EP0030919B1 - Process for the improvement, especially dyeing, optical brightening or finishing of fibrous textile materials - Google Patents

Description

The present invention relates to the finishing, in particular the dyeing and / or finishing, of textile fiber materials with a pronounced three-dimensional character (pile or pile materials), in particular carpets, with specific, foamed aqueous preparations.

DE-A-2 722 083 discloses a process for the continuous treatment of textiles or paper with the aid of foam, in which the foam is combined with a combination of 0.2 to 5% by weight of a foaming agent and 0.001 to 5% by weight. -% of a wetting agent can be generated. Specific nonionic surface-active compounds such as ethylene oxide adducts of 10 to 50 mol of ethylene oxide with C, o-C'6 fatty alcohols or alkylphenols or also fatty acid alkanolamides and specific anionic compounds such as sulfosuccinate ester salts are described as foaming agents. Ethoxylated fatty alcohols with a degree of ethoxylation of at least 6 or else silicone wetting agents can be used as wetting agents.

From DE-A-2 715 862 a method for textile treatment with finishing agents, for. B. dyes, according to which a foam is applied as a layer to textiles, the foam contains 0.5 to 8% of a foam stabilizer and the degree of foaming is 2: 1 to 20: 1. The textiles treated in this way are then dried and subjected to a steam treatment in order to fix the finishing agent. Foam stabilizers are generally metal salts of fatty acids, e.g. As potassium stearate or ammonium stearate used, mostly in combination with a thickener such as acrylic polymers. Additional foam stabilizers are u. a. Dodecyl and fatty acids. However, silicone surfactants and thus the foam agent combination according to the present invention are not disclosed in DE-A-2 715 862.

It has now been found that using a specific foaming combination consisting of an anionic or nonionic surfactant as foam stabilizer and a foam moderator in the form of a siloxaneoxyalkylene copolymer, which is distinguished in particular by an antifoam effect in the heat and a cloud point of 20 to 70 ° C has level dyeings with improved penetration of the dyes and also an improved penetration of the textile chemicals in the pole finish can achieve.

• (a) als Schaumstabilisator 1 bis 4 g/I eines anionischen oder nichtionogenen Tensides oder einer Mischung dieser Tenside und
• (b) als Schaummoderator 0,1 bis 1 g/I eines Siloxanoxyalkylen-Copolymerisats, welches einen Trübungspunkt von 20 bis 70° C und eine Antischaumwirkung in der Wärme hat,

enthält, einen Schaum herstellt, wobei der Verschäumungsgrad 1 : (6 bis 20) beträgt, diesen Schaum auf die textilen Fasermaterialien kontinuierlich in Form mindestens einer Schicht aufbringt, die Schaumschicht gegebenenfalls, vorzugsweise jedoch teilweise, in die Fasermaterialien einsaugt und diese anschließend einer Dampfbehandlung unterwirft.The present invention accordingly relates to a process for refining, in particular for dyeing, optically brightening and / or finishing textile fiber materials, in particular carpets, with an aqueous preparation in foam form which, in addition to dye or optical brightener or finishing agent, comprises a foam stabilizer, a foam moderator and, if appropriate contains further auxiliaries, characterized in that from the aqueous preparation, the

• (a) 1 to 4 g / l of an anionic or nonionic surfactant or a mixture of these surfactants as foam stabilizer and
• (b) 0.1 to 1 g / l of a siloxaneoxyalkylene copolymer as foam moderator, which has a cloud point of 20 to 70 ° C. and an antifoam effect in the heat,

contains, produces a foam, the degree of foaming is 1: (6 to 20), applies this foam to the textile fiber materials continuously in the form of at least one layer, the foam layer is optionally, but preferably partially, sucked into the fiber materials and then subjected to steam treatment .

The substrates to be treated according to the invention can be made of all conventional natural and / or synthetic fiber materials, such as. B. from cotton, regenerated cellulose, polyester, polyacrylonitrile, polyamide (6 or 6.6), wool or mixtures thereof. Pile materials and especially carpets (e.g. loop or velor carpets with a carpet weight of up to 2500 g / m ² ) made of polyacrylonitrile, wool or in particular of polyamide are preferred.

For the dyeing according to the invention, all customary classes of dyes come into consideration, e.g. B. disperse, vat, reactive, substantive, acid, basic or MetaHkomptex dyes as well as corresponding, in practice, mixtures of such dyes. Examples of dyes are described in Color Index, 3rd edition 1971, volume 4.

If textile substrates are optically lightened using the process according to the invention, optical brighteners such as. B. those of the styryl or stilbene series in question.

All chemicals suitable for use in the carpet industry, such as finishing and protective agents, are suitable as finishing agents which can be applied according to the invention. For example, antistatic, antisoil or soil releasing agents can be applied.

Components (a) and (b) of the preparations used according to the invention are the actual foaming agents (foam stabilizers, foam moderator).

The weight ratio of components (a) and (b) to one another is (2 to 40): 1.

Anionic or nonionic compounds with surface-active properties are generally suitable as foam stabilizers [component (a)].

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

These anionic surfactants are prepared by known methods by adding at least 1 mol, preferably more than 1 mol, for. B. 2 to 60 moles of ethylene oxide or propylene oxide or alternately in any order ethylene oxide and propylene oxide and then etherified or esterified the addition products and optionally converted the ether or ester into their salts. The base materials are higher fatty alcohols, i.e. H. Alkanols or alkenols, each with 8 to 22 carbon atoms, di- to hexavalent aliphatic alcohols with 2 to 9 carbon atoms, alicyclic alcohols, phenylphenols, benzylphenols, alkylphenols with one or more alkyl substituents, which together have at least 4 carbon atoms, fatty acids with 8 up to 22 carbon atoms, amines which have aliphatic and / or cycloaliphatic hydrocarbon radicals of at least 8 carbon atoms, in particular fatty amines containing such radicals, 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 Fettsäureniederalkylester, die im Fettrest 8 bis 20 Kohlenstoffatome aufweisen, z. B. Rizinolsäure und solche Fettsäuren enthaltende Öle, 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;
• - Sulfonate von Polycarbonsäureestern, z. B. Dioctylsulfosuccinate oder Sulfosuccinamide;
• - 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 Ölsäure, 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 Äthylenoxyd und/oder Propylenoxyd 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:

• - Sulphated aliphatic alcohols, the alkyl chain of which has 8 to 18 carbon atoms, e.g. B. sulfated lauryl alcohol;
• - Sulphated unsaturated fatty acids or fatty acid lower alkyl esters which have 8 to 20 carbon atoms in the fat residue, e.g. B. ricinoleic acid and oils containing such fatty acids, e.g. B. castor oil;
• - Alkyl sulfonates whose alkyl chain contains 8 to 20 carbon atoms, e.g. B. dodecyl sulfonate;
• - Alkylarylsulfonate with a straight-chain or branched alkyl chain with at least 6 carbon atoms, e.g. B. dodecylbenzenesulfonates or 3,7-diisobutyl-naphthalenesulfonates;
• - Sulfonates of polycarboxylic acid esters, e.g. B. dioctyl sulfosuccinates or sulfosuccinamides;
• - The so-called alkali metal, ammonium or amine salts of fatty acids with 10 to 20 carbon atoms, e.g. B. rosin salts;
• - Esters of polyalcohols, especially mono- or diglycerides of fatty acids with 12 to 18 carbon atoms, e.g. B. monoglycerides of lauric, stearic or oleic acid, and
• - Which with an organic dicarboxylic acid, such as. B. maleic acid, malonic acid or sulfosuccinic acid, but preferably with an inorganic polybasic acid such as o-phosphoric acid or especially sulfuric acid, adducts converted from 1 to 60 ethylene oxide and / or propylene oxide onto fatty amines, fatty acids or fatty alcohols, each with 8 to, converted into an acidic ester 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.

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

wobei die Komponenten (1), (2) und (3) einzeln oder als Gemisch verwendet werden können.Anionic surfactants which are highly suitable as foam stabilizers for component (a) are

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

components (1), (2) and (3) can be used individually or as a mixture.

oder die Formel

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 organischen Säure, p 4 bis 12 und z 2 bis 12 sind.Component (1) of the preferred foam stabilizers mentioned can, for. B. by the formula

or the formula

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 organic acid, p 4 to 12 and z 2 to 12.

The alkyl radicals on the benzene ring of formula (1) 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, in particular the octyl and nonyl radicals, are preferred.

The acid residue X is derived for example from low molecular weight dicarboxylic acids, such as. B. from 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, ie, for example, 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 (1) of formula (2) are, for. B. those having 8 to 22, especially 8 to 18 carbon atoms, such as octyl, decyl, lauryl, tridecyl, myristyl, cetyl, 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 (1). A preferred compound among the foam stabilizers of formula (2) is the sodium salt of lauryl triglycol ether sulfonic acid.

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

The following compounds are mentioned in particular for components (1) of the formulas (1) and (2):

• 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-nonylphenol;
• 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 acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of alfol (1014);
• 12. ammonium salt of the acidic 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 acidic 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 acidic 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 and 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 and 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 and 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 (2) 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. As alkyl radicals come e.g. B. n-octyl, tert-octyl, n-nonyl, tert-nonyl, n-decyl, n-dodecyl, tridecyl, myristyl, cetyl, stearyl or oleyl in question. Alkyl radicals having 8 to 12 carbon atoms are preferred, with dodecylbenzenesulfonate (sodium salt) being particularly suitable.

Component (3) is a sulfonated l-benzyi-2-aikyibenzimidazo) with 8 to 12 carbon atoms in the alkyl part. The alkyl radicals are derived from the acid esters mentioned above.

Of the sulfonated benzimidazole derivatives which can be obtained by condensing o-phenylenediamine with saturated or unsaturated fatty acids having 12 to 18, preferably 16 to 18 carbon atoms (palmitic, stearic, oleic acid), those having 2 sulfonic acid groups are preferred.

The disodium salt of 1-benzyl-2-heptadecylbenzimidazole disulfonic acid may be mentioned as the preferred compound.

Components (1) to (3) can be used alone or as mixtures with one another as foam stabilizers.

The nonionic surfactant according to component (a) is advantageously a nonionic alkylene oxide addition product of 1 to 100 moles of alkylene oxide, e.g. B. ethylene oxide and / or propylene oxide, on 1 mole of an aliphatic monoalcohol with at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol, an optionally substituted by alkyl or phenyl or a fatty acid with 8 to 22 carbon atoms.

The aliphatic monoalcohols for the production of the nonionic surfactants are e.g. B. water-insoluble monoalcohols having 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. B. 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 the abovementioned alfoles 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, such as. B. the capric, lauric, myristic, palmitic or stearic acid or the decenic, dodecenic, tetradecenic, hexadecenic, oleic, linoleic, linolenic or preferably ricinoleic acid.

• - Anlagerungsprodukte von vorzugsweise 5 bis 80 Mol Alkylenoxyden, insbesondere Äthylenoxyd, wobei einzelne Äthylenoxydeinheiten durch substituierte Epoxyde, wie Styroloxyd und/oder Propylenoxyd, 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;
• - Alkylenoxyd-, insbesondere Äthylenoxyd- und/oder Propylenoxyd-Kondensationsprodukte;
• - Umsetzungsprodukte aus einer 8 bis 22 Kohlenstoffatome aufweisenden Fettsäure und einem primären oder sekundären, mindestens eine Hydroxyniederalkyl- oder Niederalkoxyniederalkylgruppe aufweisenden Amin oder Alkylenoxyd-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 Propylenoxyd an einen drei- bis sechswertigen aliphatischen Alkohol von 3 bis 6 Kohlenstoffatomen, z. B. Glycerin oder Pentaerythrit, wobei die Polypropylenoxydaddukte 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, it being possible for individual ethylene oxide units to 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, the alkyl radicals of which have at least 4 carbon atoms;
• - Alkylene oxide, especially ethylene oxide and / or propylene oxide condensation products;
• - Reaction products from a fatty acid having 8 to 22 carbon atoms and a primary or secondary amine or alkylene oxide addition products containing these hydroxyalkyl group-containing reaction products, which have at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, the reaction taking place in such a way that the molecular quantitative ratio between hydroxyalkylamine and fatty acid is 1: 1 and greater than 1, e.g. B. 1.1: 1 to 2: 1, and
• - Adducts of propylene oxide with a trihydric to hexavalent aliphatic alcohol of 3 to 6 carbon atoms, e.g. As glycerol or pentaerythritol, the polypropylene oxide adducts having an average molecular weight of 250 to 1800, preferably 400 to 900.

• (4) Anlagerungsprodukte von 2 bis 15 Mol Äthylenoxyd 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,
• (5) gegebenenfalls mono-, di- oder triäthoxylierte Fettalkohole mit 8 bis 22 Kohlenstoffatomen im Fettalkoholrest oder

Non-ionic surfactants which are highly suitable as foam stabilizers of component (a) are

• (4) 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,
• (5) optionally mono-, di- or tri-ethoxylated fatty alcohols with 8 to 22 carbon atoms in the fatty alcohol radical or

(6) Fatty acid dialkanolamides with 8 to 22 carbon atoms in the fatty acid residue.

dargestellt werden können, worin n 8 oder 9 und z 2 bis 12 ist. Die Alkylsubstituenten am Phenolring können geradkettig oder verzweigt sein.Suitable components (4) of the foam stabilizers are advantageously octyl or preferably nonylphenol-ethylene oxide adducts with 2 to 12 ethylene oxide units, in particular by the formula

can be represented, wherein n is 8 or 9 and z is 2 to 12. The alkyl substituents on the phenol ring can be straight-chain or branched.

The following octyl and nonylphenol reaction products may be mentioned in particular: p-nonylphenol / 9 mol of ethylene oxide, p-octylphenol / 2 mol of ethylene oxide, p-nonylphenol / 10 mol of ethylene oxide, p-nonylphenol / 11 mol of ethylene oxide.

Other alkylphenol-ethylene oxide adducts can be found e.g. B. derived from butylphenol or tributylphenol.

Component (4) 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. B. lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, or synthetic alcohols, such as in particular 2-ethylhexanol, also trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or the C ₁₂ -C ₂₂ -alcohols can be reacted with ethylene oxide.

Ethylene oxide addition products of 2 to 15 moles of ethylene oxide and 1 mole of fatty acid can also be used as component (4). The fatty acids preferably have 10 to 20 carbon atoms and can be saturated or unsaturated, such as. B. the capric, lauric, myristic, palmitic or stearic acid or the decenic, dodecenic, tetradecenic, hexadecenic, oleic, linoleic or ricinoleic acid.

Component (5) is, by definition, an optionally ethoxylated fatty alcohol, the HLB value of which is expediently from 0.1 to 10, in particular from 0.5 to 10. Components (5) 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 W.C. Griffin, ISCC 5, 249 (1954) or J. T. Davis, Tenside Detergens 11 (1974), No. 3, p. 133.

The fatty alcohols which can be considered as component (5) can be saturated or unsaturated. They preferably contain 12 to 18 carbon atoms. Examples of alcohols for component (5) are lauryl, myristyl, cetyl, stearyl, oleyl, arachidyl, behenyl alcohol or C ₁₂ -C ₂₂ alfols.

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

Preferred components (5) are cetyl alcohol or diethylene glycol cetyl ether (= polyoxyethylene (2) cetyl ether) of the formula

The fatty acid-alkanolamine reaction products of component (6) are, for. B. to products which are made of 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 di-isopropanolamine, diethanolamine being preferred. Fatty acid diethanolamides having 8 to 18 carbon atoms are particularly preferred.

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

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, y1 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 Z ₁ and Z _{2 of} a hydrogen and the other is methyl, y1 to 15 and the sum of n ₁ , + n _{2 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 monoalcohols of 8 to 16 carbon atoms.

• 1. Anlagerungsprodukt von 12 Mol Äthylenoxyd und 12 Mol Propylenoxyd an 1 Mol eines C₄-C₁₈-Fettalkohols,
• 2. Anlagerungsprodukt von 5 Mol Äthylenoxyd und 5 Mol Propylenoxyd an 1 Mol Alfol (12 -14),
• 3. Anlagerungsprodukt von 9 Mol Äthylenoxyd und 7 Mol Propylenoxyd an 1 Mol C₁₆-C₁₈-Fettalkohol,
• 4. Anlagerungsprodukt von 9,5 Mol Äthylenoxyd und 9,5 Mol Propylenoxyd an 1 Mol Nonylphenol.

The following addition products are examples of the alkylene oxide reaction products of the formula (4):

• 1. adduct of 12 moles of ethylene oxide and 12 moles of propylene oxide with 1 mole of a C ₄ -C ₁₈ fatty alcohol,
• 2. adduct of 5 moles of ethylene oxide and 5 moles of propylene oxide with 1 mole of alfol (12-14),
• 3. adduct of 9 moles of ethylene oxide and 7 moles of propylene oxide with 1 mole of C ₁₆ -C ₁₈ fatty alcohol,
• 4. Addition product of 9.5 mol of ethylene oxide and 9.5 mol of propylene oxide with 1 mol of nonylphenol.

Preferred foam stabilizers for component (a) are combinations of components (1), (2), (4), (5) and (6) and optionally also of component (3). Components (1), (2), (4), (5) and (6) can advantageously also be used alone as foam stabilizers.

Preferred individual components are the reaction product from 1 mol of nonylphenol and 2 mol of ethylene oxide, the ammonium salt of the acidic sulfuric acid ester of the reaction product from 1 mol of nonylphenol and 2 mol of ethylene oxide, sodium dodecylphenylsulfonate or a fatty acid diethyl ethylenol amide with 8-fatty acid diethyl ether amide ).

• (1) Nonylphenol-Äthylenoxydaddukten mit 10 bis 12 Äthylenoxydeinheiten, Natriumsalzen von Schwefelsäureestern von Fettalkohol-Äthylenaddukten mit 10 bis 12 Kohlenstoffatomen im Alkoholteil und 2 bis 4 Alkylenoxydeinheiten und Kokosfettsäurediäthanolamid,
• (2) Umsetzungsprodukte von 7 bis 15 Mol Äthylenoxyd an 1 Mol Stearylalkohol, Kokosfettsäurediäthanolamid und Cetylalkohol oder diäthoxyliertem Cetylalkohol,
• (3) Dodecylbenzolsulfonat, Lauryltriglykoläthersulfat-NatFium, Kokosfettsäurediäthanolamid und dem Dinatriumsalz der 1-Benzyl-2-stearyl-benzimidazoldisulfonsäure oder
• (4) Lauryltriglykoläthersulfat-Natrium und Fettsäurediäthanolamide mit 8 bis 18 Kohlenstoffatomen im Fettsäurerest.

Preferred mixtures of foam stabilizers are e.g. B. from

• (1) nonylphenol-ethylene oxide adducts with 10 to 12 ethylene oxide units, sodium salts of sulfuric acid esters of fatty alcohol-ethylene adducts with 10 to 12 carbon atoms in the alcohol part and 2 to 4 alkylene oxide units and coconut fatty acid diethanolamide,
• (2) reaction products of 7 to 15 mol of ethylene oxide with 1 mol of stearyl alcohol, coconut fatty acid diethanolamide and cetyl alcohol or diethoxylated cetyl alcohol,
• (3) dodecylbenzenesulfonate, lauryl triglycol ether sulfate NatFium, coconut fatty acid diethanolamide and the disodium salt of 1-benzyl-2-stearyl-benzimidazole disulfonic acid or
• (4) Lauryl triglycol ether sulfate sodium and fatty acid diethanolamides with 8 to 18 carbon atoms in the fatty acid residue.

The foam components or foam stabilizers (a) are very good foaming agents, i.e. that is, on the one hand they can form the foam in sufficient quantity with a very small amount of use and on the other hand they can also stabilize the foam formed.

The siloxaneoxyalkylene copolymers used as foam moderators [component (b)] are, for. B. reaction products from halogen-substituted organopolysiloxanes and alkali metal salts of polyoxyalkylene, for. B. polyethylene or polypropylene glycols.

dargestellt werden, worin q 3 bis 50, zweckmäßigerweise 3 bis 25, r 2 oder 3, s 0 bis 15, t 1 bis 25, x 3 bis 15, vorzugsweise 3 bis 10, und R, Alkyl mit 1 bis 6 Kohlenstoffatomen, vorzugsweise Methyl, istSuch compounds which have a polydimethylsiloxane skeleton can be represented by the formula

are represented, in which q 3 to 50, advantageously 3 to 25, r 2 or 3, s 0 to 15, t 1 to 25, x 3 to 15, preferably 3 to 10, and R, alkyl having 1 to 6 carbon atoms, preferably Is methyl

Such connections are e.g. B. described in DE-AS 1 719 328.

Representatives of the siloxaneoxyalkylene copolymers of the formula (5) can be described by the following formulas:

worin R₂ und R₃ je Alkyl mit 1 bis 4 Kohlenstoffatomen, vorzugsweise Methyl, a 1 bis 20, b 2 bis 20, c 2 bis 50, d 1 oder 2 und m 2 bis 5 bedeuten.Further polyether siloxanes which can be used as foam moderators in accordance with component (b) correspond to the formula

wherein R ₂ and R _{3 are} each alkyl with 1 to 4 carbon atoms, preferably methyl, a 1 to 20, b 2 to 20, c 2 to 50, d 1 or 2 and m 2 to 5.

Such siloxane compounds are described in DE-AS 1 795 557.

Typical representatives of these siloxane-polyalkylene oxide polymers are:

Preferred polyether siloxanes used as foam moderators in accordance with component (b) have a cloud point of about 20 to 70 ° C., preferably 25 to 50 ° C. The glycol content, consisting of oxyethylene groups or oxyethylene and oxypropylene groups, is advantageously from 35 to 80, preferably from 40 to 70 percent by weight, based on the total weight of the polyether siloxane.

Component (b) does not interfere with the production of the foam, but has the property of destroying the foam when exposed to moisture and heat, i.e. H. to disintegrate. This effect is based on the property of these components to have a cloud point, in particular at 40-50 ° C., in aqueous solution, ie. that is, these products have an anti-foaming effect in heat.

Depending on the desired effect, the foams to be used according to the invention may also contain further additives, such as acids, alkalis, catalysts, urea, oxidizing agents, solvents or emulsifiers. The acids and the alkalis serve primarily to adjust the pH of the liquor used according to the invention, which is generally 4 to 10, depending on the substrate to be treated.

The addition of a thickener is not necessary since the foams are sufficiently stable even without a thickener, i.e. H. Foam half-lives can have up to 60 minutes. Their penetration properties are good; wetting and easy penetration of the foam is guaranteed.

In the production of the foams, the procedure is expediently such that the foaming components (a) and (b) are first dissolved separately and then mixed with one another and thus lead to aqueous solutions of 0.1 to 0.5 percent by weight of foaming components.

The foams are preferably produced mechanically using high-speed stirrers, mixers or special foam pumps, the latter also being able to produce the foams continuously. It has proven to be expedient to predissolve or predisperse the individual components before they are fed to the foaming apparatus.

According to the invention, degrees of foaming, i. H. Volume ratios of unfoamed to foamed preparation from 1: 6 to 1:20, preferably 1: 8 to 1:12, 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 immediately disintegrate (drain) when applied to the substrate. The foams used according to the invention preferably have half-lives of 5 to 30 minutes. The bubble diameters in the foams are approximately 1 to 100 µ.

The foams are generally applied at room temperature, i. H. about 15 to 30 ° C.

For the dyeing or finishing of carpets and pile fabrics made of polyamide, wool, polyacrylonitrile or polyester, a treatment liquor is foamed and the foam from a foam container (with an adjustable squeegee for setting the desired foam layer thickness) is applied to the pile using an application roller with a squeegee . The substrates do not necessarily have to be pretreated, but can also be prewetted at room temperature (with aqueous liquors of conventional wetting agents, e.g. 1 g / l liquor of an alkylphenol-ethylene oxide adduct) or prewashed at temperatures up to 80 ° C (with conventional detergents ) and be pre-bagged. If these pretreatments are carried out, it is appropriate to apply a residual moisture content of 40 to 100 percent by weight, preferably 40 to 50, to the substrates before the foam application Weight percent, based on the substrate weight, to drain. By applying a vacuum to the back of the substrates (approx. 0.1 bar negative pressure), the foam layer is partially sucked into the substrate (the carpet pile) without loss of liquor. The foam height can be reduced by about 10 to 70% of the original height. This distributes the foam evenly from the pile tips to almost the pile foot. A second foam layer can then optionally be applied using a doctor blade. The total liquor application, based on the weight of the dry carpet, is advantageously between 70 and 250%, preferably 70 to 200 and in particular 120 to 170%. This process also makes it possible to dye polyamide carpet pile material that can be dyed differently and to obtain a good differential dyeing effect.

The vacuum to be selected essentially depends on the weight per square meter of the carpet, the construction of the backing material, the density of the carpet, the length of the pile material and also on the degree of foaming of the foam. In the range of> 0-1 bar vacuum, the foam blanket can be partially sucked into the carpet by drainage. It is important that the foam layer remaining on the pile side remains as thick as possible. Excessive vacuuming leads to loss of liquor and can lead to uneven dyeing or dyeing with a frosting effect (gray haze).

The carpet now runs into the damper with a foam blanket still on the pole side. When entering the damper, the foam blanket begins to foam slightly, this prevents the formation of gray fog; then the foam - with the help of the foam moderator = component (b) - is evenly destroyed by the action of saturated steam, d. H. it drains, the liquor penetrates further into the pile material, so that a level frosting-free coloring results. The foam must be completely destroyed after <20 seconds in order to achieve good surface levelness.

Before the foam is applied, the substrate can advantageously be pre-fouled with a padding liquor which preferably contains foaming agents, in particular components (a) and (b). The impregnation is preferably carried out with a liquor absorption of 40 to 100 percent by weight. The subsequent foam application is usually 50 to 180 percent by weight, preferably 50 to 150 percent by weight. After pre-fouling the substrate with an impregnating liquor, which may already contain a foaming agent, and then applying the foam, one can successfully dispense with sucking the foam into the textile material and carry out the steam treatment directly.

The dyes and finishing agents are fixed by steaming the substrate, e.g. B. at temperatures of 95 to 180 ° C, preferably by steaming at 98 to 102 ° C, z. B. with saturated steam or superheated steam.

After fixing it can be washed out as usual (wash off with water), rinsed and dried, e.g. B. at temperatures from 100 to 30 ° C. Equipment only drying and fixing.

The method according to the invention offers very significant advantages over known methods.

Since in foam dyeing low moisture over the conventional continuous process, wherein the amount of the dye liquor, based on the carpet material, up to 500% by weight, is applied, and only _{^1/3 of} the order is carried out are, higher production rates possible. In addition, there is a better development of the bulk, which leads to an increase in quality. Furthermore, the longitudinal streak is avoided with polyamide velor qualities.

As a result of the small amounts of liquid, the wastewater will only have a slight impact on the operation, which is valuable from an ecological point of view. The saving in water and energy is also an advantageous consequence of the present invention and no loss of paint liquor in the damper.

= Mischung aus (16)

und Farbstoff der Formel (10)

= Mischung aus (25)

und

The dyes / optical brighteners used in the examples below correspond to the formulas:

= Mixture of (16)

and dye of formula (10)

= Mixture of (25)

and

Optical brighteners

In the examples below, parts and percentages are by weight.

example 1

500 m ^{2 of} a polyamide (6.6) cut pile carpet (velor with polypropylene tape back) with a square meter weight of 535 g are continuously pre-wetted in a liquor which contains 1 g of the reaction product of 1 mol of nonylphenol and 9 mol of ethylene oxide per liter and then on a liquor absorption aspirated from 40 weight percent.

In a foaming device (mixer), a color foam is produced from the following aqueous liquor, the degree of foaming of which is 1:10:

This foam is then applied from a foam container, which has an adjustable doctor blade for setting the desired foam thickness, via an applicator roller by means of a slide to the pole side of the carpet running through the dyeing system (running speed 9 m / minute). The layer height of the foam is 8 mm. The color foam application is 135%.

The carpet then goes through a vacuum passage, in which the foam layer is partially sucked into the carpet from the back (negative pressure of '-0.1 bar), which reduces the height of the foam layer somewhat. The carpet then runs over a transport roller into a damper (102 ° C, saturated steam), where a slight foaming takes place and then the foam is destroyed. The carpet is then sprayed with water at about 80 ° C., then suctioned off and dried at 100 to 30 ° C. on a sieve drum dryer.

The carpet material obtained is irrelevant, dyed in a beige color, shows excellent through-coloring, the softness and bulkiness of the material is positively influenced by the foam coloring.

Other foam stabilizer mixtures which can also be used with good success are those composed of dodecylbenzenesulfonate, coconut fatty acid ethanolamide, lauryl triglycol ether sulfate sodium and the disodium salt of 1-benzyl-2-stearylbenzimidazole disulfonic acid (0.5 / 1/1/1); a mixture of lauric acid diethanolamide and lauryl triglycol ether sulfate sodium (1/1) and the compounds dodecylbenzenesulfonate (sodium salt), coconut fatty acid diethanolamide, lauryl triglycol ether sulfate sodium, the adduct of 1 mole of nonylphenol and 9 moles of ethylene oxide and the non-phenylene oxide of the ammonium oxide of the non-phenylene oxide of the adduct of 2 moles of ethylene oxide and the moles of ethylene oxide of the non-ammonium oxide of the ammonium oxide or the mole of ethylene oxide of the adduct of ammonium oxide or the mole of ethylene oxide of the adduct of ammonium oxide or the mole of ethylene oxide of the adduct of ammonium oxide or the mole of ethylene oxide of the adduct or the mole of ethylene oxide of the adduct of ammonium oxide or the mole of ethylene oxide of the adduct or the mole of ethylene oxide of the adduct of the ammonium oxide or the mole of ethylene oxide of the adduct of ammonium oxide or the mole of ethylene oxide of the additive or ammonium oxide of the adduct.

The compounds of the formulas (7) to (15) or mixtures thereof can also be used as the foam moderator.

Example 2

sowie eine Natriumhydroxydlösung (30° Be) zur Einstellung der Flotte auf einen pH-Wert von 8.A polyamide (6) carpet with a square meter weight of 2000 g is impregnated on a foulard with the following liquor with a liquor absorption of 70%:

and a sodium hydroxide solution (30 ° Be) to adjust the liquor to a pH of 8.

The following liquor is then foamed and applied in the same manner as described in Example 1:

The degree of foaming is 1: 8.

This foam is applied to the pile side of the carpet which has already been impregnated, the foam application being 70%, based on the weight of the dry carpet. The carpet is then treated in a horizontal steamer at 98 ° C. with saturated steam for 4 minutes, then rinsed and dried. A beige coloration is obtained with excellent light and wet fastness properties.

Example 3

A polyamide (6.6) cut pile carpet with a weight of 610 g per square meter is continuously pre-wetted in a liquor which contains 1 g of the adduct of 9 mol of ethylene oxide with 1 mol of nonylphenol per liter and is suctioned off to a liquor absorption of 50% by weight.

In a foaming device, a colored foam is produced from the following aqueous liquor, the degree of foaming of which is 1: 9:

This foam is then applied to the pile side of the carpet in the same manner as described in Example 1, the foam application being 160%, based on the weight of the dry carpet. Then, the carpet is treated in a horizontal steamer at 98 ° C with saturated steam for 4 _^1/2 minutes, then rinsed and dried.

A streak-free, level, green color is obtained with excellent light and wet fastness properties.

Example 4

A polyamide (6.6) cut pile carpet with a weight of 2300 g is impregnated on a foulard with the following liquor with a liquor absorption of 100%:

The following liquor is then foamed and applied in the same manner as described in Example 1:

The degree of foaming is 1: 8.

This foam is applied to the pile side of the carpet which has already been impregnated, the foam application being 100%, based on the weight of the dry carpet. The carpet is then treated in a steamer at 98-100 ° C. with saturated steam for 6 minutes, the foam on the surface of the carpet disintegrating after only 12 seconds. After rinsing and drying you get a level, streak-free, golden yellow color with excellent light and wet fastness properties.

Example 5

A polyamide (6.6) cut pile carpet with a square meter weight of 1750 g is impregnated on a foulard with the following liquor with a liquor absorption of 100%:

The following liquor is then foamed and applied in the same manner as described in Example 1:

The degree of foaming is 1: 8.

This foam is applied to the pile side of the carpet which has already been impregnated, the foam application being 100%, based on the weight of the dry carpet. Then, the carpet is treated in a steamer at 100 ° C with saturated steam for 5 _^1/2 minutes, then rinsed and dried. You get a level, streak-free, green color with excellent light and wet fastness.

Example 6

• 1 g/I Natriumazetat

sowie Essigsäure zur Einstellung der Flotte auf einen pH-Wert von 6,0.A polyamide (6.6) cut pile carpet with a weight of 1885 g is impregnated on a foulard with the following liquor with a liquor absorption of 40%:

• 1 g / l sodium acetate

and acetic acid to adjust the liquor to a pH of 6.0.

The following liquor is then foamed and applied in the same manner as described in Example 1:

The degree of foaming is 1: 9.

This foam is applied to the pile side of the carpet which has already been impregnated, the foam application being 80%, based on the weight of the dry carpet. The carpet is then treated in a steamer at 98-100 ° C. with saturated steam for 6 minutes, then rinsed and dried. You get a level, brown color with excellent light and wet fastness.

Example 7

A polyamide (6.6) cut pile carpet with a square meter weight of 580 g is impregnated on a foulard with the following liquor with a liquor absorption of 100%:

The following liquor is then foamed and applied in the same manner as described in Example 1:

The degree of foaming is 1: 8.

This foam is applied to the pile side of the carpet which has already been impregnated, the foam application being 140%, based on the weight of the dry carpet. Then, the carpet is treated in a steamer at 100 ° C with saturated steam for 5 _^1/2 minutes, then rinsed and dried. You get a level, brown color with excellent light and wet fastness.

Example 8

A polyamide (6.6) cut pile carpet with a weight of 720 g per square meter is continuously pre-wetted in a liquor which contains 1 g of the adduct of 9 mol of ethylene oxide with 1 mol of nonylphenol per liter and is suctioned off to a liquor absorption of 50% by weight.

In a foaming device, a colored foam is produced from the following aqueous liquor, the degree of foaming of which is 1: 9:

This foam is then applied to the pile side of the carpet in the same manner as described in Example 1, the foam application being 160%, based on the weight of the dry carpet. The carpet is then treated in a horizontal steamer at 100 ° C. with saturated steam for 4 minutes, then rinsed and dried.

A streak-free, level, golden yellow color is obtained with excellent light and wet fastness properties.

Example 9

A polyamide (6.6) cut pile carpet with a square meter weight of 600 g is continuously pre-wetted in a liquor which contains 1 g of the adduct of 9 mol of ethylene oxide with 1 mol of nonylphenol per liter and is suctioned off to a liquor absorption of 50% by weight.

In a foaming device, a colored foam is produced from the following aqueous liquor, the degree of foaming of which is 1: 8:

This foam is then applied to the pile side of the carpet in the same manner as described in Example 1, the foam application being 180%, based on the weight of the dry carpet. The carpet is then treated in a horizontal steamer at 100 ° C. with saturated steam for 4 minutes, then rinsed and dried.

A streak-free, level, beige color with excellent light and wet fastness properties is obtained.

Example 10

A polyamide (6.6) cut pile carpet with a weight of 720 g per square meter is continuously pre-wetted in a liquor which contains 1 g of the adduct of 9 mol of ethylene oxide with 1 mol of nonylphenol per liter and is suctioned off to a liquor absorption of 50% by weight.

In a foaming device, a colored foam is produced from the following aqueous liquor, the degree of foaming of which is 1: 8:

This foam is then applied to the pile side of the carpet in the same manner as described in Example 1, the foam application being 150%, based on the weight of the dry carpet. Then, the carpet is treated in a horizontal steamer at 100 ° C with saturated steam for 4 _^1/2 min followed by rinsing and drying.

A streak-free, level, green color is obtained with excellent light and wet fastness properties.

In Examples 2 to 10, the polyether siloxanes of the formulas (7) to (15) can also be used as foam moderators.

Claims (27)

1. A method of treating, especially dyeing, whitening and/or finishing, textile fabrics with an aqueous foam composition which, in addition to containing dye or fluorescent whitening agent and/or finishing agent, contains a foam stabiliser, a foam regulator, and optionally other assistants, which method comprises preparing a foam from an aqueous composition which contains

(a) 1 to 4 g/litre of an anionic or non-ionic surfactant, or a mixture thereof, as foam stabiliser, and

(b) 0.1 to 1 g/litre of an oxyalkylene-siloxane copolymer as foam regulator which has a cloud point of 20° to 70° C an antifoam properties at elevated temperature,

said foam having a blow ratio of 1 : (6 to 20), applying said foam continuously, in the form of at least one layer, to the textile fabric, if desired vacuuming said fabric to effect penetration of the layer of foam through the fabric, and subsequently subjecting the fabric to a steam treatment.

2. A method according to claim 1, wherein the anionic surfactant is

(1) an acid ester, or salt thereof, of a polyadduct of 2 to 15 moles of ethylene oxide and 1 mole of a fatty alcohol containing 8 to 22 carbon atoms or 1 mole of an alkylphenol containing 4 to 12 carbon atoms in the alkyl moiety,

(2) an alkylphenylsulfonate containing 8 to 18 carbon atoms in the alkyl moiety, or

(3) a sulfonated 1-benzyl-2-alkylbenzimidazole containing 8 to 22 carbon atoms in the alkyl moiety,

which components (1), (2) and (3) are used individually or in admixture.

3. A method according to either of claims 1 or 2, wherein the non-ionic surfactant is

(4) a polyadduct of 2 to 15 moles of ethylene oxide and 1 mole of a fatty alcohol or fatty acid, each containing 8 to 22 carbon atoms, or 1 mole of an alkylphenol containing a total of 4 to 12 carbon atoms in the alkyl moiety,

(5) a fatty alcohol which can be mono-, di- or triethoxylated and which contains 8 to 22 carbon atoms in the fatty alcohol radical, or

(6) a fatty acid dialkanolamide containing 8 to 22 carbon atoms in the fatty acid radical,

which components (4), (5) and (6) are used individually or in admixture.

4. A method according to either of claims 1 to 3, wherein the foam stabiliser (a) is

(1) an acid ester, or a salt thereof, of a polyadduct of 2 to 15 moles of ethylene oxide and 1 mole of a fatty alcohol containing 8 to 22 carbon atoms or 1 mole of an alkylphenol containing 4 to 12 carbon atoms in the alkyl moiety,

(2) an alkylphenylsulfonate containing 8 to 18 carbon atoms in the fatty acid radical,

(4) a polyadduct of 2 to 15 moles of ethylene oxide and 1 mole of a fatty alcohol or fatty acid, each containing 8 to 22 carbon atoms, or 1 mole of an alkylphenol containing a total of 4 to 12 carbon atoms in the alkyl moiety,

(5) a fatty alcohol which can be mono-, di- or triethoxylated and which contains 8 to 22 carbon atoms in the fatty alcohol radical, and

(6) a fatty acid dialkanolamide containing 8 to 12 carbon atoms in the fatty acid radical and, optionally,

(3) a sulfonated 1-benzyl-2-alkylbenzimidazole containing 8 to 22 carbon atoms in the alkyl moiety.

5. A method according to claim 4, wherein the foam stabiliser (a) is a nonylphenol/ethylene oxide polyadduct containing 2 to 12 ethylene oxide units.

6. A method according to claim 4, wherein the foam stabiliser (a) is a sulfuric or phosphoric acid ester of an alkylphenol/ethylene oxide polyadduct containing 8 to 12 carbon atoms in the alkyl moiety and 2 to 12 ethylene oxide units, or an alkali metal salt, ammonium salt or amine salt thereof.

7. A method according to claim 4, wherein the foam stabiliser (a) is a sulfuric acid ester of a fatty alcohol/ethylene oxide polyadduct containing 8 to 18 carbon atoms in the alcohol radical and 2 to 4 ethylene oxide units, or an alkali metal salt thereof.

8. A method according to claim 4, wherein the foam stabiliser (a) is an alkylphenylsulfonate containing 8 to 12 carbon atoms in the alkyl moiety.

9. A method according to claim 4, wherein the foam stabiliser (a) is a fatty acid diethanolamide containing 8 to 18 carbon atoms in the fatty acid radical.

10. A method according to claim 4, wherein the sulfonated 1-benzyl-2-alkylbenzimidazole contains 16 to 18 carbon atoms in the alkyl moiety.

11. A method according to claim 4, wherein the foam stabiliser (a) is a mixture of the polyadduct of 7 to 15 moles of ethylene oxide and 1 mole of stearyl alcohol, coconut fatty acid diethanolamide and cetyl alcohol or diethoxylated cetyl alcohol.

12. A method according to claim 4, wherein the foam stabiliser (a) is a mixture of a nonylphenol/ethylene oxide polyadduct containing 10 to 12 ethylene oxide units, the sodium salt of a sulfuric acid ester of a fatty alcohol/ethylene oxide polyadduct containing 10 to 12 carbon atoms in the alcohol radical and 2 to 4 ethylene oxide units and coconut fatty acid diethanolamide.

13. A method according to claim 4, wherein the foam stabiliser (a) is the polyadduct of 1 mole of nonylphenol and 2 moles of ethylene oxide, the ammonium salt of the acid sulfuric acid ester of the polyadduct of 1 mole of nonylphenol and 2 moles of ehtylene oxide, sodium lauryl triglycol ether sulfate, sodium dodecylphenylsulfonate, or a fatty acid diethanolamide containing 8 to 18 carbon atoms in the fatty acid radical.

14. A method according to claim 4, wherein the foam stabiliser (a) is a mixture of dodecylbenzenesulfonate, sodium lauryl triglycol ether sulfate, coconut fatty acid diethanolamide and the disodium salt of 1-benzyl-2-stearylbenzimidazole-disulfonic acid.

15. A method according to claim 4, wherein the foam stabiliser (a) 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.

16. A method according to claim 4 of dyeing and/or finishing textile pile fabrics with an aqueous foam composition which contains a dye or a fluorescent whitening agent and/or a finishing agent, a foam stabiliser, a foam regulator and optionally other assistants, which method comprises preparing a foam from an aqueous composition which contains

(a) as foam stabiliser, 1 to 4 g/litre of

(1a) an ester of a polybasic acid of an alkylphenol/ethylene oxide polyadduct containing 4 to 12 carbon atoms in the alkyl moiety and 2 to 12 ethylene oxide units, or a salt thereof,

(1b) an ester of a polybasic acid of a fatty alcohol/ethylene oxide adduct containing 1 to 4 ethylene oxide units, or a salt thereof,

(2) an alkylphenylsulfonate containing 8 to 18 carbon atoms in the alkyl moiety,

(4a) an alkylphenol/ethylene oxide polyadduct containing 8 or 9 carbon atoms in the alkyl moiety and 2 to 12 ethylene oxide units, or

(6) a fatty acid dialkanolamide containing 8 to 12 carbon atoms in the fatty acid radical, and optionally

(3) a sulfonated 1-benzyl-2-alkylbenzimidazole containing 8 to 22 carbon atoms in the alkyl moiety, which components are used individually or in admixture, and

(b) as foam regulator, 0.1 to 1 g/litre of an oxyalkylene-siloxane copolymer,

the blow ratio of said foam being 1 : (6 to 20), applying said foam continuously, in the form of at least one layer, to the textile pile fabrics, vacuuming said fabrics to effect partial penetration of the layer of foam through the fabrics, and subsequently subjecting them to a steam treatment.

17. A method according to claim 1, wherein the non-ionic surfactant is an alkylene oxide polyadduct of the formula

wherein R' is hydrogen, alkyl or alkenyl, each containing at most 18, preferably 8 to 16, carbon atoms, o-phenylphenyl or alkylphenyl containing 4 to 12 carbon atoms in the alkyl moiety, one of Z, and Z₂ is hydrogen and the other is methyl, y is 1 to 15, and the sum of n_i + n₂ is 3 to 15.

18. A method according to claim 17, wherein the non-ionic surfactant is a polyadduct of 3 to 10 moles of ethylene oxide and 3 to 10 moles of propylene oxide with an aliphatic monoalcohol containing 8 to 16 carbon atoms.

19. A method according to any one of claims 1 to 18, wherein the foam regulator (b) is a polyether siloxane with a cloud point of 20° to 70° C, preferably from 25° to 50° C.

20. A method according to any one of claims 1 to 18, wherein the foam regulator (b) is a reaction product of a halogen-substituted organopolysiloxane and an alkali metal salt of a polyoxyalkylene.

21. A method according to any one of claims 1 to 20, wherein a foamed dye composition is applied continuously, in the form of a layer, to the textile fabric with an applicator roll, a vacuum of > 0 to 1 bar is then applied to effect sufficient penetration of the foam into the fabric that the layer of foam remaining on the surface thereof is reduced in height, and the fabric is then subjected to a steam treatment, rinsed with water, and finally dried.

22. A method according to any one of claims 1 to 21, wherein a first layer of foam is applied to the pile side of a carpet, then a vacuum is applied to effect penetration of the foam, a second layer of foam is then applied, and the carpet is thereafter subjected to a steam treatment and subsequently, if desired, rinsed with water and dried.

23. A method according to claim 22, wherein the carpet is dyed with the foam, steamed, rinsed with water and finally dried.

24. A method according to any one of claims 1 to 23, wherein a foamed finishing composition is applied continuously with an applicator roll, in a layer, to the textile fabric, a vacuum of > 0 to 1 bar is applied to effect sufficient penetration of the foam into the fabric that the layer of foam remaining on the surface thereof is reduced in height, and the fabric is subsequently subjected to a steam treatment.

25. A method according to claim 24, wherein the foamed finishing composition is applied to the textile fabric in succession from each side.

26. A method according to any one of claims 1 to 20, wherein the carpet is impregnated with an aqueous dye liquor, then the foamed composition is applied, and the dyeing is fixed by steaming.

27. A method according to claim 26, wherein the dye liquor also contains components (a) and (b).