

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 American Dyestuff Reporter 3 (1980), pages 19 and 20. However, inorganic or organic copper salts often have the disadvantage that they are insufficiently and unevenly applied to the polyamide fiber and are therefore used in high concentrations and are often used only in an aftertreatment process can be.

Attempts have therefore been made to use the copper in the form of compounds which have an affinity for polyamide fiber. For example, recommended in EP 00 18 775 copper phosphate, which should behave similar to a disperse dye and absorbs accordingly on the nylon fiber. However, such known copper compounds generally have too little water solubility, which likewise has a negative effect on the degree of exhaustion. In addition, the copper remaining in the dye bath leads to a high level of wastewater pollution.

The object underlying the present invention was to find a process for the photochemical stabilization of synthetic polyamide fiber materials which does not have the disadvantages described above and which meets today's requirements.

This object is achieved in that water-soluble copper complex dyes are used instead of the known copper compounds which have little affinity for fibers or are poorly water-soluble. These dyes are fiber-affine and contain water-solubilizing groups.

The present invention thus relates to a process for the photochemical stabilization of fiber materials made of synthetic polyamides, which is characterized in that the fiber material is treated with at least one water-soluble copper complex dye or with a mixture of copper complex compounds, at least one component being a water-soluble copper complex dye.

The term photochemical stabilization here refers to both the light fastness and the maintenance of the mechanical properties of the undyed or dyed polyamide fiber, i.e. Photochemical stabilization against visible and UV light.

With the process according to the invention, colored, synthetic polyamide materials of very high photochemical stability are obtained, in particular with simultaneous exposure to light and heat.

• a) wasserlösliche Kupferkomplexfarbstoffe, insbesondere wasserlösliche Kupferkomplexazo- oder -azomethinfarbstoffe, einschliesslich der Formazanfarbstoffe,
• b) Mischungen von wasserlöslichen Kupferkomplexfarbstoffen oder ganz besonders bevorzugt
• c) Mischungen enthaltend mindestens einen wasserlöslichen Kupferkom- pl_fxfarbstoff und mindestens eine wasserlösliche Kupferkomplexverbindung ohne Farbstoffcharakter verwendet. Die genannten Kupferkomplexverbindungen werden zweckmässigerweise in einer Menge eingesetzt, dass auf 1 g Polyamidfasermaterial 2 bis 1 000 µg Kupfer, insbesondere 5 bis 200 ug Kupfer, zukommt.

Preferred embodiments of the method according to the invention are characterized in that

• a) water-soluble copper complex dyes, in particular water-soluble copper complex azo or azomethine dyes, including the formazan dyes,
• b) Mixtures of water-soluble copper complex dyes or very particularly preferred
• c) mixtures comprising at least one water-soluble pl _f xfarbstoff Kupferkom- used and at least one water-soluble copper complex compound without dye character. The copper complex compounds mentioned are expediently used in an amount such that 2 to 1,000 μg of copper, in particular 5 to 200 μg of copper, are added to 1 g of polyamide fiber material.

verwendet, worin D ein Rest der Benzol- oder Naphthalinreihe, X ein Stickstoffatom oder die CH-Gruppe, Y die HO-, GH₃O- oder HOOC- Gruppe und Y' die HO- oder eine Aminogruppe ist, und worin K, für den Fall, dass X ein Stickstoffatom ist, den Rest einer Kupplungskomponente der Benzol-, Naphthalin- oder heterocyclischen Reihe oder den Rest einer Ketomethylenverbindung bedeutet, oder, für den Fall, dass X die CH-Gruppe ist, K den Rest eines o-Hydroxyaldehyds bedeutet.A particularly preferred embodiment of the process according to the invention is characterized in that copper complexes of azo or azomethine dyes of the formula which contain water-solubilizing groups

where D is a residue of the benzene or naphthalene series, X is a nitrogen atom or the CH group, Y is the HO, GH ₃ O or HOOC group and Y 'is the HO or an amino group, and wherein K, is for in the case that X is a nitrogen atom, the residue of a coupling component of the benzene, naphthalene or heterocyclic series or the residue of a ketomethylene compound, or, in the case that X is the CH group, K is the residue of an o-hydroxyaldehyde means.

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

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

Suitable sulfone groups are alkyl sulfone and in particular C _1-4 alkyl sulfone groups.

Particularly suitable as the N-mono- or N, N-dialkylsulfonamide group is one having one or two C _1-4 -alkyl radicals.

In particular, copper complex dyes with one to two water-solubilizing groups, in particular with a single water-solubilizing group, are used in the process according to the invention.

verwendet, worin A ein gegebenenfalls substituierter Carboxyphenyl-oder Sulfophenylrest, R Wasserstoff oder C_l-4-Alkyl, X ein Stickstoffatom oder die CH-Gruppe und K, für den Fall, dass X ein Stickstoffatom ist, der Rest einer Kupplungskomponente der Benzol-, Naphthalin-, Pyrazolon-, Aminopyrazol-, Acetoacetanilid-, 2,4-Dioxy-' chinolin-, Pyridon- oder Pyridinreihe ist, oder, falls X die CH-Gruppe ist, der Rest eines o-Hydroxybenzaldehyds 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 a copper complex dye of the formula

is used in which A is an optionally substituted carboxyphenyl or sulfophenyl radical, R is hydrogen or C _l-4 alkyl, X is a nitrogen atom or the CH group and K, in the event that X is a nitrogen atom, the radical of a coupling component of the benzene , Naphthalene, pyrazolone, aminopyrazole, acetoacetanilide, 2,4-dioxy- 'quinoline, pyridone or pyridine series, or, if X is the CH group, is the residue of an o-hydroxybenzaldehyde, and the ring B may optionally be further substituted, for example by chlorine or nitro.

diazotiert und auf eine Kupplungskomponente der Formel

kuppelt.Many metallizable azo and azomethine 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

diazotized and on a coupling component of the formula

couples.

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

Examples of suitable amines of the formula (3) are: 2-amino-l-hydroxybenzene, 2-amino-l-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-acetylamino-6-nitro -2-amino-l-hydroxybenzene, 6-acetylamino and 6-chloro-4-nitro-2-amino-l-hydroxybenzene, 4-cyano-2-amino-1-hydroxybenzene, 4-methoxy-2-amino- 1-hydroxybenzene, 2-amino-l-hydroxybenzene-5-methyl- and -5-benzylsulfone, 2-amino-l-hydroxybenzene-4-methyl-, -ethyl-, -chloromethyl- and -butylsulfone, 6-chlorine -, 5-nitro- and 6-nitro-2-amino-l-hydroxybenzene-4-methylsulfone, 2-amino-l-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-l-hydroxybenzene, 4-methyl-2-amino-l-hydroxybenzene, 4-chloro 5-nitro-2-amino-1-hydroxybenzene, 5-nitro-4-methyl-2-amino-1-hydroxybenzene, 5-nitro-4-methoxy-2-amine ol-hydroxybenzene, 3,4,6-trichloro-2-amino-l-hydroxybenzene, 6-acetylamino-4-chloro-2-amino-l-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-β-hydroxyethylsulfone, 4-methyl-6-sulfo-2-amino-l-hydroxybenzene, 2-amino-4-sulfo-l-hydroxybenzene, 4-chloro-6-sulfo-2- amino-l-hydroxybenzene, 6-chloro-4-sulfo-2-amino-l-hydroxybenzene, 5-nitro-4-sulfo-2-amino-l-hydroxybenzene, 4-nitro-6-sulfo-2-amino- l-hydroxybenzene, 6-nitro-4-sulfo-2-amino-l-hydroxybenzene, 4-acetylamino-2-amino-l-hydroxybenzene, 4-acetylamino-6-sulfo-2-amino-l-hydroxybenzene, 5- Acetylamino-2-amino-1-hydroxybenzene, 6-acetylamino-4-sulfo 2-amino-1-hydroxybenzene, 4-chloro-2-amino-l-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-acetamidonaphthalene, 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, C_1-4-Alkyl, C_1-4-Alkoxy, Sulfonamido-, N-mono- oder N,N-disubstituierten Sulfonamidogruppen, Sulfo-und Sulfongruppen substituiert sind.
• - In o-Stellung zur Aminogruppe kuppelnde Naphthylamine, die gegebenenfalls mit Halogen, insbesondere Brom, C_1-4-Alkyl, C_1-4-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, C_1-4-Alkyl- und-Alkoxygruppen, Sulfonamino-, N-alkylierten Sulfonamidgruppen, Sulfogruppen, Sulfongruppen und insbesondere Aminogruppen substituierten Phenyl- oder Naphtylrest besitzen.
• - 2,6-Dihydroxy-3-cyano- oder -3-carbonamido-4-alkylpyridine und 6-Hydroxy-2-pyricone, die in 1-Stellung durch gegebenenfalls substituiertes C_1-4-Alkyl, z.B. Methyl, Isopropyl, ß-Hydroxyäthyl, ß-Aminoäthyl, y-Isopropoxypropyl oder durch -NH₂ oder eine substituierte Aminogruppe, wie z.B. Dimethylamino oder Diäthylamino substituiert sind, in 3-Stellung eine Cyano- oder Carbonamidogruppe und in 4-Stellung eine C_1-4-Alkylgruppe, insbesondere Methyl, tragen.
• - Acetessigsäureanilide und Benzoylessigsäureanilide, die im Anilidkern gegebenenfalls mit C_1-4-Alkyl-, -Alkoxy-, -Alkylsulfonylgruppen, C_1-4-Hydroxyalkyl-, Alkoxyalkyl- oder Cyanalkylsulfonylgruppen, Sulfonamido-,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, optionally substituted with chlorine, amino, acylamino, acyl, C _1-4 alkyl, C _1-4 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 _1-4 alkyl, C _1-4 alkoxy, sulfonamido, mono- or disubstituted sulfonamido, sulfo or sulfone groups.
• - 5-pyrazolones or 5-aminopyrazoles, which in the 1-position may be substituted with chlorine, nitro, C _1-4 alkyl and alkoxy groups, sulfonamino, N-alkylated sulfonamide groups, sulfo groups, sulfone groups and in particular amino groups, and in particular amino groups Have naphthyl.
• - 2,6-Dihydroxy-3-cyano- or -3-carbonamido-4-alkylpyridines and 6-hydroxy-2-pyricones, which are in the 1-position by optionally substituted C _1-4 alkyl, for example methyl, isopropyl, ß -Hydroxyäthyl, ß-Aminoäthyl, y-isopropoxypropyl or by -NH ₂ or one substituted amino groups, such as dimethylamino or diethylamino, are substituted in the 3-position by a cyano or carbonamido group and in the 4-position by a C _1-4 alkyl group, especially methyl.
• - Acetoacetic anilides and benzoylacetic anilides, optionally in the anilide core with C _1-4 alkyl, alkoxy, alkyl sulfonyl groups, C _1-4 hydroxyalkyl, alkoxyalkyl or cyanoalkylsulfonyl groups, sulfonamido, N-alkylated sulfonamido groups, sulfo, sulfo, sulfo 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 K-acetylaminonaphthalin-3-sulfonsäure, 2-Naphthol-6-ß-hydroxyäthyl- sulfon, 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'-aminophenyl)aminonaphthalin-3-sulfonsäure, 1-Hydroxy-5-aminonaphthalin-3-sulfonsäure, 1-Propionylamino-7-naphthol, 2-Hydroxy-6-aminonaphthalin-4-sulfonsäure, 1-Carbomethoxy- amino-7-naphthol, 1-Hydroxy-8-aminonaphthalin-5-sulfonsäure, 1-Carbo- äthoxy-amino-7-naphthol, 1-Hydroxy-8-aminonaphthalin-5,7-disulfonsäure, l-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-1-naphthol, 4-Acetylamine-1-naphthol, 1-Naphthol-3-, -4- oder -5-sulfonamid, 2-Naphthol-3-, -4-, -5-, -6-, -7-oder -8-sulfonamid, 5,8-Dichlor-l-naphthol, 5-Chlor-1-naphthol, 2-Naphthylamin, 2-Naphthylamin-l-sulfonsäure, 2-Ariinonaphthalin-5-, -6-oder -7-sulfonamid, 2-Aminonaphthalin-6-sulfonsäure-N-methyl-, -äthyl-, -isopropyl-, -β-oxyäthyl- oder-γmethoxypropylamid, 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-aminonaphthalin, 2-Phenylaminonaphthalin, 2-N-Methylaminonaphtlalin, 2-N-Aethylaminonaphthalin, 2-Phenylaminonaphthalin-S-, -6- oder -7-sulfonamid, 2-(3'-Chlorphenyl- amino)-naphthalin-5-, -6- oder -7-sulfonamid, 6-Methyl-2-aminonaphthalin, 6-Bron-2-amino-naphthalin, 6-Methoxy-2-aminonaphthalin, 1,3-Dimethylpyrazolon, 3-Methhyl-5-pyrazolon, 1-Phenyl-3-methyl-5-pyrazolon, 1-Phenyl-3-carbonamido-5-pyrazolon, 1-(2'-, 3'- oder 4'-Methylphenyl)-3-methyl-5-pyrazclon, 1-[3'- oder 4'-(ß-Hydroxyäthylsulfonyl)-phenyl]-3-methyl-5-pyrazolon, l-(2'-Methoxyphenyl)-3-methyl-5-pyraolon, 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'-Methylsulfonylphenyl)-3-methyl-5-pyrazolon, 2,6-Dihydroxy-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-(β-hydroxyäthylsulfonyl)-anilid, Acetoacet-o-anisidid, Acetoacetnaphthylarid, 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-Dialkylaminophenol, besonders 3-Dimethylamino- und 3-Diäthylaminophenol, 4-t-Butylphenol, 4-t-Amylphenol, 2- oder 3-Acetylamino-4-methylphenol, 2-Methoxy- carbonylamino-4-methylphenol, 2-Aethoxycarbonylamino-4-methylphenzl, 3,4-Dimethylphenol und 2,4-Dimethylphenol, 1-(4'-Aminophenyl)-3-methyl-5-pyrazolon, 1-(2'-, 3'- oder 4'-Sulfophenyl)-3-methyl-5-pyrazolon, 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'-sulfo- naphthyl(2')]-3-methyl-5-pyrazolon, 1-[4"-_Amino-2',2"-disulfostilben-(4')]-3-methyl-5-pyrazolon, 1-Aethyl-3-cyano-4-methyl-6-hydroxy- pyridon-(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-hydroxypyridin, 5-Ethylmercapto-2,3-dihydroxypyridin,5-Phenylsulfonyl-2,3-dihydroxypyridin, 2,3-Dyhydroxy-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 K-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'-aminophenyl) aminonaphthalene-3-sulfonic acid, 1-hydroxy-5-aminonaphthalene-3-sulfonic acid, 1-propionylamino-7-naphthol, 2-hydroxy-6-aminonaphthalene-4-sulfonic acid, 1-carbomethoxy - amino-7-naphthol, 1-hydroxy-8-aminonaphthalene-5-sulfonic acid, 1-carbo-ethoxy-amino-7-naphthol, 1-hydroxy-8-aminonaphthalene-5,7-disulfonic acid, l-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- disulfonic acid, 4-acetylamino-2-naphthol, 2-hydroxy-5-aminonaphthalene-4,7-disulfonic acid, 4-methoxy-1-naphthol, 4-acetylamine-1-naphthol, 1-naphthol-3-, -4- or -5-sulfonamide, 2-naphthol-3-, -4-, -5-, -6-, -7- or -8-sulfonamide, 5,8-dichloro-l-naphthol, 5-chloro-1-naphthol, 2-naphthylamine, 2-naphthylamine-l-sulfonic acid, 2-ariinonaphthalene-5-, -6-or -7- sulfonamide, 2-aminonaphthalene-6-sulfonic acid-N-methyl-, -ethyl-, -isopropyl-, -β-oxyethyl- or-γmethoxypropylamide, 2-aminonaphthalene-6-sulfanilide, 2-aminonaphthalene-6-sulfonic acid-N- methylanilide, 1-aminonaphthalene-3-, -4- or -5-sulfonamide, 1-aminonaphthalene-5-methyl- or -ethylsulfone, 5,8-dichloro-1-aminonaphthalene, 2-phenylaminonaphthalene, 2-N-methylaminonaphtlalin, 2-N-ethylaminonaphthalene, 2-phenylaminonaphthalene-S-, -6- or -7-sulfonamide, 2- (3'-chlorophenylamino) -naphthalene-5-, -6- or -7-sulfonamide, 6-methyl -2-aminonaphthalene, 6-bron-2-amino-naphthalene, 6-methoxy-2-aminonaphthalene, 1,3-dimethylpyrazolone, 3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone, 1 -Phenyl-3-carbonamido-5-pyrazolone, 1- (2'-, 3'- or 4'-methylphenyl) -3-methyl-5-pyrazclone, 1- [3'- or 4 '- (ß-hydroxyethylsulfonyl ) -phenyl] -3-methyl-5-pyrazolone, l- (2'-methoxyphenyl ) -3-methyl-5-pyraolone, 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-dihydroxy-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, acetoacetnaphthylaride, acetoacet-o -toluidide, acetoacet-o-chloroanilide, acetoacet-m- or -p-chloroanilide, acetoacetanilide-3- or -4-sulfonamide, acetoacet-3- or -4-aminoanilide, acetoacet-m-xylidide, benzoylacetic acid anilide, 4-methylphenol , 3-dialkylaminophenol, especially 3-dimethylamino and 3-diethylaminophenol, 4-t-butylphenol, 4-t-amylphenol, 2- or 3-acetylamino-4-methy lphenol, 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-pyrazolone, 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- ^p yrazolone, 1- (5'-sulfonaphthyl (2 ')] - 3-methyl-5-pyrazolone, 1 - [4 "- _A mino-2 ', 2" -disulfostilben- (4')] - 3-methyl-5-pyrazolone, 1-ethyl-3-cyano-4-methyl-6-hydroxy-pyridone- (2nd ), 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxypyridone- (2), 2,6-dihydroxy-3-cyano-4-sulfomethylpyridine, 2,4,6-trihydroxypyrimidine, 2,3-dihydroxypyridine, 5-bromo- (chloro) -2,3-dihydroxypyridine, 2-amino-3-hydroxypyridine, 5-bromo-2-amino-3-hydroxypyridine, 5-ethylmercapto-2,3-dihydroxypyridine, 5-phenylsulfonyl-2, 3-dihydroxypyridine, 2,3-dyhydroxy-pyridine-5-sulfonic acid and 2-amino-3-hydroxypyridine-5-sulfonic acid.

For the preparation of the azomethine dyes of the formula (1), the above-mentioned aromatic amines of the formula (3) are condensed with o-hydroxybenzaldehydes or o-hydroxynaphthaldehydes in a known manner.

• 2-Hydroxybenzaldehyd, 3- und 5-Methyl-2-hydroxybenzaldehyd, 3,5- und 3,6-Dimethyl-2-hydroxybenzaldehyd, 5-Butyl-2-hydroxybenzaldehyd, 5-Chlor- oder -Brom-2-hydroxybenzaldehyd, 3- und 4-Chlor-2-hydroxybenzaldehyd, 3,5-Dichlor-2-hydroxybenzaldehyd, 3-Chlor-5-methyl-2-hydroxybenzaldehyd, 3-Methyl-5-chlor-2-hydroxybenzaldehyd, 3- und 4-und 5-Kitro-2-hydroxybenzaldehyd, 3,5-Dinitro- und 4-Chlor-5-nitro-2-hydroxybenzaldehyd, 4-Methoxy-2-hydroxybenzaldehyd, 1-Hydroxy-2-naphthaldehyd und dessen in 4-Stellung chlorierter Abkömmling; und 2-Hydroxy-l-naphthaldehyd.

Suitable aldehydes are, for example:

• 2-hydroxybenzaldehyde, 3- and 5-methyl-2-hydroxybenzaldehyde, 3,5- and 3,6-dimethyl-2-hydroxybenzaldehyde, 5-butyl-2-hydroxybenzaldehyde, 5-chloro or -bromo-2-hydroxybenzaldehyde, 3- and 4-chloro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 3-chloro-5-methyl-2-hydroxybenzaldehyde, 3-methyl-5-chloro-2-hydroxybenzaldehyde, 3- and 4- and 5-kitro-2-hydroxybenzaldehyde, 3,5-dinitro- and 4-chloro-5-nitro-2-hydroxybenzaldehyde, 4-methoxy-2-hydroxybenzaldehyde, 1-hydroxy-2-naphthaldehyde and its chlorinated in the 4-position Descendant; and 2-hydroxy-l-naphthaldehyde.

A process variant for the preparation of the copper complex of an azomethine dye of the formula (1) is characterized in that the copper complex can also be prepared with a mixture of the amine of the formula (3) and an o-hydroxyaldehyde instead of with the azomethine of the formula (1).

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 method according to the invention is characterized in that a mixture containing 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, is used.

The copper complex dyes mentioned in the above mixture are suitable as copper complex dyes.

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 1 "er Schiff bases of aliphatic, .cycloaliphatic or aro understood diamines, wherein the aldehydes and ketones have an OH group in the o-position to the formyl or acyl radical. 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. The ligands contain one or more sulfo groups which are located in the aldehyde or ketone part and / or in the bisazomethine bridge.

• a) der Formel
  
  verwendet, worin Me Kupfer, R₂ Wasserstoff oder einen gegebenenfalls substituierten Alkyl- oder Arylrest und Z einen gegebenenfalls substituierten Alkylen-, Cycloalkylen- oder Arylenrest bedeuten und n 1, 2 oder 3 ist; oder
• b) der Formel
  
  verwendet, worin ^Me Kupfer bedeutet und ^R ₃ und R₄ unabhängig voneinander dieselbe Bedeutung wie für R₂ angegeben haben; oder
• c) der Formel
  
  verwendet, worin Me Kupfer, R Wasserstoff oder einen gegebenenfalls substituierten Alkyl- oder Arylrest und V ein Sauerstoff- oder Schwefelatom bedeuten.

Preferred embodiments of the methods according to the invention are characterized in that a mixture comprising a copper complex dye and a copper complex without a color character

• a) of the formula
  
  used, in which Me is copper, R _{2 is} hydrogen or an optionally substituted alkyl or aryl radical and Z is an optionally substituted alkylene, cycloalkylene or arylene radical and n is 1, 2 or 3; or
• b) the formula
  
  used, in which ^{Me is} copper and ^R ₃ and R ₄ independently of one another have the same meaning as given for R ₂ ; or
• c) the formula
  
  used, in which Me is copper, R is hydrogen or an optionally substituted alkyl or aryl radical and V is an oxygen or sulfur atom.

If R ₂ , R ₃ or R ₅ denotes an optionally substituted alkyl radical, preference is given to a C ₁ to C ₈ 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 C ₁ 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 R _{5 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, iso-isopropyl, butyl , Isobutyl, sec. -Butyl and tert-butyl, C ₁ -C ₄ alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and ter-butoxy, halogen, such as fluorine, chlorine and bromine, C ₂ -C _S alkanoylamino, such as acetylamino, propionylamino 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 C2 to C ₈ alkylene chain which is interrupted by oxygen or, in particular, nitrogen is also suitable, 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.

If Z is an arylene radical, it is primarily a phenylene radical, in particular an o-phenylene radical. This can also be substituted by C ₁ to C ₄ alkyl or C ₁ to C ₄ alkoxy.

Examples of suitable substituents for the benzene rings M and N are: C ₁ 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 and / or in the bridging member Z, if this denotes an arylene radical, are preferably in the form of an alkali metal salt, in particular a sodium salt or also an amine salt.

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

If R _{4 is} 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 to C ₄ alkoxy, such as methoxy or ethoxy, further 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 _1-4 alkyl, such as methyl, ethyl ', propyl, isopropyl, butyl, isobutyl, sec-butyl, is particularly suitable and tert-butyl, C _1-4 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen, such as fluorine, chlorine and bromine, C _{2- 5} -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 formulas (6) and (7), the ligands of which are derived from sulfosalicylaldehyde or the corresponding phenyl ketones, 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.

The copper complexes of the formulas (5) and (6) are preferably used in the present process for photochemical stabilization.

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

The mixing ratio depends on the number of copper complex dyes used and the desired color depth of the dyeings.

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 the 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 copper complexes of the formulas (5) to (7) are preferably used, 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.

Another preferred embodiment of the process according to the invention is characterized in that at least one copper complex dye is used together with acid dyes, in particular in the same dye bath.

As acid dyes come e.g. metal-free mono- or polyazo dyes, 1: 2-chromium or 1: 2-cobalt complex azo dyes, anthraquinone, dioxazine, phthalocyanine, nitroaryl or stilbene dyes which contain at least one acid group, such as e.g. Carboxyl or preferably have a sulfonic acid group.

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

The polyamide fiber material used in the process according to the invention is that of synthetic polyamides, such as Polyamide-6, polyamide-66 or polyamide-12 used.

In principle, the polyamide fiber material can be in a wide variety of processing forms, e.g. Fiber, yarn, woven or knitted fabric, in particular textile fiber material.

The dyes containing sulfo groups used in the process according to the invention are present either in the form of their free sulfonic acid or preferably as their salts.

Examples of suitable salts are the alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine. Examples include the sodium, lithium, potassium or ammonium salts or the salt of triethanolamine.

The dyes used in the process according to the invention generally contain further additives such as Cooking salt or dextrin.

The process according to the invention for dyeing synthetic polyamide fiber materials can be applied to the customary dyeing processes.

In addition to water and the dyes, the dyeing liquors can contain further additives, for example wetting agents, anti-foaming agents, leveling agents, salts, acids or buffer substances.

With the method according to the invention, synthetic polyamide fiber materials are stabilized photochemically, i.e. protected against exposure, especially hot exposure, with visible and UV light

A particularly noteworthy advantage of the method according to the invention is that, in comparison to previously known methods for the photochemical stabilization of synthetic polyamide fiber materials, no pretreatment or tiling treatment of the fiber material is required.

The mixtures of copper complex dyes used with the process according to the invention with the copper complex compounds which have no dye character show the advantage that independently. the desired color depth of the dyeings contained with the copper complex dyes, a constant copper content of the fiber can be set, i.e. the protective effect is not subject to nuance-related fluctuations.

The photochemical stabilization of the fiber material is checked e.g. in a fade-ometer at a "black panel temperature" of 83 ° C [hot exposure] or by exposure in a Xenotest apparatus according to DIN 75.202, draft (= Fakra, hot exposure) or SN (Swiss standard) -ISO 105 B 02 (= Xenon) with subsequent testing of the tensile strength and elongation of the material according to SNV standards 97461 and 198.461.

In the following examples, parts represent parts by weight. The temperatures are degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters. The tensile strength and elongation values of untreated and unexposed polyamide fiber material are set equal to 100%.

• Behandlungsbad 1: kein Farbstoffzusatz, mit Belichtung und mit Behandlung;
• Behandlungsbad 2: 0,025 % des gelben Farbstoffes der Formel
  
• Behandlungsbad 3: 0,5 % des Farbstoffs der Formel (100);
• Behandlungsbad 4: 0,025 % des roten Farbstoffs der Formel
  
• Behandlungsbad 5: 0,5 % des Farbstoffes der Formel (101);
• Behandlungsbad 6: 0,025 % des blauen Farbstoffes der Formel
  
• Behandlungsbad 7: 0,5 % des Farbstoffs der Formel (102);

Example 1: Seven skeins of 10 g each of polyamide-66 are treated in a dyeing machine (for example a dyeing machine with open treatment baths) with liquors (liquor ratio 1:20) which generally contain 2% ammonium sulfate (pH 6.5) and the following dyes:

• Treatment bath 1: no dye added, with exposure and with treatment;
• Treatment bath 2: 0.025% of the yellow dye of the formula
  
• Treatment bath 3: 0.5% of the dye of formula (100);
• Treatment bath 4: 0.025% of the red dye of the formula
  
• Treatment bath 5: 0.5% of the dye of formula (101);
• Treatment bath 6: 0.025% of the blue dye of the formula
  
• Treatment bath 7: 0.5% of the dye of formula (102);

First the yarn is treated at 50 ° for 5 minutes in the prepared liquors, then the baths at 2 ° / minute heated to 95 ° C. To exhaust the dye baths, 2% acetic acid (80%) is added after 15 minutes at 95 ° C. and treated for a further 30 minutes and then cooled to 70 °. The treated yarn is rinsed warm and cold, centrifuged and dried at 80 ° in a drying cabinet.

A portion of the yarn of the individual treatments is wound up on cardboard and exposed in a fade-ometer (manufacturer: Atlas Electric Devices Co., Chicago) for 250 hours and a "black panel temperature" of 83 °.

Another portion of the yarn of the individual treatments is wound up on cardboard and exposed in a Xenotest apparatus (manufacturer: Quarzlampengesellschaft, Hanau) for 1,000 hours [SN (Swiss standard) - ISO 105 B02].

The yarn of both exposure tests is then tested for its tensile strength and elongation values in accordance with SNV (Swiss Standards Association) standard 97 461. The following results are obtained, the tensile strength and elongation values of unexposed and untreated polyamide 66 fiber material being set equal to 100%:

From the table it can be seen that the dyed polyamide fiber material is given good to excellent protection against photochemical degradation by the presence of the dyes in the treatment baths (2) to (7). Protection occurs even with a minimal copper content in the fiber [treatment baths (2), (4) and (6)].

• Behandlungsbad 1: kein Farbstoffzusatz, mit Belichtung und mit Behandlung;
• Behandlungsbad 2: 0,07 % des Farbstoffes der Formel (100), 0,012 % des Farbstoffes der Formel (101) und 0,015 % des Farbstoffes der Formel (102);
• Behandlungsbad 3: 0,055 % des Farbstoffes der Formel (100), 0,036 % des Farbstoffes der Formel
  
  und 0,003 % des Farbstoffs der Formel
  
• Behandlungsbad 4: 0,04 % des 1:2-Kobaltkomplexes des Farbstoffes der Formel
  
  0,025 % des Farbstoffes der Formel (103) und 0,003 % des Farbstoffes der Formel (104).

Example 2: 4 yarn skeins made of polyamide 66 fiber material are dyed with the following dye combinations analogously to the procedure of Example 1:

• Treatment bath 1: no dye added, with exposure and with treatment;
• Treatment bath 2: 0.07% of the dye of the formula (100), 0.012% of the dye of the formula (101) and 0.015% of the dye of the formula (102);
• Treatment bath 3: 0.055% of the dye of the formula (100), 0.036% of the dye of the formula
  
  and 0.003% of the dye of the formula
  
• Treatment bath 4: 0.04% of the 1: 2 cobalt complex of the dye of the formula
  
  0.025% of the dye of formula (103) and 0.003% of the dye of formula (104).

The dye combinations described result in a beige of the same shade in all 3 cases.

The dyed yarn is dyed and tested as described in Example 1, but only 200 hours were exposed in the fadeometer at a black panel temperature of 83 °.

The following results are obtained:

It can be seen from the table that the treatment bath (4) with a dye combination of the dyes of the formulas (103), (104) and (105) has practically no protective effect on the fiber structure; as soon as on the other hand, one or more Cu complex dyes are on the fiber [treatment baths (2) and (3)], very good fiber protection occurs.

Example 3: As described in Example 1, 4 skeins of 10 g each are dyed from polyamide 66 fiber material and finished.

• Behandlungsbad 1: kein Farbstoffzusatz, mit Belichtung und mit Behandlung;
• Behandlungsbad 2: 0,105 % des Farbstoffes der Formel (100), 0,02 % des Farbstoffes der Formel (101) und 0,065 % des Farbstoffes der Formel (102);
• Behandlungsbad 3: 0,055 % des Farbstoffes der Formel (100), 0,008 % des.Farbstoffes der Formel (101), 0,08 % des 1:2-Kobaltkomplexes der Farbstoffe der Formeln
  
  und 0,035 % des 1:2-Kobaltkomplexes des Farbstoffes der Formel (105);
• Behandlungsbad 4: 0,05 % des 1:2-Kobaltkomplexes des Farbstoffes der Formel
  
  • 0,085 % des 1:2-Kobalktomplexes der Farbstoffe der Formeln (106) und
  • 0,035 % des Farbstoffes der Formel (104).

The same olive shade is produced with the 3 different dye combinations of the different metal complex dyes.

• Treatment bath 1: no dye added, with exposure and with treatment;
• Treatment Bath 2: 0.105% of the dye of formula (100), 0.02% of the dye of formula (101) and 0.065% of the dye of formula (102);
• Treatment bath 3: 0.055% of the dye of the formula (100), 0.008% of the dye of the formula (101), 0.08% of the 1: 2 cobalt complex of the dyes of the formulas
  
  and 0.035% of the 1: 2 cobalt complex of the dye of formula (105);
• Treatment bath 4: 0.05% of the 1: 2 cobalt complex of the dye of the formula
  
  • 0.085% of the 1: 2 cobalt complex of the dyes of the formulas (106) and
  • 0.035% of the dye of formula (104).

As described in Example 1, the 4 dyed polyamide yarns are exposed hot for 200 hours and then tested for tear strength and elongation. The results can be found in the table below.

The comparison clearly shows that the presence of copper complex dyes in the polyamide fiber material results in better fiber stabilization [treatment baths (2) and (3)] than is the case with the cobalt complex dyes [treatment bath (4)].

Example 4: As described in Example 1, six combinations of two are dyed with the three dyes noted there, as indicated below.

The dyed polyamide yarn is exposed to heat for 200 hours (see Example 1) and then tested for tensile strength and elongation in accordance with SNV 97.461. The values are based on untreated, unexposed polyamide fiber material (= 100%). The following results are obtained for the exposed yarn.

wiederholt und sodann dem Heissbelichtungstest im Fade-Ometer und dem Belichtungstest in der Xenotest-Apparatur wie in Beispiel 1 beschrieben unterworfen. Die unter Zusatz der Verbindung der Formel (108) erhaltenen Färbungen werden in der folgenden Tabelle als Behandlungsbad lA, 2A, 4A und 6A gekennzeichnet, und werden den Ergebnissen des Beispiels 1 gegenübergestellt.Example 5: The experiments described in Example 1, which lead to bright yellow, red and blue colors (treatment baths 2, 4 and 6), as well as the blind treatment (treatment bath 1), with the addition of 0.075% (based on the Product weight) of the compound of the formula

repeated and then subjected to the hot exposure test in the fade-ometer and the exposure test in the Xenotest apparatus as described in Example 1. The dyeings obtained with the addition of the compound of the formula (108) are identified in the following table as treatment bath 1A, 2A, 4A and 6A and are compared with the results of Example 1.

Tabelle 4 macht deutlich, dass die fotochemische Stabilität von hellen Färbungen mit Kupferkomplexfarbstoffen auf synthetischen Polyamidmaterialien [Behandlungsbäder (2), (4) und (6)] durch Zusatz von farblosen faseraffinen Kupferkomplexverbindungen noch weiter verbessert werden kann [Behandlungsbäder (2A), (4A) und (6A).The test of the exposed dyeings and blind treatments for tear strength and elongation shows the results noted in the table below:

Table 4 shows that the photochemical stability of light dyeings with copper complex dyes on synthetic polyamide materials [treatment baths (2), (4) and (6)] can be further improved by adding colorless fiber-affine copper complex compounds [treatment baths (2A), (4A ) and (6A).

oder 0,075 % der Verbindung der Formel

anstelle des Kupferkomplexes der Formel (108) durchgeführt und anschliessend dem Heissbelichtungstest im Fade-0-meter und dem Belichtungstest in der Xenotestapparatur wie in Beispiel 5 beschrieben unterworfen, so erhält man ebenfalls eine deutliche zusätzliche Verbesserung der fotochemischen Stabilität der Färbungen.Be the dyeing experiments described in Example 5 using 0.075% (based on the weight of the goods) of the compound.

or 0.075% of the compound of the formula

carried out instead of the copper complex of the formula (108) and then subjected to the hot exposure test in the fade-0-meter and the exposure test in the xenote apparatus as described in Example 5, this also gives a significant additional improvement in the photochemical stability of the dyeings.

Example 6: Dyings on nylon filament yarn are carried out using 0.05% dye of the formula (100) as described in Example 1, but at 95 ° C. and in each case using 0.05% of each of the copper complex compounds of the formulas (108) (109) and (110). And with the addition of 2% acetic acid 80%.

The material is exposed according to DIN 75202 (Fakra) and xenon (SN-ISO 105 B ₀ 2) and tested for its tensile strength and elongation. The following results are obtained, the tensile strength values and elongation values of unexposed and untreated polyamide fiber material being set equal to 100%.

Example 7: 10 g of nylon filament yarn (glossy) are dyed in a laboratory dyeing machine with open dye baths at a liquor ratio of 1:30 in liquors which contain 2% (by weight of the product) ammonium sulfate and 0.1% of the following dyes of the formulas (111) - (118) included. The yarn is passed into the dyebath at 40 ° C., treated for 5 minutes and the temperature is increased to 95 ° C. At this temperature you dye for 45 minutes. Then it is cooled to about 60 ° C. and the dyeings are rinsed with cold water and dried at 105 ° C. in a drying cabinet.

The yarn is then wound on cardboard and exposed in a fade ometer at a temperature of 83 ° C.

The unexposed and exposed yarn is finally tested for tensile strength and elongation in accordance with SNV 97.461.

With all copper complex dyes - as the comparison with blind dyeing (= yarn treated without dye) or a conventional dyeing with the dyes of formulas (104), (106) and (107) shows a significant improvement in the photochemical stability of the fiber material.

Example 8:

• Behandlungsbad 1: kein Farbstoff
• Behandlungsbad 2: 0,5% Farbstoff der Formel (100) Behandlungsbäder 3, 4: 0,15% oder 0,5% Farbstoff der Formel(119)
  
  1:2 Co - Komplex
• Behandlungsbäder 5, 6: 0,5% Farbstoff der Formel (100) kombiniert mit 0,15% oder 0,5% Farbstoff der Formel (119)
• Behandlungsbäder 7, 8: 0,15% oder 0,5% Farbstoff der Formel (120)
  
• Behandlungsbäder 9, 10: 0,5% Farbstoff der Formel (100) kombiniert mit 0,15% oder 0,5% Farbstoff der Formel (120).

Ten 10 g of nylon 66 staple skeins are dyed as noted in Example 7 with the dyes mentioned below

• Treatment bath 1: no dye
• Treatment bath 2: 0.5% dye of the formula (100) Treatment baths 3, 4: 0.15% or 0.5% dye of the formula (119)
  
  1: 2 Co complex
• Treatment baths 5, 6: 0.5% dye of the formula (100) combined with 0.15% or 0.5% dye of the formula (119)
• Treatment baths 7, 8: 0.15% or 0.5% dye of the formula (120)
  
• Treatment baths 9, 10: 0.5% dye of the formula (100) combined with 0.15% or 0.5% dye of the formula (120).

The yarn dyeings are wrapped on cardboard, exposed for 150 hours in accordance with DIN 75.202 (draft) and checked for tensile strength and elongation in accordance with SNV 97.461. The results are shown in Table 7.

Example 9:

Ten 10g nylon 66 staple skeins as in Examples 7 and 8 are noted, dyed, exposed and tested. The results are shown in Table 8. The treatment baths contain the following dyes

• Behandlungsbad 15: je 0,1% der Farbstoffe der Formeln (115) und (121)
• Behandlungsbad 16: 0,2% Farbstoff der Formel (115) und 0,3_% Farbstoff der Formel(121)
  

Treatment baths 11.12: 0.1% and 0.2% dye of the formula (115) Treatment baths 13.14: 0.1% and 0.3% dye of the formula (121)

• Treatment bath 15: 0.1% each of the dyes of the formulas (115) and (121)
• Treatment bath 16: 0.2% dye of the formula (115) and 0.3 _% dye of the formula (121)
  

Claims (16)

1. A process for the photochemical stabilization of fiber materials made of synthetic polyamides, characterized in that the fiber materials are treated with at least one water-soluble copper complex dye or with a mixture of copper complex compounds, at least one component being a water-soluble copper complex dye. 2. The method according to claim 1, characterized in that at least one water-soluble copper complex or azomethine dye is used. _3rd A method according to claim 2, characterized in that water-soluble copper complexes of azo or azomethine dyes of the formula

used, wherein D is a residue of the benzene or naphthalene series, X is a nitrogen atom or the CH group, Y is the HO, CH ₃ O or HOOC group and Y 'is the HO or an amino group, and wherein K, is in the event that X is a nitrogen atom, the residue of a coupling component of the benzene, naphthalene or heterocyclic series or the residue of a ketomethylene compound, or in the case that X is the CH group, K is the residue of an o-hydroxyaldehyde . 4. The method according to claim 3, characterized in that a copper complex dye of the formula

used, wherein A is an optionally substituted carboxyphenyl or sulfophenyl radical, R _{1 is} hydrogen or C _1-4 alkyl, X is a nitrogen atom or the CH group and K, in the event that X is a nitrogen atom, the rest of a coupling component of benzene -, naphthalene, pyrazolone, aminopyrazole, acetoacetanilide, 2,4-dioxyquinoline, pyridone or pyridine series, or, if X is the CH group, the residue of an o-hydroxybenzaldehyde, and the ring B optionally can be further substituted. 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 contains a copper complex dye and a fiber-affine water-soluble copper complex of bisazomethines, acylhydrazones, 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, in which Me is copper, R _{2 is} hydrogen or an optionally substituted alkyl or aryl radical and Z is an optionally substituted alkylene, cycloalkylene or arylene radical and n is 1, 2 or 3. 8. The method according to claim 5, characterized in that the fiber-affine, water-soluble copper complex is one of the formula

used, where Me is copper and 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 as affinity for the fiber, water-soluble copper omplex _k such of the formula

used, in which Me is copper, 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 fiber-affine water-soluble copper complex compound 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 1,000 µg of copper are added to 1 g of polyamide material, in particular that 5 to 200 µg of copper are added to 1 g of polyamide. 12. The method according to claim 1, characterized in that at least one copper complex dye or the mixture of copper complex compounds is used 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 in the same dye bath. 14. The method according to claim 12 or 13, characterized in that the acid dyes used are metal-free monoazo or polyazo dyes, 1: 2-chromium or 1: 2-cobalt complex azo dyes, anthraquinone, dioxazine, phthalocyanine, nitroaryl or stilbene dyes, which have at least one acid group, in particular a sulfonic acid 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. Aqueous dye liquor, characterized in that it contains a water-soluble copper complex dye or a mixture of copper complex compounds containing at least one water-soluble copper complex dye.