EP0436470B1 - Process of photochemical stabilization of dyed polyamid-fibre materials - Google Patents

Abstract

There is disclosed a process for the photochemical stabilization of dyed polyamide fibre materials, which comprises treating the dyed material with an aqueous foamed composition which contains at least a non-dyeing copper complex of bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic aldehydes or ketones or oximes. By means of the process of this invention it is possible to prevent wastewater from being contaminated with copper-containing impurities.

Description

The present invention relates to a process for the photochemical stabilization of dyed polyamide fiber materials, preferably with a pronounced three-dimensional character (pile and pile materials) and in particular carpets with the aid of foam.

EP-A-0 245 204 describes a process for the photochemical stabilization of polyamide fiber material with a mixture of an organic copper complex, a light stabilizer and optionally an antioxidant,
which is applied to the polyamide fiber material from an aqueous bath.

From EP-A-0 200 843 it is known to use copper complexes of bias zomethines to improve the light fastness of polyamide dyeings, the copper complexes being applied in the dye bath. With this process, it is inevitable that liquor waste containing copper-containing contaminants is generated.

Surprisingly, it has been possible to prevent this waste by applying these copper complex compounds to the colored textile material in a post-treatment by means of a foamed, aqueous preparation.

• (a) einen nicht färbenden Kupferkomplex von Bisazomethinen, Acylhydrazonen, Semicarbazonen oder Thiosemicarbazonen aromatischer Aldehyde oder Ketone oder Oximen und
• b) ein anionisches oder nichtionogenes Tensid oder eine Mischung dieser Tenside enthält,

wobei man die wässrige Zubereitung vor der Behandlung des Fasermaterials verschäumt.The present invention accordingly relates to a process for the photochemical stabilization of dyed textile polyamide fiber materials, which is characterized in that the dyed fiber material is treated after the dyeing process with an aqueous preparation, which at least

• (a) a non-coloring copper complex of bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic aldehydes or ketones or oximes and
• b) contains an anionic or nonionic surfactant or a mixture of these surfactants,

whereby the aqueous preparation is foamed before the treatment of the fiber material.

Bisazomethines of aromatic aldehydes or ketones are understood here as Schiff bases of aliphatic or aromatic diamines, the aldehydes and ketones having an OH group in the o-position to the formyl or acyl radical. The bond with the metal atom takes place via these two OH groups and the two nitrogen atoms in the bisazaomethine part. Accordingly, these are tidentate ligands. These can contain one or more sulfo groups, which are in the aldehyde or Part of the ketone 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 are preferably used as component (a)

in which R represents hydrogen or an optionally substituted alkyl or aryl radical,
Q is an optionally substituted alkylene, cycloalkylene or arylene radical and
n means 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, then preferably a C₁-C₈-alkyl radical, in particular a C₁-C₄-alkyl radical, which can be branched or unbranched and optionally substituted, by halogen such as fluorine, chlorine or bromine, by C₁- C₄-alkoxy such as methoxy or ethoxy, by a phenyl or carboxyl radical, by C₁-C₄-alkoxycarbonyl such as the acetyl radical or by hydroxy or a mono- or dialkylated amino group. In addition, there is also the cyclohexyl radical, which can also be substituted, for example by C₁-C₄-alkyl or C₁-C₄-alkoxy.

If R is an optionally substituted aryl radical, a phenyl or naphthyl radical is particularly suitable, which can be substituted by C₁-C₄-alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, C₁ -C₄-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy, halogen such as fluorine, chlorine or bromine, C₂-C₅-alkanoylamino such as acetylamino, propionylamino or butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.

If Q is an alkylene radical, it is primarily an optionally substituted C₂-C₄ alkylene radical, in particular a -CH₂-CH₂ bridge. However, a C₂-C₈-alkylene chain interrupted by oxygen or in particular by nitrogen is also possible, in particular the - (CH₂) ₃-NH- (CH₂) ₃ bridge.

If Q is an arylene radical, it is primarily a phenylene radical, in particular an o-phenylene radical. This can optionally be substituted by C₁-C₄-alkyl or by C₁-C₄-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, -SO₂NH₂, -SO₂NHR₀ or -SO₂N (R₀) ₂, where R₀ is alkyl or alkoxyalkyl and wherein alkyl and alkoxy are each to be understood to be residues with 1-4 carbon atoms, or one of residues ortho to one another, together with the carbon atoms to which they are attached are formed benzene residue.

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

worin
R' Wasserstoff oder C₁-C₃-Alkyl
R₁, R₂, R₃ und R₄ je Wasserstoff, Halogen, Hydroxy, Hydroxyalkyl, Alkyl, Alkoxy, Alkoxyalkoxy, Alkoxyalkoxyalkoxy, Carboxymethoxy, Alkylamino, Dialkylamino, -SO₂NH₂, -SO₂NHR oder -SO₂NR₂ 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,
X₁ und Y₁ je Wasserstoff, C₁-C₄-Alkyl oder einen aromatischen Rest bedeuten oder X₁ und Y₁ 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 are of particular importance in the copper complexes of the formula (1)

wherein
R 'is hydrogen or C₁-C₃ alkyl
R₁, R₂, R₃ and R₄ are each hydrogen, halogen, hydroxy, hydroxyalkyl, alkyl, alkoxy, alkoxyalkoxy, alkoxyalkoxyalkoxy, carboxymethoxy, alkylamino, dialkylamino, -SO₂NH₂, -SO₂NHR₂ or -SO₂NR₂, where R is alkyl or alkoxyalkyl and is alkyl or alkoxy in each case groups with 1-4 C atoms are to be understood, or
R₁ and R₂ or R₂ and R₃ or R₃ and R₄ together with the carbon atoms to which they are attached form a benzene radical,
X₁ and Y₁ each represent hydrogen, C₁-C₄ alkyl or an aromatic radical or X₁ and Y₁ together with the C atoms to which they are attached form a cycloaliphatic radical with 5-7 C atoms.

C₁ to C₄ alkyl for X₁ and Y₁ means e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Aromatic radicals for X₁ and Y₁ are especially optionally substituted naphthyl and especially phenyl radicals.

In general, the copper complex compounds of the formula (2) are water-insoluble, provided they have no carboxymethoxy radicals (-O-CH₂-COOH) or their salts.

The cycloaliphatic radicals are cyclopentylene, cyclohexylene or cycloheptylene radicals.

Preferably R₁ to R bedeuten each independently represent hydrogen, chlorine, bromine, methyl, ethyl, butyl, methoxy, ethoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino or R₁ and R₂ together form a condensed benzene radical.

Of the substituents X₁ and Y₁ is preferably one hydrogen and the other hydrogen, methyl, ethyl or phenyl or X₁ and Y₁ together form a cyclohexylene radical.

zum Einsatz, worin R₅ bis R₈ unabhängig voneinander je Wasserstoff, Hydroxy, Brom, Methyl, tert. Butyl, Methoxy, Methoxyethoxy, Ethoxyethoxyethoxy oder Diethylamino, X₂ Wasserstoff, Methyl, Ethyl, oder Phenyl und Y₂ Wasserstoff bedeuten oder R₅ und R₆ zusammen einen ankondensierten Benzolrest oder X₂ und Y₂ zusammen einen Cyclohexylenrest bilden.Water-insoluble copper complexes of the formula are preferably used

used in which R₅ to R₈ independently of one another each hydrogen, hydroxy, bromine, methyl, tert. Butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino, X₂ is hydrogen, methyl, ethyl, or phenyl and Y₂ is hydrogen or R₅ and R₆ together form a condensed benzene radical or X₂ and Y₂ together form a cyclohexylene radical.

worin
R₉, R₁₀ und R₁₁ unabhängig voneinander je Wasserstoff, Chlor, Brom, Methyl oder Methoxy bedeuten oder worin R₉ und R₁₀ zusammen einen ankondensierten Benzolring bilden und
X₃ Wasserstoff, Methyl, Ethyl oder Phenyl ist.Compounds of the formula are of particular interest

wherein
R₉, R₁₀ and R₁₁ each independently represent hydrogen, chlorine, bromine, methyl or methoxy or wherein R₉ and R₁₀ together form a fused-on benzene ring and
X₃ is hydrogen, methyl, ethyl or phenyl.

In the foreground of interest are, however, compounds of formula (4) in which R₉, R₁₀, R₁₁ and X₃ are hydrogen.

worin R₁ und R₁₂ 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

worin R₁ die unter Formel (5) angegebene Bedeutung hat und Z₂ für Sauerstoff oder Schwefel steht.For copper complexes of acylhydrazone aromatic aldehydes and ketones, which as Component (a) are used, it is primarily the complexes of the formula

wherein R₁ and R₁₂ independently of one another are 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

wherein R₁ has the meaning given by formula (5) and Z₂ represents oxygen or sulfur.

If in the formulas (5) and (5a) R₁ and / or R₁₂ 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, C₁-C₄-alkoxy such as methoxy or ethoxy, also phenyl or carbonyl, C₁-C₄alkoxycarbonyl such as e.g. Acetyl or hydroxy, mono- or dialkylamino.

If in the formulas (5) and (5a) R₁ and / or R₁₂ is an optionally substituted aryl radical, a phenyl or naphthyl radical, which can be substituted by C₁-C₄-alkyl such as methyl, ethyl, propyl, isopropyl, is particularly suitable , Butyl, isobutyl, sec-butyl or tert-butyl, C₁-C₄-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy, halogen such as fluorine, chlorine or bromine, C₂-C₅ Alkanoylamino such as acetylamino, propionylamino or butyrylamino, nitro, cyano, sulfo or a mono- or dialkylated amino group.

Such complexes of the formula (5) are preferably used in which R₁ is hydrogen and R₁₂ is hydrogen, methyl or in particular the phenyl radical, and especially the complexes in which the sulfo group is in turn in the p-position to the oxygen.

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

wherein R is hydrogen, hydroxy, alkyl or cycloalkyl and in which the ring A may optionally be further substituted, such as copper compounds of salicylaldoxime and salicyldroxamic acid.

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

The complexes of formulas (1) to (5) are preferably in neutral form, i.e. used as alkali salt, especially sodium or amine salt.

The compounds which can be used as component (a) are known and can be prepared by processes known per se. They are e.g. known from EP-A 51 188, 113 856 and 162 811 and can be prepared by known methods.

The copper complexes which can be used as component (a) are expediently applied from an aqueous bath, these being used advantageously in an amount such that 5 to 200 »g, in particular 10 to 100» g copper are added to 1 g polyamide fiber material.

If the compounds of component (a) are water-insoluble, they are expediently used as finely divided dispersions, which are more common by grinding in the presence of Dispersants can be obtained.

In addition to component (a), the aqueous preparation contains
(b) an anionic surfactant or a nonionic surfactant or a mixture of these surfactants and optionally
(c) a salt of a hydrolyzed polymaleic anhydride and
(d) a polar organic solvent.

Component (b) of the aqueous preparation constitutes the actual foaming agent. Anionic or nonionic surfactants or mixtures of anionic and nonionic surfactants are generally suitable for this.

The anionic surfactants of component (b) are preferably alkylene oxide adducts, e.g. acidic ether groups or preferably ester groups of inorganic or organic acids, addition products of alkylene oxides, especially ethylene oxide and / or propylene oxide or styrene oxide onto aliphatic hydrocarbon radicals with a total of at least 2 carbon atoms, organic hydroxyl, carboxyl, amino and / or amido compounds or mixtures thereof Fabrics. These acidic ethers or esters can be used as free acids or as salts, e.g. Alkali metal, alkaline earth metal, ammonium or amine salts are present.

These anionic surfactants are prepared by known methods by adding at least 1 mol, preferably more than 1 mol, for example 2 to 60 mol, of ethylene oxide or propylene oxide to the organic hydroxyl, carboxyl, amino and / or amido compounds, or alternately in any order Add ethylene oxide and propylene oxide and then etherify or esterify the adducts and, if appropriate, convert the ethers or the esters into their salts. The basic materials are higher fatty alcohols, ie alkanols or alkenols each with 8 to 22 carbon atoms, dihydric to hexavalent aliphatic alcohols with 2 to 9 carbon atoms, alicyclic alcohols, phenylphenols, benzylphenols, alkylphenols with one or more alkyl substituents, or at least together Have 4 carbon atoms, fatty acids with 8 to 22 carbon atoms, amines which have aliphatic and / or cycloaliphatic hydrocarbon radicals of at least 8 carbon atoms, particularly fatty amines containing such, hydroxyalkylamines, hydroxyalkylamides and aminoalkyl esters of fatty acids or dicarboxylic acids and higher alkylated aryloxycarboxylic acids.

• sulfatierte aliphatische Alkohole, deren Alkylkette 8 bis 18 Kohlenstoffatome aufweist, z.B. sulfatierter Laurylalkohol;
• sulfatierte ungesättigte Fettsäuren oder Festtsäureniederalkylester, die im Fettrest 8 bis 20 Kohlenstoffatome aufweisen, z.B. Rizinolsäure und solche Fettsäuren enthaltende Oele, z.B. Rizinusöl;
• Alkylsulfonate, deren Alkylkette 8 bis 20 Kohlenstoffatome enthält, z.B. Dodecylsulfonat;
• Alkylarylsulfonate mit geradkettiger oder verzweigter Alkylkette mit mindestens 6 Kohlenstoffatomen, z.B. Dodecylbenzolsulfonate oder 3,7-Diisobutyl-naphthalinsulfonate;
• die als Seifen bezeichneten Alkalimetall-, Ammonium- oder Aminsalze von Fettsäuren mit 10 bis 20 Kohlenstoffatomen, z.B. Kolophoniumsalze;
• Ester von Polyalkoholen, insbesondere Mono- oder Diglyceride von Fettsäuren mit 12 bis 18 Kohlenstoffatomen, z.B. Monoglyceride der Laurin-, Stearin- oder Oelsäure, und
• die mit einer organischen Dicarbonsäure wie z.B. Maleinsäure, Malonsäure oder Sulfobernsteinsäure, vorzugsweise jedoch mit einer anorganischen mehrbasischen Säure wie o-Phosphorsäure oder insbesondere Schwefelsäure in einen sauren Ester übergeführten Anlagerungsprodukte von 1 bis 60 Mol Ethylenoxid und/oder Propylenoxid an Fettamine, Fettsäuren oder Fettalkohole je mit 8 bis 22 Kohlenstoffatomen, an Alkylphenole mit 4 bis 16 Kohlenstoffatomen in der Alkylkette oder an drei- bis sechswertige Alkanole mit 3 bis 6 Kohlenstoffatomen,

Examples of suitable anionic surfactants are:

• sulfated aliphatic alcohols, the alkyl chain of which has 8 to 18 carbon atoms, for example sulfated lauryl alcohol;
• sulfated unsaturated fatty acids or solid lower alkyl esters which have 8 to 20 carbon atoms in the fat residue, for example ricinoleic acid and oils containing such fatty acids, for example castor oil;
• Alkyl sulfonates whose alkyl chain contains 8 to 20 carbon atoms, for example dodecyl sulfonate;
• Alkylarylsulfonates with a straight-chain or branched alkyl chain with at least 6 carbon atoms, for example dodecylbenzenesulfonates or 3,7-diisobutyl-naphthalenesulfonates;
• the so-called alkali metal, ammonium or amine salts of fatty acids with 10 to 20 carbon atoms, for example rosin salts;
• Esters of polyalcohols, in particular mono- or diglycerides of fatty acids having 12 to 18 carbon atoms, for example monoglycerides of lauric, stearic or oleic acid, and
• those with an organic dicarboxylic acid such as maleic acid, malonic acid or sulfosuccinic acid, but preferably with an inorganic polybasic acid such as o-phosphoric acid or, in particular, sulfuric acid, adducts of 1 to 60 moles of ethylene oxide and / or propylene oxide with fatty amines, fatty acids or fatty alcohols each converted into an acid ester with 8 to 22 carbon atoms, on alkylphenols with 4 to 16 carbon atoms in the alkyl chain or on tri- to hexavalent alkanols with 3 to 6 carbon atoms,

• (I) saure Ester oder deren Salze eines Polyadduktes von 2 bis 15 Mol Ethylenoxid an 1 Mol Fettalkohol mit 8 bis 22 Kohlenstoffatomen oder an 1 Mol Alkylphenol mit 4 bis 12 Kohlenstoffatomen im Alkylteil,
• (II) Alkylphenylsulfonate mit 8 bis 18 Kohlenstoffatomen im Alkylrest,
• (III) sulfonierte 1-Benzyl-2-alkylbenzimidazole mit 8 bis 22 Kohlenstoffatomen im Alkylrest,

wobei die Komponenten (I), (II) und (III) einzeln oder als Gemisch verwendet werden können.Anionic surfactants of component (b) are highly suitable

• (I) acidic esters or their salts of a polyadduct of 2 to 15 moles of ethylene oxide with 1 mole of fatty alcohol with 8 to 22 carbon atoms or with 1 mole of alkylphenol with 4 to 12 carbon atoms in the alkyl part,
• (II) alkylphenyl sulfonates with 8 to 18 carbon atoms in the alkyl radical,
• (III) sulfonated 1-benzyl-2-alkylbenzimidazoles with 8 to 22 carbon atoms in the alkyl radical,

the components (I), (II) and (III) can be used individually or as a mixture.

oder die Formel



        (8)   R-O-(CH₂CH₂-O)_z-X



dargestellt werden, worin R Alkyl oder Alkenyl mit je 8 bis 22 Kohlenstoffatomen, X der Säurerest einer anorganischen, Sauerstoff enthaltenden Säure oder der Rest einer anorganischen Säure, p 4 bis 12 und z 2 bis 15 sind.Component (I) of the preferred anionic surfactants mentioned can be, for example, by the formula

or the formula



(8) RO- (CH₂CH₂-O) _z -X



in which R is alkyl or alkenyl each having 8 to 22 carbon atoms, X is the acid residue of an inorganic, oxygen-containing acid or the rest of an inorganic acid, p 4 to 12 and z 2 to 15.

The alkyl radicals on the benzene ring of the formula (7) can be butyl, hexyl, n-octyl, n-nonyl, p-tert-octyl, p-tert-nonyl, decyl or dodecyl. The alkyl radicals having 8 to 12 carbon atoms are preferred, in particular the octyl and nonyl radicals.

The acid residue X is derived, for example, from low molecular weight dicarboxylic acids, such as Maleic acid, malonic acid, succinic acid or sulfosuccinic acid and is connected to the ethyleneoxy part of the molecule via an ester bridge. In particular, however, X is derived from inorganic polybasic acids such as orthophosphoric acid and especially sulfuric acid. The acid residue X is preferably in salt form, i.e. e.g. as an alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.

The fatty alcohols for the preparation of component (I) of formula (8) are e.g. those with 8 to 22, in particular with 8 to 18 carbon atoms, such as octyl, decyl, lauryl, tridecyl, myristyl, ceryl, stearyl, oleyl, arachidyl or behenyl alcohol.

The ester formation generally takes place with the same acids which are mentioned for the compounds of the formula (7). A preferred compound of formula (8) is the sodium salt of lauryl triglycol ether sulfonic acid.

• 1. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol p-tert.-Nonylphenol;
• 2. Natriumsalz des sauren Maleinsäureesters des Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol p-Nonylphenyl;
• 3. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol p-Butylphenol;
• 4. Ammoniumsalz des sauren Phosphorsäureester des Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol p-Nonylphenol;
• 5. Natriumsalz des Disulfobernsteinsäureesters des Anlagerungsproduktes von 4 Mol Ethylenoxid an 1 Mol n-Octylphenol;
• 6. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 9 Mol Ethylenoxid an 1 Mol p-Nonylphenol;
• 7. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 6 Mol Ethylenoxid an 1 Mol p-Nonylphenol;
• 8. Natriumsalz des Monosulfobernsteinsäureesters des Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol p-Nonylphenol;
• 9. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 6 Mol Ethylenoxid an 1 Mol Dodecylphenol;
• 10. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Octylphenol;
• 11. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Alfol (1014);
• 12. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Stearylalkohol;
• 13. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol 2-Ethylhexanol;
• 14. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 15 Mol Ethylenoxid an 1 Mol Stearylalkohol;
• 15. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol Tridecylalkohol;
• 16. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 4 Mol Ethylenoxid an 1 Mol Hydroabietylalkohol;
• 17. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol Alfol (2022);
• 18. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol Laurylalkohol;
• 19. Di-(β-hydroxy-ethyl)-aminsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol Laurylalkohol;
• 20. Natriumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Laurylalkohol;
• 21. Natriumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol Laurylalkohol;
• 22. Saurer Phosphorsäureester des Anlagerungsproduktes von 5 Mol Ethylenoxid an 1 Mol 2-Ethyl-n-hexanol;
• 23. Ammoniumsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol eines Alkoholgemisches mit 20 bis 22 Kohlenstoffatomen.
• 24. Diphosphorsäureester des Anlagerungsproduktes von 8 Mol Ethylenoxid an 1 Mol Dodecylamin.
• 25. Ammoniumsalz des sauren Phosphorsäureesters des Anlagerungsproduktes von 8 Mol Ethylenoxid an 1 Mol Talgfettamin.

The following compounds are mentioned in particular for component (I) of the formulas (7) and (8):

• 1. ammonium salt of the acidic sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-tert-nonylphenol;
• 2. sodium salt of the acidic maleic acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenyl;
• 3. ammonium salt of the acidic sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of p-butylphenol;
• 4. ammonium salt of the acidic phosphoric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol;
• 5. sodium salt of the disulfosuccinic acid ester of the adduct of 4 moles of ethylene oxide and 1 mole of n-octylphenol;
• 6. ammonium salt of the acidic sulfuric acid ester of the adduct of 9 moles of ethylene oxide and 1 mole of p-nonylphenol;
• 7. ammonium salt of the acidic sulfuric acid ester of the adduct of 6 moles of ethylene oxide and 1 mole of p-nonylphenol;
• 8. sodium salt of the monosulfosuccinic acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol;
• 9. ammonium salt of the acidic sulfuric acid ester of the adduct of 6 moles of ethylene oxide and 1 mole of dodecylphenol;
• 10. ammonium salt of the acidic sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of octylphenol;
• 11. ammonium salt of the acidic sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of alfol (1014);
• 12. ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of stearyl alcohol;
• 13. ammonium salt of the acidic sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of 2-ethylhexanol;
• 14. ammonium salt of the acid sulfuric acid ester of the adduct of 15 moles of ethylene oxide and 1 mole of stearyl alcohol;
• 15. ammonium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of tridecyl alcohol;
• 16. ammonium salt of the acidic sulfuric acid ester of the adduct of 4 moles of ethylene oxide and 1 mole of hydroabietyl alcohol;
• 17. Ammonium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of alfol (2022);
• 18. Ammonium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide to 1 mole of lauryl alcohol;
• 19. Di- (β-hydroxy-ethyl) amine salt of the acidic sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of lauryl alcohol;
• 20. Sodium salt of the acidic sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of lauryl alcohol;
• 21. Sodium salt of the acidic sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of lauryl alcohol;
• 22. Acidic phosphoric acid ester of the adduct of 5 moles of ethylene oxide and 1 mole of 2-ethyl-n-hexanol;
• 23. Ammonium salt of the acidic sulfuric acid ester of the adduct of 3 moles of ethylene oxide with 1 mole of an alcohol mixture having 20 to 22 carbon atoms.
• 24. Diphosphoric acid ester of the adduct of 8 moles of ethylene oxide with 1 mole of dodecylamine.
• 25. Ammonium salt of the acidic phosphoric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of tallow fatty amine.

The alkylphenyl sulfonates of component (II) are generally alkali metal salts of the corresponding monosulfonic acids having 8 to 18 carbon atoms in the alkyl part which is straight-chain or branched, saturated or unsaturated. Examples of alkyl radicals are N-octyl, tert-octyl, n-nonyl, tert-nonyl, n-decyl, n-dodecyl, tridecyl, myristyl, cetyl, stearyl or oleyl. Alkyl radicals having 8 to 12 carbon atoms are preferred, dodecylbenzenesulfonate (sodium salt) being particularly suitable.

Components (I) and (II) can be used alone or as mixtures with one another.

The nonionic surfactants according to component (b) are advantageously nonionic alkylene oxide addition products of 1 to 100 moles of alkylene oxide, e.g. Ethylene oxide and / or propylene oxide in 1 mol of an aliphatic monoalcohol with at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol, a phenol which is optionally substituted by alkyl or phenyl or a fatty acid with 8 to 22 carbon atoms.

The aliphatic monoalcohols for producing the nonionic surfactants are, for example, water-soluble monoalcohols with at least 4 carbon atoms, preferably 8 to 22 carbon atoms. These alcohols can be saturated or unsaturated and branched or straight-chain and can be used alone or in a mixture. Natural alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol or synthetic alcohols such as in particular 2-ethylhexanol, also trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or fatty alcohols can be reacted with the alkylene oxide.

Other aliphatic alcohols that can be reacted with alkylene oxide are 3- to 6-valent alkanols. These contain 3 to 6 carbon atoms and are in particular glycerol, trimethylolpropane, erythritol, mannitol, pentaerythritol and sorbitol. The 3- to 6-valent alcohols are preferably reacted with propylene oxide or ethylene oxide or mixtures of these alkylene oxides.

Suitable optionally substituted phenols are, for example, phenol, o-phenylphenol or alkylphenols, the alkyl radical of which has 1 to 16, preferably 4 to 12, carbon atoms. Examples of these alkylphenols are p-cresol, butylphenol, tributylphenol, octylphenol and especially nonylphenol.

The fatty acids preferably have 8 to 12 carbon atoms and can be saturated or unsaturated, e.g. capric, lauric, myristic, palmitic or stearic acid or decenic, dodecenic, tetradecenic, hexadecenic, oleic, linoleic, linolenic or preferably ricinoleic acid.

• Anlagerungsprodukte von vorzugsweise 5 bis 80 Mol Alkylenoxiden, insbesondere Ethylenoxid, wobei einzelne Ethylenoxideinheiten durch substituierte Epoxide, wie Styroloxid und/oder Propylenoxid ersetzt sein können, an höhere ungesättigte oder gesättigte Fettalkohole, Fettsäuren, Fettamine oder Fettamide mit 8 bis 22 Kohlenstoffatomen oder an Phenylphenol oder Alkylphenole, deren Alkylreste mindestens 4 Kohlenstoffatome aufweisen;
• Alkylenoxid-, insbesondere Ethylenoxid- und/oder Propylenoxid-Kondensationsprodukte;
• Umsetzungsprodukte aus einer 8 bis 22 Kohlenstoffatome aufweisenden Fettsäure und einem primären oder sekundären, mindestens eine Hydroxyniederalkyl- oder Niederalkoxyniederalkylgruppe aufweisenden Amin oder Alkylenoxid-Anlagerungsprodukte dieser hydroxyalkylgruppenhaltigen Umsetzungsprodukte, wobei die Umsetzung so erfolgt, dass das molekulare Mengenverhältnis zwischen Hydroxyalkylamin und Fettsäure 1:1 und grösser als 1, z.B. 1,1:1 bis 2:1 sein kann, und
• Anlagerungsprodukte von Propylenoxid an einen drei- bis sechswertigen aliphatischen Alkohol von 3 bis 5 Kohlenstoffatomen, z.B. Glycerin oder Pentaerythrit, wobei die Polypropylenoxidaddukte ein durchschnittliches Molekulargewicht von 250 bis 1800, vorzugsweise 400 bis 900, aufweisen.

Examples of nonionic surfactants are:

• Addition products of preferably 5 to 80 mol of alkylene oxides, in particular ethylene oxide, where individual ethylene oxide units can be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, with higher unsaturated or saturated fatty alcohols, fatty acids, fatty amines or fatty amides with 8 to 22 carbon atoms or with phenylphenol or Alkylphenols whose alkyl radicals have at least 4 carbon atoms;
• Alkylene oxide, especially ethylene oxide and / or propylene oxide condensation products;
• Reaction products of a fatty acid having 8 to 22 carbon atoms and a primary or secondary amine or alkylene oxide adducts of these hydroxyalkyl group-containing reaction products having at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, the reaction being so takes place that the molecular quantitative ratio between hydroxyalkylamine and fatty acid can be 1: 1 and greater than 1, for example 1.1: 1 to 2: 1, and
• Addition products of propylene oxide onto a trihydric to hexavalent aliphatic alcohol of 3 to 5 carbon atoms, for example glycerol or pentaerythritol, the polypropylene oxide adducts having an average molecular weight of 250 to 1800, preferably 400 to 900.

• (IV) Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxid an 1 Mol Fettalkohol oder Fettsäure mit jeweils 8 bis 22 Kohlenstoffatomen oder an 1 Mol Alkylphenol mit insgesamt 4 bis 12 Kohlenstoffatomen im Alkylteil,
• (V) gegebenenfalls mono-, di- oder triethoxylierte Fettalkohole mit 8 bis 22 Kohlenstoffatomen im Fettalkoholrest, oder
• (VI) Fettsäuredialkanolamide mit 8 bis 22 Kohlenstoffatomen im Fettsäurerest.

Non-ionic surfactants of component (b) are highly suitable

• (IV) addition products of 2 to 15 mol of ethylene oxide with 1 mol of fatty alcohol or fatty acid each with 8 to 22 carbon atoms or with 1 mol of alkylphenol with a total of 4 to 12 carbon atoms in the alkyl part,
• (V) optionally mono-, di- or triethoxylated fatty alcohols having 8 to 22 carbon atoms in the fatty alcohol residue, or
• (VI) fatty acid dialkanolamides with 8 to 22 carbon atoms in the fatty acid residue.

Component (IV) advantageously includes octyl or preferably nonylphenol-ethylene oxide adducts with 2 to 12 ethylene oxide units.

The following compounds may be mentioned in particular: p-octylphenol / 2 mol ethylene oxide, p-nonylphenol / 9 mol ethylene oxide, p-nonylphenol / 10 mol ethylene oxide, p-nonylphenol / 11 mol ethylene oxide.

Further alkylphenol-ethylene oxide adducts can be e.g. derived from butylphenol or tributylphenol.

Component (IV) can expediently also be an adduct of 2 to 15 mol, preferably 7 to 15 mol, of ethylene oxide with 1 mol of an aliphatic monoalcohol having 8 to 22 carbon atoms.

The aliphatic monoalcohols can be saturated or unsaturated and can be used alone or as mixtures. Natural alcohols such as e.g. Lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol or synthetic alcohols such as in particular 2-ethylhexanol, furthermore triemethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or C₁₂-C₂₂ fatty alcohols are reacted with ethylene oxide.

Ethylene oxide addition products of 2 to 15 moles of ethylene oxide to 1 mole can also be used Fatty acid can be used as component (IV). The fatty acids preferably have 10 to 20 carbon atoms and can be saturated or unsaturated, such as, for example, capric, lauric, myristic, palmitic or stearic acid or decene, dodecene, tetradecene, hexadecene, oil, Linoleic or ricinoleic acid.

Component (V) is, by definition, optionally ethoxylated fatty alcohol, the HLB value of which is expediently 0.1 to 10, in particular 0.5 to 10. Components (V) with HLB values in the range from 0.1 to 7.0 have proven to be particularly advantageous. The HLB value is a measure of the "hydrophilic-lipophilic balance" in a molecule. The HLB values can be determined or calculated experimentally according to WC Griffin, ISCC 5 , 249 (1954) or JT Davis, Tenside Detergens 11 (3), 133 (1974).

The fatty alcohols which can be considered as component (V) can be saturated or unsaturated. They preferably contain 12 to 18 carbon atoms. Examples of alcohols for component (V) may be lauryl, myristyl, cetyl, stearyl, oleyl, arachidyl, behenyl alcohol or C₁₂-C₂₂ fatty alcohols.

These fatty alcohols can advantageously be mono-, di- or triethoxylated.

Preferred components (V) are cetyl alcohol or diethylene glycol cetyl ether (= polyoxyethylene (2) cetyl ether) of the formula C₁₆H₃₃-O- (CH₂CH₂O) ₂-H.

The fatty acid-alkanolamine reaction products of component (VI) are e.g. products which are produced from fatty acids with 8 to 22, preferably 8 to 18 carbon atoms and alkanolamines with 2 to 6 carbon atoms, such as ethanolamine, diethanolamine, isopropanolamine or diisopropanolamine, diethanolamine being preferred. Fatty acid diethanolamines having 8 to 18 carbon atoms are particularly preferred.

Suitable fatty acids are e.g. Caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, oleic, linoleic, linolenic, arachidonic or coconut fatty acids.

Preferred examples of such reaction products are coconut fatty acid diethanolamide and lauric acid or stearic acid diethanolamide.

worin R' Wasserstoff, Alkyl oder Alkenyl mit höchstens 18 Kohlenstoffatomen, vorzugsweise 8 bis 16 Kohlenstoffatomen, o-Phenylphenyl oder Alkylphenyl mit 4 bis 12 Kohlenstoffatomen im Alkylteil, von Z₁ und Z₂ eines Wasserstoff und das andere Methyl, y 1 bis 15 bedeuten und die Summe von n₁ + n₂ 3 bis 15 beträgt.Other highly suitable nonionic surfactants are alkylene oxide reaction products of the formula

wherein R 'is hydrogen, alkyl or alkenyl with at most 18 carbon atoms, preferably 8 to 16 carbon atoms, o-phenylphenyl or alkylphenyl with 4 to 12 carbon atoms in the alkyl part, of Z₁ and Z₂ one hydrogen and the other methyl, y is 1 to 15 and the Sum of n₁ + n₂ is 3 to 15.

Particularly advantageous nonionic surfactants are fatty alcohol polyglycol mixed ethers, in particular addition products of 3 to 10 moles of ethylene oxide and 3 to 10 moles of propylene oxide with aliphatic mono-carbon of 8 to 16 carbon atoms.

The following attachment products are examples of that
Alkylene oxide reaction products of the formula (9):
a1. Adduct of 12 moles of ethylene oxide and 12 moles of propylene oxide with 1 mole of a C₄-C₁₈ fatty alcohol,
a2. Adduct of 5 moles of ethylene oxide and 5 moles of propylene oxide with 1 mole of C₁₂-C₁₄ fatty alcohol,
a3. Adduct of 9 moles of ethylene oxide and 7 moles of propylene oxide with 1 mole of C₁₆-C₁₈ fatty alcohol,
a4. Addition product of 9.5 mol of ethylene oxide and 9.5 mol of propylene oxide with 1 mol of nonylphenol.

Combinations of components (I), (II), (III), (IV), (V) and (VI) are preferably used for component (b).

Preferred as component (a) are a non-coloring copper complex of bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic aldehydes or ketones or oximes and as component (b) combinations of components (I), (II), (III), (IV) , (V) and (VI) are used.

A copper complex compound of the formula (2) and component (b) combinations of components (I), (II), (III), (IV), (V) and (VI) are particularly preferably used as component (a).

• (1) Nonylphenol-Ethylenoxidaddukten mit 10 bis 12 Ethylenoxideinheiten, Natriumsalzen von Schwefelsäureestern von Fettalkohol-Ethylenoxidaddukten mit 8 bis 12 Kohlenstoffatomen im Alkoholteil und 2 bis 4 Ethylenoxideinheiten und Kokosfettsäurediethanolamid,
• (2) Umsetzungsprodukte von 7 bis 15 Mol Ethylenoxid an 1 Mol Stearylalkohol, Kokosfettsäurediethanolamid und Cetylakohol oder diethoxyliertem Cetylalkohol, oder
• (3) Dodecylbenzolsulfonat, Lauryltrigylkolethersulfat-Natrium, Kokosfettsäurediethanolamid und dein Dinatriumsalz der 1-Benzyl-2-stearyl-benzimidazoldisulfonsäure.

Very particularly preferred mixtures of component (b) are, for example, those of

• (1) nonylphenol-ethylene oxide adducts with 10 to 12 ethylene oxide units, sodium salts of sulfuric acid esters of fatty alcohol-ethylene oxide adducts with 8 to 12 carbon atoms in the alcohol part and 2 to 4 ethylene oxide units and coconut fatty acid diethanolamide,
• (2) reaction products of 7 to 15 moles of ethylene oxide with 1 mole of stearyl alcohol, coconut fatty acid diethanolamide and cetylic alcohol or diethoxylated cetyl alcohol, or
• (3) dodecylbenzenesulfonate, lauryltrigylcol ether sulfate sodium, coconut fatty acid diethanolamide and your disodium salt of 1-benzyl-2-stearyl-benzimidazole disulfonic acid.

Of primary interest are mixtures of a sulfuric acid ester of a fatty alcohol-ethylene oxide adduct with 8 to 18 carbon atoms in the alcohol part and 2 to 4 ethylene oxide units or its alkali metal salts and a fatty acid diethanolamide with 8 to 18 carbon atoms in the fatty acid residue.

Mixtures of lauryl triglycol ether sulfate sodium and fatty acid diethanolamide with 8 to 18 carbon atoms are of particular interest.

The compounds of component (b) are very good foaming agents, i.e. on the one hand, they can form the foam in sufficient quantity with a very small amount used, and on the other hand they can also stabilize the foam formed.

As optional component (c) of the aqueous preparation, hydrolyzed polymaleic anhydride is used, which advantageously has a molecular weight of 300 to 5000 and which is at least partially present as a water-soluble salt of such a polymaleic anhydride. Polymers of this type are suitable as complexing agents for binding the impurities present in the fiber material, such as calcium and / or magnesium salts.

Polymaleic anhydride is a homopolymer of maleic anhydride and can be hydrolyzed very easily, for example by heating with water to form a polymeric product which contains free carboxylic acid groups on a main carbon chain. The product is not a pure polymaleic acid. The exact constitution of the product is not known. Therefore, in the context of this invention, this polymeric product formed by hydrolysis of polymaleic anhydride is referred to as hydrolyzed polymaleic anhydride. This hydrolyzed polymaleic anhydride can be prepared from a polymer obtained by addition polymerization from a starting monomer consisting essentially of maleic anhydride under the conditions of bulk polymerization or by solution polymerization. Maleic anhydride is preferably polymerized in an inert organic solvent such as toluene or xylene in the presence of a polymerization catalyst, in particular a radical initiator such as benzoyl peroxide, di-tertiary-butyl peroxide or monobutyl hydroperoxide at temperatures up to 150 ° C, e.g. 120 ° to 145 ° C. The main chain of the primary polymer is essentially formed by non-hydrolyzable bonds. The primary non-hydrolyzed polymer product is then hydrolyzed with water or a water-soluble alkali after being freed from unreacted monomer and other non-polymeric types of molecules and so used. If necessary, it can also be added to the aqueous treatment baths in a non-hydrolyzed form.

During the polymerization or the subsequent hydrolysis, decarboxylation of the polymer can occur, so that the acid number of the hydrolyzed polymaleic anhydride found is lower than the theoretical value of 1143 mg KOH / g. However, such a decarboxylation does not go so far that the acid number falls below 350 mg KOH / g. The acid number can be determined by potentiometric titration in aqueous solution against 0.1N potassium hydroxide solution, graphing ΔpH: ΔV and considering the highest peak as the end point; ΔpH means the pH change, ΔV the volume change and V the titrated volume.

It is important that the molecular weight of the hydrolyzed polymaleic anhydride is in the specified low range. Polymaleic anhydride having a molecular weight which does not exceed 2000 and is preferably in the range from 350 to 1000 is preferably used.

The molecular weight of the polymaleic anhydride is generally determined arithmetically from osmometric data of the polymaleic anhydride before the hydrolysis.

Further details on the nature of the hydrolyzed polymaleic anhydride, including its preparation, are described in British Patents GB-A-1 369 429, GB-A-1 411 063 and GB-A 1 491 978 and Swiss Patent CH-A-624 256 .

By adding bases to the hydrolyzed polymaleic anhydride, their carboxyl groups are present as water-soluble salt groups when using medium-strong to strong bases. When using weak bases, the carboxyl groups are only partially present as water-soluble salts. As salt groups e.g. Alkali metal, alkyl ammonium, alkanol ammonium or ammonium salts called. The alkali metal salts include, in particular, the sodium or potassium salt and the alkylammonium or alkanolammonium salts include the trimethylammonium, monoethanolammonium, diethanolammonium or triethanolammonium salt. The sodium or ammonium salt is preferred.

As a rule, the component (c) is the salt of the hydrolyzed polymaleic anhydride of the type indicated as an aqueous, about 40 to 60 percent by weight solution.

Suitable polar organic solvents for the optional component (d) of the process according to the invention are preferably solvents soluble in water in any ratio. Component (d) serves to improve the solubility of the individual components during use. Examples of water-soluble, organic solvents are aliphatic C₁-C₄ alcohols such as methanol, ethanol or the propanols; Alkylene glycols such as ethylene glycol or propylene glycol; Monoalkyl ethers of glycols such as ethylene glycol monomethyl, ethyl or butyl ether and diethylene glycol monomethyl or ethyl ether; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol; Ethers and acetals such as diisopropyl ether, diphenyl oxide, dioxane, tetrahydrofuran, also tetrahydrofurfuryl alcohol, pyridine, acetonitrile, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, tetramethyl urea and tetramethylene sulfone. Mixtures of the solvents mentioned can also be used. Preferred are the alcohols, monoalkyl ethers of the glycols and ketones of the type mentioned, especially the ethylene glycols, e.g. Ethylene and especially propylene glycol, and diacetone alcohol.

The dyeing is carried out in the customary manner, for example using metal complex dyes or also using anthraquinone dyes or azo dyes. As metal complex dyes known types, in particular the 1: 2 chromium or 1: 2 cobalt complexes of mono- or disazo or -azomethine dyes used, which are described in large numbers in the literature. In addition to these, dyes from other classes of dyes are of course also possible, such as disperse or vat dyes.

The foam-forming mixtures can also be used for fiber materials tinted white with optical brighteners. Depending on the substrate, anionic or cationic and water-dispersible optical brighteners can be used. The optical brighteners can belong to the coumarin, oxazine, naphthalimide, stilbene, styril, pyrazine, pyrazoline, triazolyl, benzofuranyl, benzoxazolyl, bisbenzoxazolyl, thiophene bisbenzoxazolyl or benzimidazolyl series.

The foamed aqueous preparation can be prepared by simply stirring the individual components (a), (b) and, if appropriate, (c) and (d) with water.

The foamed aqueous preparation advantageously contains, based in each case on the mixture:
2 to 20 percent by weight, preferably 6 to 14 percent by weight of component (a),
0.5 to 10 percent by weight, preferably 1 to 4 percent by weight of component (b),
0 to 2 percent by weight, preferably 0 to 1 percent by weight of component (c),
0 to 5 weight percent, preferably 0 to 1.5 weight percent of component (d) and
ad 100% water.

The amounts used in which the foamed preparations are added to the treatment liquors vary, depending on the dyeing or finishing process, between 1 and 30 g, preferably between 4 and 20 g, per liter of treatment liquor. With these quantities used, the copper content per 1 g of polyamide fiber material is between 5 to 200 »g.

Synthetic polyamide, e.g. Polyamide 6, polyamide 66 or polyamide 12 understood. In addition to the pure polyamide fibers, fiber mixtures made of polyurethane and polyamide are also considered, e.g. made of polyamide / polyurethane material in a mixing ratio of 70:30. In principle, the pure or mixed polyamide material can be in a wide variety of processing forms, e.g. as fiber, yarn, fabric, pile fabric or knitted fabric.

Pole fabrics made of polyamide or polyamide / polyurethane mixtures are preferred.

The present method is particularly suitable for the treatment of polyamide material which is exposed to light and heat and e.g. used as car upholstery or carpet.

The aftertreatment and dyeing liquors can also contain conventional additives, suitably electrolytes such as salts, e.g. Sodium sulfate, ammonium sulfate, sodium or ammonium phosphates or polyphosphates, ammonium acetate or sodium acetate and / or acids such as e.g. Mineral acids, such as sulfuric acid or phosphoric acid, or organic acids, suitably contain lower aliphatic carboxylic acids, such as formic, acetic or oxalic acid. The acids serve primarily to adjust the pH of the liquors used according to the invention, which is generally 4 to 8, depending on the substrate to be treated.

Depending on the desired effect, the aftertreatment and dyeing liquors can also contain further additives or auxiliaries such as catalysts, ureas, oxidizing agents, retardants, dispersants, stabilizers or emulsifiers.

The foams are preferably produced mechanically by means of high-speed stirrers, dynamic or static mixers or also special foam pumps, with the latter also being able to produce the foams continuously.

According to the invention, degrees of foaming, i.e. Volume ratios of unfoamed to foamed preparation from 1: 6 to 1:12, preferably 1: 8 to 1:10 have been found to be suitable.

The foams used according to the invention are notable for the fact that they are stable over a long period of time and do not disintegrate immediately when applied to the substrate. The foams used according to the invention preferably have half-lives of 2 to 10 minutes. The bubble diameters in the foams are about 1 to 100 ».

The foams can be applied uniformly to the fiber materials using various application techniques. Examples of some possibilities are: sucking in, rolling up, rolling up / sucking, doctor blades with fixed knives or roller doctor blades (one or both sides), padding, blowing in, pressing in, printing, passing the textile substrate through a chamber that is continuously foam is loaded and in which the foam is under a certain pressure. Single-sided roller doctor blades, padding and pressing are preferred application techniques. The above-mentioned procedures destroy the foam structure by dewatering the foam and wetting the textile material.

The foamed preparation is generally applied at room temperature, i.e. around 15 to 30 ° C. Based on the treated fabric, the foam application is usually 10 to 100, in particular 30 to 80 percent by weight.

For the photochemical stabilization of the dyed textiles, a treatment liquor is foamed and the foam from a foam container, preferably with an adjustable doctor blade, is brought continuously to the front of the fabric via an application roller. If desired, the foam application can be repeated on the back of the fabric. When applying foam on the front and back of the fabric, intermediate drying between the application on the front and that on the back is not necessary. It is also possible to apply different treatment liquors to the front and back of the textile goods.

Another possibility of applying the foam is to pad the substrate with a padding liquor containing the foamed preparation. The impregnation is preferably carried out with a liquor absorption of 40 to 100 percent by weight.

After the foam application, the textile is dried at temperatures between 100 and 160 ° C.

In the following examples, the percentages are by weight unless otherwise specified.

0,014 % des Farbstoffes der Formel

und 0,095 % eines Farbstoffgemisches der Formeln

Nach Zugabe der Farbstoffkombination wird noch 5 Minuten bei gleicher Temperatur weiterbehandelt. Anschliessend erhöht man die Temperatur innerhalb von 45 Minuten auf 98°C. Danach färbt man noch weitere 45 Minuten bei dieser Temperatur. Example 1: 5 carpet samples with a weight of 500 g / m² are prepared. The carpets are wetted in an aqueous liquor which contains 1 to 2% of a nonionic leveling agent based on alkylamine polyglycol ether per liter in a reel runner at 20 ° C. for 5 minutes. The pH is 7. Then the following dye combination is added to the liquor:
0.22% of the dye of the formula

0.014% of the dye of the formula

and 0.095% of a dye mixture of the formulas

After adding the dye combination, the treatment is continued for 5 minutes at the same temperature. The temperature is then raised to 98 ° C. within 45 minutes. Then dye for another 45 minutes at this temperature.

The samples are removed from the dye bath and rinsed cold.

• a) 1 g/l der Zusammensetzung aus
  2,0% 50%iger NaOH
  5,0 % einer 50%igen, wässrigen Polymaleinsäure
  15,0 % Kokosfettsäurediethanolamid
  25,0 % Lauryltriglykolethersulfat
  9,0 % Diacetonalkohol und
  44 % Wasser
  sowie
• b) 16 g/l einer Zusammensetzung aus
  10,0 % des Kupferkomplexes der Formel
  
  4,3 % Natriumsulfat
  2,5 % eines Ethylenoxid/Propylenoxidblockpolymers
  10 % Mg-Al-Silikat
  0,75 % 1,2-Propylenglykol
  0,3 % eines Polysaccharids und
  81,15% Wasser

enthält, ein Schaum hergestellt, dessen Verschäumungsgrad 1:9 beträgt. Die Schaumhalbwertszeit beträgt 5 Minuten.In a foaming device, a liquor that

• a) 1 g / l of the composition
  2.0% 50% NaOH
  5.0% of a 50% aqueous polymaleic acid
  15.0% coconut fatty acid diethanolamide
  25.0% lauryl triglycol ether sulfate
  9.0% diacetone alcohol and
  44% water
  such as
• b) 16 g / l of a composition
  10.0% of the copper complex of the formula
  
  4.3% sodium sulfate
  2.5% of an ethylene oxide / propylene oxide block polymer
  10% Mg-Al silicate
  0.75% 1,2-propylene glycol
  0.3% of a polysaccharide and
  81.15% water

contains, produced a foam whose degree of foaming is 1: 9. The foam half-life is 5 minutes.

• Muster 1: Der Teppich wird nach dem Färben bei 140° getrocknet. Es erfolgt keine Nachbehandlung.
• Muster 2: Mit der Verschäumungsflotte wird das Teppichmuster auf einem Foulard bei einer Flottenaufnahme von 50 % imprägniert. Anschliessend wird bei 140°C getrocknet.
• Muster 3: Der Schaum wird mittels einer verstellbaren Rakel zur Einstellung der gewünschten Schaumdicke über eine Auftragwalze mittels einer Rutsche auf die Polseite des Teppichs kontinuierlich aufgebracht. Die Flottenaufnahme beträgt 50 %. Die Warenlaufgeschwindigkeit ist 12 m/Minute. Die Schichthöhe des Schaumes beträgt 10 mm. Der Schaumauftrag beträgt 50 %. Anschliessend wird der Teppich bei 140° getrocknet.
• Muster 4: Man verfährt wie bei Muster 3, jedoch beträgt die Flottenaufnahme 100 %.

The individual carpets are treated as follows:

• Pattern 1: The carpet is dried at 140 ° after dyeing. There is no post-treatment.
• Sample 2: The foaming liquor is used to impregnate the carpet sample on a foulard with a liquor absorption of 50%. The mixture is then dried at 140 ° C.
• Pattern 3: The foam is applied continuously by means of an adjustable squeegee to adjust the desired foam thickness via an applicator roller using a slide on the pile side of the carpet. The fleet intake is 50%. The speed of the goods is 12 m / minute. The layer height of the foam is 10 mm. The foam application is 50%. The carpet is then dried at 140 °.
• Pattern 4: The procedure is the same as for pattern 3, but the fleet absorption is 100%.

• Beispiel 2: Ein Teppichmuster (= Muster 5) mit einem Gewicht von 500 g/m² wird wie in Beispiel 1 beschrieben, genetzt, gefärbt und kalt gespült. Die Nachbehandlung erfolgt entsprechend Muster 2, mit dem Unterschied, dass 12 g/l der Zusammensetzung b) eingesetzt wird.
• Beispiel 3: Man verfahrt wie in Beispiel 2 mit dem Unterschied, dass 8 g/l der Zusammensetzung b) eingesetzt wird (= Muster 6).
• Beispiel 4: Man verfährt wie in Beispiel 2 mit dem Unterschied, dass 4 g/l der Verbindung der Zusammensetung b) eingesetzt wird. (= Muster 7).

Examples 2 to 4: In these examples, the concentration of the copper complex compound of the formula (104) is varied.

• Example 2: A carpet sample (= sample 5) with a weight of 500 g / m² is wet, dyed and rinsed cold as described in Example 1. The aftertreatment is carried out in accordance with sample 2, with the difference that 12 g / l of composition b) are used.
• Example 3: The procedure is as in Example 2, with the difference that 8 g / l of composition b) are used (= sample 6).
• Example 4: The procedure is as in Example 2, with the difference that 4 g / l of the compound of composition b) are used. (= Pattern 7).

The lightfastness of the dyed and post-treated carpets is determined in accordance with DIN 75.202 (FAKRA). The results are summarized in Table 1: Table 1 Exposure according to DIN 75 202 (FAKRA) 1 × Fakra (= 72 h) 2 × fakra (= 144 h) 3 × Fakra (= 216 h) Pattern 1 4-5 3H⁺ 2H Pattern 2 5 -5 4-5 Pattern 3 5 5 -5 Pattern 4 5 5 -5 Pattern 5 4-5 4th + 3-4 Pattern 6 4-5 4th 3-4 Pattern 7 4-5 4th -3-4

The results show that the lightfastness of the dyeings which are treated with the preparation according to the invention are significantly better than comparative dyeings without aftertreatment in accordance with sample 1.

Claims (21)

1. A process for the photochemical stabilisation of dyed polyamide textile fibre materials, which comprises treating the dyed fibre material after the dyeing process with an aqueous formulation which contains at least

   (a) a non-dyeing copper complex of bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic aldehydes or ketones or oximes, and

   (b) an anionic or nonionic surfactant or a mixture of these surfactants,

   the aqueous formulation being foamed prior to the treatment of the fibre material.
2. A process according to claim 1, wherein component (a) is a copper complex of the formula

   

   in which R is hydrogen or a substituted or unsubstituted alkyl or aryl radical, Q is a substituted or unsubstituted alkylene, cycloalkylene or arylene radical and n is 0, 1, 2 or 3.
3. A process according to one of claims 1 and 2, wherein component (a) is a bisazomethine complex of the formula

   

   in which R' is hydrogen or C₁-C₃alkyl, R₁, R₂, R₃ and R₄ are each hydrogen, halogen, hydroxyl, hydroxyalkyl, alkyl, alkoxy, alkoxyalkoxy, alkoxyalkoxyalkoxy, carboxymethoxy, alkylamino, dialkylamino, -SO₂NH₂, -SO₂NHR or -SO₂NR₂, R being alkyl or alkoxyalkyl, and alkyl or alkoxy each being understood as groups having 1-4 carbon atoms, or R₁ and R₂ or R₂ and R₃ or R₃ and R₄, together with the carbon atoms to which they are linked, form a benzene radical, and X₁ and Y₁ are each hydrogen, C₁-C₄alkyl or an aromatic radical or X₁ and Y₁ form together with the carbon atoms to which they are linked a cycloaliphatic radical of 5-7 carbon atoms.
4. A process according to claim 3, wherein a copper complex of the formula

   

   is used in which R₅ to R₈ are each and independently of each other hydrogen, hydroxyl, bromine, methyl, tert.butyl, methoxy, methoxyethoxy, ethoxyethoxyethoxy or diethylamino, X₂ is hydrogen, methyl, ethyl or phenyl and Y₂ is hydrogen or R₅ and R₆ together form a fused-on benzene ring or X₂ and Y₂ together form a cyclohexylene radical.
5. A process according to claim 4, wherein a copper complex of the formula

   

   is used in which R₉, R₁₀ and R₁₁ are each independently of one another hydrogen, chloro, bromo, methyl or methoxy, or wherein R₉ and R₁₀ together form a fused-on benzene ring, and X₃ is hydrogen, methyl, ethyl or phenyl.
6. A process according to claim 5, wherein a compound of the formula (4) is used in which R₉, R₁₀, R₁₁ and X₃ are hydrogen.
7. A process according to claim 1, wherein component (a) is a copper complex of the formula

   

   in which R₁ and R₁₂ independently of one another are hydrogen or a substituted or unsubstituted alkyl or aryl radical.
8. A process according to claim 1, wherein component (a) is a copper complex of the formula

   

   in which R₁ is as defined under the formula (5) and Z₂ is oxygen or sulfur.
9. A process according to claim 1, wherein component (a) is a copper complex of the formula

   

   in which R is hydrogen, hydroxy, alkyl or cycloalkyl, and in which the ring A is unsubstituted or further substituted.
10. A process according to claim 1, wherein component (b) is a combination of the components

    (I) acid esters or their salts of a polyadduct of 2 to 15 mol of ethylene oxide with 1 mol of a fatty alcohol containing 8 to 22 carbon atoms or with 1 mol of an alkylphenol containing 4 to 12 carbon atoms in the alkyl moiety,

    (II) alkylphenylsulfonates containing 8 to 18 carbon atoms in the alkyl moiety,

    (III) sulfonated 1-benzyl-2-alkylbenzimidazoles containing 8 to 22 carbon atoms in the alkyl moiety,

    (IV) adducts of 2 to 15 mol of ethylene oxide with 1 mol of a fatty alcohol or fatty acid, each containing 8 to 22 carbon atoms, or with 1 mol of an alkylphenol containing a total of 4 to 12 carbon atoms in the alkyl moiety,

    (V) a fatty alcohol or a mono-, di- or triethoxylated fatty alcohol containing 8 to 22 carbon atoms in the fatty alcohol radical, and

    (VI) a fatty acid dialkanolamide containing 8 to 12 carbon atoms in the fatty acid radical.
11. A process according to one of claims 1 to 10, wherein component (a) is a non-dyeing copper complex of bisazomethines, acylhydrazones, semicarbazones or thiosemicarbazones of aromatic aldehydes or ketones or oximes, and component (b) is a combination of components (I), (II), (III), (IV), (V) and (VI).
12. A process according to one of claims 1 to 10, wherein component (a) is a copper complex of the formula (2), and component (b) is a combination of components (I), (II), (III), (IV), (V) and (VI).
13. A process according to one of claims 1 to 12, wherein component (b) is a mixture of a sulfate of an adduct of a fatty alcohol and ethylene oxide containing 8 to 18 carbon atoms in the alcohol moiety and 2 to 4 ethylene oxide units, or the alkali metal salt thereof, and a fatty acid diethanolamide containing 8 to 18 carbon atoms in the fatty acid radical.
14. A process according to claim 1, wherein component (b) is a mixture of sodium lauryl triglycol ether sulfate and a fatty acid diethanolamide containing 8 to 18 carbon atoms in the fatty acid radical.
15. A process according to claim 1, wherein the foamed aqueous formulation additionally comprises
    as component (c) a salt of a hydrolysed polymaleic anhydride.
16. A process according to claim 1, wherein the foamed aqueous formulation additionally comprises
    as component (d) a polar organic solvent.
17. A process according to claim 15, wherein optional component (c) is a sodium or ammonium salt of a hydrolyzed polymaleic anhydride having a molecular weight of 300 to 5000.
18. A process according to claim 16, wherein optional component (d) is ethylene or propylene glycol and diacetone alcohol.
19. A process according to one of claims 1 to 18, wherein the foamed aqueous formulation comprises
    2 to 20 percent by weight of component (a),
    0.5 to 10 percent by weight of component (b),
    0 to 2 percent by weight of component (c),
    0 to 5 percent by weight of component (d), and
    water to make up 100%.
20. A process according to one of claims 1 to 19, wherein the foaming ratio is 1:6 to 1:12.
21. A process according to one of claims 1 to 20, which comprises applying the foamed treatment liquor continuously via an applicator roll to the dyed textile fibre material and drying the treated material after possible dewatering of the foam.