EP0151091B1 - Process for printing cellulosic textile goods - Google Patents

Description

The present invention relates to a method for printing cellulose-containing textile material with reactive dyes with the help of foam printing inks.

It is known that cellulosic fiber materials can be dyed using foamed ink compositions. Pigments or pigment preparations are used as color components, which are always combined with binders. These compositions containing binders have the disadvantage that they impair the handle of the goods.

In contrast, no binders are generally used when printing with reactive dyes. There is therefore no influence on the grip. However, in order to achieve good stability with reactive dyes, large amounts of thickeners are required. The disadvantage of using the thickener is that it still has to be washed out after printing and fixing the dye. This post-wash requires considerable mechanical effort and increases the consumption of energy, water and various chemicals. From the Journal of Macromolecular Science, Reviews of Macromolecular Chemistry and Physics, 24 (3), 409 (1984), the use of polyacrylamide as a thickener in a process for printing on cotton is known.

It has now been found that, with the thickeners excluded, the desired stability can be achieved if cellulose-containing textile goods are printed with the process described below.

The present invention accordingly relates to a process for printing cellulose-containing textile material with reactive dyes by printing the textile material with a foamed, aqueous preparation and fixing the dyes by the action of heat, the preparation dyes, foaming agents and optionally other auxiliaries, such as e.g. Contains fixing alkalis, characterized in that the preparation additionally contains a graft polymer which can be obtained from an adduct of an alkylene oxide with an at least trihydric aliphatic alcohol having 3 to 10 carbon atoms and acrylamide or methacrylamide. The preparation can also contain mixtures of the polymers mentioned.

The amounts used, in which the required acrylic acid amide polymers are added alone or as a mixture to the preparations to be foamed, can range from 0.5 to 20 g / l in the form of aqueous solutions, depending on the printing process. Quantities of 0.5 to 20 g, advantageously 0.5 to 10 g and preferably 1 to 5 g in the form of 2 to 10% aqueous solutions, per liter of defoamed printing ink have proven to be advantageous.

Preference is given to graft polymers which can be obtained by graft polymerization of methacrylamide or, in particular, acrylamide onto an adduct of 4 to 100 mol, preferably 40 to 80 mol, of porpylene oxide with trivalent to hexavalent alkanols having 3 to 6 carbon atoms. These alkanols can be straight-chain or branched. Examples include glycerol, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, mannitol or sorbitol.

Further suitable graft polymers are those which are prepared by grafting methacrylamide or acrylamide onto addition products of mixtures of ethylene oxide and propylene oxide or else of ethylene oxide alone with the polyhydric alcohols mentioned.

Graft polymers of acrylamide and addition products of 40 to 80 moles of propylene oxide with 1 mole of glycerol have proven to be particularly suitable.

The graft polymers used according to the invention advantageously contain 2.5 to 50% by weight of the defined adduct as a parent chain and 50 to 97.5% of grafted methacrylamide or preferably acrylamide as side chains.

The graft polymers preferably have 2.5 to 30% by weight of the alkylene oxide adduct by definition and 70 to 97.5% by weight of grafted methacrylamide or, in particular, acrylamide. The amide content is more preferably 80 to 97.5% by weight, based on the graft polymer.

Among these products, those which contain 4 to 20% by weight of the adduct of 40 to 80 mol of propylene oxide with 1 mol of glycerol and 80 to 96% by weight of acrylamide as the parent chain are particularly preferred.

The percentages given relate to the entire graft polymer.

The graft polymers used according to the invention are prepared by methods known per se, expediently in such a way that (1) an adduct of an alkylene oxide with an at least trihydric aliphatic alcohol of 3 to 10 carbon atoms with (2) acrylamide or methacrylamide and in the presence of Catalysts, advantageously polymerized at a temperature of 40 to 100 ° C. This gives predominantly graft polymers in which the alkylene oxide adduct forms the parent chain which contains the grafted-on acrylamide or methacrylamide in the form of side chains on individual carbon atoms.

Free radical-forming organic or preferably inorganic initiators are expediently used as catalysts. Suitable organic initiators for carrying out the radical polymerization are, for example, symmetrical peroxidicarbonates, butyl peroctoates, butyl perbenzoates, peracetates or peroxidicarbamates. Suitable inorganic initiators are hydrogen superoxide, perborates, persulfates or peroxidisulfates.

The preferred initiator or activator is potassium peroxydisulfate.

These catalysts can be used in amounts of 0.05 to 5 percent by weight, advantageously 0.05 to 2 percent by weight and preferably 0.1 to 1 percent by weight, based on the starting products.

The graft polymerization is advantageously carried out in an inert atmosphere e.g. carried out in a nitrogen atmosphere.

The graft polymers are obtained as a very viscous mass. By dissolving and diluting with what _- ser was gel-like products can with a dry content of for example 0.5 to 20 wt .-%, preferably 2 to 20 wt .-% produced. To preserve and / or improve the storage stability of the aqueous graft polymer solutions obtained, preservatives, such as, for example, chloroacetamide, N-hydroxymethylchloroacetamide, pentachlorophenolates, alkali metal nitrites, triethanolamine or preferably hydroquinone monomethyl ether or else antibacterial agents, such as, for example, sodium azide or surface-active fatty acid quaternary, contain a quaternary , are added. Mixtures of these preservatives and germicidal compounds can also advantageously be used.

The particularly preferred 2 to 5% solutions of the graft polymers obtained have a viscosity of 3,000 to 150,000, preferably 15,000 to 120,000 and in particular 40,000 to 80,000 mPas (milli Pascal second) at 25 ° C. The polyalkylene oxide adducts used to prepare the graft polymers generally have a molecular weight of 400 to 6,000, preferably 3,000 to 4,500.

Anionic or nonionic compounds with surface-active properties, hereinafter referred to as surfactants, are generally suitable as foaming agents. The surfactants reduce the surface tension of solutions and thus facilitate and stabilize foam formation. Both the anionic and the nonionic surfactants can be present as individual compounds, as mixtures with one another or as combinations of anionic and nonionic surfactants.

• - sulfatierte aliphatische Alkohole, deren Alkylkette 8 bis 18 Kohlenstoffatome aufweist, z.B. sulfatierter Laurylalkohol;
• - sulfatierte ungesättigte Fettsäuren oder Fettsäurenniederalkylester, 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 oder Pentadecylsulfonat;
• - Alkylarylsulfonate mit einer oder zwei geradkettigen oder verzweigten Alkylketten mit insgesamt mindestens 6 Kohlenstoffatomen, z.B. Dodecylbenzolsulfonate, Dibutylnaphthalinsulfonate oder 3,7-Diisobutyl-naphthalinsulfonate;
• - sulfonierte 1-Benzyl-2-alkylbenzimidazole mit 8 bis 22 Kohlenstoffatomen im Alkylrest;
• - 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 z.B. o-Phosphorsäure oder insbesondere Schwefelsäure in einen sauren Ester übergeführten Anlagerungsprodukte von 1 bis 60, vorzugsweise 2 bis 30 Mol, Äthylenoxid und/oder Propylenoxid an Fettamine, Fettamide, Fettsäuren oder Fettalkohole je mit 8 bis 22 Kohlenstoffatomen, an Alkylphenole mit 4 bis 16 Kohlenstoffatomen in der Alkylkette, o-Phenylphenol, Benzylphenol 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;
• - Sulphated unsaturated fatty acids or fatty acid 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 or pentadecyl sulfonate;
• Alkylarylsulfonates with one or two straight-chain or branched alkyl chains with a total of at least 6 carbon atoms, for example dodecylbenzenesulfonates, dibutylnaphthalenesulfonates or 3,7-diisobutylnaphthalenesulfonates;
• - Sulfonated 1-benzyl-2-alkylbenzimidazoles with 8 to 22 carbon atoms in the alkyl radical;
• Sulfonates of polycarboxylic acid esters, for example dioctylsulfosuccinates or sulfosuccinamides;
• 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 with 12 to 18 carbon atoms, for example monoglycerides of lauric, stearic or oleic acid, and
• - The addition products converted into an acidic ester with an organic dicarboxylic acid, such as maleic acid, malonic acid or sulfosuccinic acid, but preferably with an inorganic polybasic acid, such as, for example, o-phosphoric acid or in particular sulfuric acid, from 1 to 60, preferably 2 to 30, moles of ethylene oxide and / or propylene oxide on fatty amines, fatty amides, fatty acids or fatty alcohols each with 8 to 22 carbon atoms, on alkylphenols with 4 to 16 carbon atoms in the alkyl chain, o-phenylphenol, benzylphenol or on tri- to hexavalent alkanols with 3 to 6 carbon atoms.

The acid residue of these anionic surfactants is usually 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.

• (1 ) 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 Alkylrest;
• (2) Alkylsulfate, deren Alkylkette 8 bis 20 Kohlenstoffatome enthält z.B. Laurylsulfat;
• (3) Alkylphenylsulfonate mit 8 bis 18 Kohlenstoffatomen im Alkylrest; oder
• (4) Dialkylnaphthalinsulfonate mit 3 bis 5 Kohlenstoffatomen pro Alkylrest.

Anionic surfactants are highly suitable as foaming agents

• (1) 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 radical;
• (2) alkyl sulfates, the alkyl chain of which contains 8 to 20 carbon atoms, for example lauryl sulfate;
• (3) alkylphenyl sulfonates having 8 to 18 carbon atoms in the alkyl radical; or
• (4) Dialkylnaphthalenesulfonates with 3 to 5 carbon atoms per alkyl group.

Components (1) to (4) can be used alone or as mixtures with one another as foaming agents.

The nonionic surfactant is advantageously a nonionic alkylene oxide adduct of 1 to 100 moles of alkylene oxide, e.g. Ethylene oxide and / or propylene oxide, on 1 mol 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.

• - Fettalkohole mit 8 bis 22 Kohlenstoffatomen, vor allem Cetylalkohol;
• - Anlagerungsprodukte von vorzugsweise 2 bis 80 Mol Alkylen oxyden, insbesondere Ethylenoxyd, wobei einzelne Ethylenoxydeinheiten durch substituierte Epoxyde, wie Styroloxyd und/oder Propylenoxyd, ersetzt sein können, an höhere ungesättigte oder gesättigte Monoalkohole, Fettsäuren, Fettamine oder Fettamide mit 8 bis 22 Kohlenstoffatomen oder an Phenylphenol oder Alkylphenole, deren Alkylreste mindestens 4 Kohlenstoffatome aufweisen;
• - Alkylenoxyd-, insbesondere Ethylenoxyd-und/oder Propylenoxyd-Kondensationsprodukte (Blockpolymerisate);
• - 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 1 800, vorzugsweise 400 bis 900, aufweisen.

Examples of nonionic surfactants are:

• - fatty alcohols with 8 to 22 carbon atoms, especially cetyl alcohol;
• - Addition products of preferably 2 to 80 mol of alkylene oxides, especially ethylene oxide, where individual ethylene oxide units can be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, to higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty amides with 8 to 22 carbon atoms or to phenylphenol or alkylphenols whose alkyl radicals have at least 4 carbon atoms;
• - Alkylene oxide, in particular ethylene oxide and / or propylene oxide condensation products (block polymers);
• - Reaction products from a fatty acid having 8 to 22 carbon atoms and a primary or secondary amine or alkylene oxide addition products containing at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group of these reaction products containing hydroxyalkyl groups, the reaction taking place in such a way that the molecular quantitative ratio between hydroxyalkylamine and fatty acid is 1: 1 and can be 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 6 carbon atoms, for example glycerol or pentaerythritol, the polypropylene oxide adducts having an average molecular weight of 250 to 1,800, preferably 400 to 900.

• (5) Anlagerungsprodukte von 2 bis 15 Mol Ethylenoxyd an 1 Mol eines aliphatischen Monoalkohols oder Fettsäure mit jeweils 8 bis 22 Kohlenstoffatomen oder an 1 Mol Alkylphenol mit insgesamt 4 bis 12 Kohlenstoffatomen im Alkylteil,
• (6) Fettsäuredialkanolamide mit 8 bis 22 Kohlenstoffatomen im Fettsäurerest und 2 bis 6 Kohlenstoffatomen im Alkanolteil.

Well-suited non-ionic surfactants as foaming agents are:

• (5) adducts of 2 to 15 moles of ethylene oxide with 1 mole of an aliphatic monoalcohol or fatty acid each with 8 to 22 carbon atoms or with 1 mole of alkylphenol with a total of 4 to 12 carbon atoms in the alkyl part,
• (6) Fatty acid dialkanolamides with 8 to 22 carbon atoms in the fatty acid residue and 2 to 6 carbon atoms in the alkanol part.

oder der Formel

worin R Wasserstoff, Alkyl oder Alkenyl mit höchstens 18 Kohlenstoffatomen, vorzugsweise 8 bis 16 Kohlenstoffatomen, o-Phenylphenyl oder AIkylphenyl mit 4 bis 12 Kohlenstoffatomen im Alkylteil, von Z, und Z₂ eines Wasserstoffs und das andere Methyl, y 1 bis 75, vorzugsweise 3 bis 50 und x 1 bis 30 bedeuten und die Summe von n, + n₂ 3 bis 30, vorzugsweise 3 bis 15 und von y, + y₂ 2 bis 30, vorzugsweise 4 bis 20 beträgt und n₂ und y₂ auch 0 sein können.Other highly suitable nonionic surfactants are block polymers of the formula

or 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, and Z _{2 of} a hydrogen and the other methyl, y 1 to 75, preferably 3 to 50 and x are 1 to 30 and the sum of n, + n _{2 is} 3 to 30, preferably 3 to 15 and of y, + y _{2 is} 2 to 30, preferably 4 to 20 and n ₂ and y _{2 are} also 0 could be.

Preferred block polymers of the formula (1) are those in which R is alkyl or alkenyl of 4 to 18, preferably 8 to 16 carbon atoms, y 1 to 15, preferably 3 to 15, n, 3 to 15 and n ₂ 0.

Particularly advantageous block polymers are fatty alcohol polyglycol mixed ethers, in particular addition products of 3 to 10 ethylene oxide and 3 to 10 mol of propylene oxide with aliphatic monoalcohols of 8 to 16 carbon atoms, preferably alkanols of 8 to 16 carbon atoms.

These block polymers are advantageously composed of 10 to 50 percent by weight of ethylene oxide and 50 to 90 percent by weight of units derived from propylene oxide and have a molecular weight of 250 to 6,000, in particular 350 to 3,000.

Siloxane-oxyalkylene copolymers can also be used as nonionic surfactants. These polymers are reaction products of halogen-substituted organopolysiloxanes and alkali metal salts of polyoxyalkylene, e.g. Polyethylene or polypropylene glycols. Such connections are e.g. described in European Patent Specification 30 919 or 49 832.

Preferred block polymers and siloxane-oxyalkylene copolymers which are used as foaming agents or foam moderators expediently have a cloud point of 15 to 70 ° C., preferably 25 to 50 ° C. The cloud point is e.g. determined according to DIN 53917.

The foaming agents used according to the invention are preferably used in the form of mixtures of the above-mentioned anionic and / or nonionic surfactants.

In addition to the anionic and / or nonionic surfactants mentioned, the foam-forming mixtures can contain quaternary ammonium salts. The latter can, for example, by reacting aliphatic fatty amines whose alkyl or alkenyl radicals have 8 to 24 carbon atoms, such as, for example, dodecylamine, hexadecylamine, heptadecylamine, octadecylamine, tallow fatty amine, behenylamine or oleylamine or di- and triamines, such as, for example, dodecylpropylenediamine and octadecylenediamine and octadecylenediamine and octadecylenediamine and octadecylenediamine 35 equivalents of an alkylene oxide, for example propylene oxide, but especially ethylene oxide or a mixture of propylene oxide and ethylene oxide and optionally additionally with 1 to 2 equivalents of styrene oxide and through final reaction with conventional quaternizing agents, such as methyl, ethyl or benzyl halide, diethyl sulfate and especially dimethyl sulfate, halohydrides, halocarboxamides, such as chloroacetamide.

Mixtures of these cationic auxiliaries can also be used.

Particularly suitable cationic auxiliaries have been dimethyl sulfate, diethyl sulfate or C _i -C ₂ alkyl halides, for example methyl chloride or iodide, quaternized products of addition products of 2 to 35 moles of ethylene oxide and optionally additionally 1 mole of styrene oxide with alkylamines or alkenylamines with 12 to 24 carbon atoms or their mixtures have been proven.

• (A) Alkylsulfonaten mit 8 bis 10 Kohlenstoffatomen und Fettalkoholen mit 12 bis 22 Kohlenstoffatomen oder Anlagerungsprodukten von 1 bis 4 Mol Ethylenoxid an diese Fettalkohole,
• (B) Anlagerungsprodukten von 2 bis 12 Mol Ethylenoxid an 1 Mol Alkylphenol mit 4 bis 12 Kohlenstoffatomen im Alkylteil, Natriumsalzen von Schwefelsäureestern von Fettalkohol-Ethylenoxidaddukten mit 10 bis 12 Kohlenstoffatomen im Alkoholteil und 2 bis 4 Ethylenoxideinheiten, und Fettsäurediethanolamiden mit 8 bis 18 Kohlenstoffatomen im Fettsäurerest,
• (C) Anlagerungsprodukten von 1 bis 15 Mol Ethylenoxid an 1 Mol Fettalkohol mit 12 bis 22 Kohlenstoffatomen, Fettsäurediethanolamiden mit 8 bis 18 Kohlenstoffatomen im Fettsäurerest,
• (D) Natriumsalzen von Schwefelsäureestern von Fettalkoholethylenoxidaddukten mit 10 bis 22 Kohlenstoffatomen im Alkoholteil und 2 bis 4 Ethylenoxideinheiten, Fettsäurediethanolamiden mit 8 bis 18 Kohlenstoffatomen im Fettsäurerest und gegebenenfalls Anlagerungsprodukten von 1 bis4 Mol Ethylenoxid an C₁₂-C₂₂-Fettalkohole,
• (E) Natriumsalzen von Schwefelsäureestern von Fettalkoholethylenoxidaddukten mit 10 bis 22 Kohlenstoffatomen im Alkoholteil und 2 bis 4 Ethylenoxideinheiten, Fettsäurediethanolamiden mit 8 bis 18 Kohlenstoffatomen im Fettsäurerest, Alkylbenzolsulfonaten mit 8 bis 12 Kohlenstoffatomen im Alkylteil und gegebenenfalls zusätzlich dem Dinatriumsalz der 1-Benzyl-2-C,₇-C,₈-A1- kylbenzimidazoldisulfonsäure,
• (F) einem Schwefelsäureester oder dessen Salze eines Anlagerungsproduktes von 2 bis 15 Mol Ethylenoxid an 1 Mol eines aliphatischen Monoalkohols mit 8 bis 18 Kohlenstoffatomen oder insbesondere an 1 Mol eines Alkylphenols mit 4 bis 12 Kohlenstoffatomen im Alkylrest, und einem Anlagerungsprodukt von 3 bis 10 Mol Ethylenoxid und 3 bis 10 Mol Propylenoxid an 1 Mol eines aliphatischen Monoalkohols mit 8 bis 16 Kohlenstoffatomen, oder
• (G) einem Schwefelsäureester oder dessen Salze (insbesondere Diethanolaminsalze), eines Anlagerungsproduktes von 2 bis 15 Mol Ethylenoxid an 1 Mol eines aliphatischen Monoalkohols mit 8 bis 18 Kohlenstoffatomen, einem Fettsäurediethanolamid mit 8 bis 18 Kohlenstoffatomen im Fettsäurerest, einem Dialkylnaphthalinsulfonat mit 3 bis 5 Kohlenstoffatomen pro Alkylrest und gegebenenfalls einem Anlagerungsprodukt von 2 bis 80 Mol Ethylenoxid an 1 Mol Fettalkohol mit 12 bis 22 Kohlenstoffatomen und/oder einem mit Dimethylsulfat quaternisierten Anlagerungsprodukt von 1 Mol Styroloxid und 10 bis 30 Mol Ethylenoxid an ein Fettamin mit 12 bis 22 Kohlenstoffatomen.

Preferred mixtures of foaming agents are, for example, combinations of components (1), (2), (3), (4), (5) and (6) and especially those made from

• (A) alkyl sulfonates with 8 to 10 carbon atoms and fatty alcohols with 12 to 22 carbon atoms or adducts of 1 to 4 moles of ethylene oxide with these fatty alcohols,
• (B) addition products of 2 to 12 moles of ethylene oxide with 1 mole of alkylphenol with 4 to 12 carbon atoms in the alkyl part, sodium salts of sulfuric acid esters of fatty alcohol-ethylene oxide adducts with 10 to 12 carbon atoms in the alcohol part and 2 to 4 ethylene oxide units, and fatty acid diethanolamides with 8 to 18 carbon atoms in the Fatty acid residue,
• (C) addition products of 1 to 15 moles of ethylene oxide with 1 mole of fatty alcohol with 12 to 22 carbon atoms, fatty acid diethanolamides with 8 to 18 carbon atoms in the fatty acid residue,
• (D) sodium salts of sulfuric acid esters of fatty alcohol ethylene oxide adducts with 10 to 22 carbon atoms in the alcohol part and 2 to 4 ethylene oxide units, fatty acid diethanolamides with 8 to 18 carbon atoms in the fatty acid residue and optionally addition products of 1 to 4 mol of ethylene oxide with C ₁₂ -C ₂₂ fatty alcohols,
• (E) Sodium salts of sulfuric acid esters of fatty alcohol ethylene oxide adducts with 10 to 22 carbon atoms in the alcohol part and 2 to 4 ethylene oxide units, fatty acid diethanolamides with 8 to 18 carbon atoms in the fatty acid residue, alkylbenzenesulfonates with 8 to 12 carbon atoms in the alkyl part and optionally also the disodium salt of 1-benzyl-2- C, ₇ -C, ₈ -A1- alkylbenzimidazole disulfonic acid,
• (F) a sulfuric acid ester or its salts of an adduct of 2 to 15 moles of ethylene oxide with 1 mole of an aliphatic monoalcohol with 8 to 18 carbon atoms or in particular with 1 mole of an alkylphenol with 4 to 12 carbon atoms in the alkyl radical, and an adduct of 3 to 10 moles Ethylene oxide and 3 to 10 moles of propylene oxide over 1 mole of an aliphatic monoalcohol with 8 to 16 carbon atoms, or
• (G) a sulfuric acid ester or its salts (especially diethanolamine salts), an adduct of 2 to 15 moles of ethylene oxide with 1 mole of an aliphatic monoalcohol with 8 to 18 carbon atoms, a fatty acid diethanolamide with 8 to 18 carbon atoms in the fatty acid residue, a dialkylnaphthalenesulfonate with 3 to 5 carbon atoms per alkyl radical and optionally an adduct of 2 to 80 mol of ethylene oxide with 1 mol of fatty alcohol with 12 to 22 carbon atoms and / or an adduct of quaternized with dimethyl sulfate of 1 mol of styrene oxide and 10 to 30 mol of ethylene oxide with a fatty amine with 12 to 22 carbon atoms.

The foam-forming mixtures can be prepared by simply stirring the components with water. If desired, the foaming agents can be added to the treatment liquors in the form of one or more mixtures. The individual mixtures can also serve as a foam moderator, foam stabilizer or wetting agent.

The amounts in which the foaming agents, preferably in the form of mixtures, are added to the treatment liquors are, depending on the printing process, between 0.5 and 200 g, preferably between 1.5 and 150 g, per liter of treatment liquor to be foamed.

The dyes used in the process according to the invention are the reactive dyes usually used for dyeing or printing cellulose textile materials.

Reactive dyes are understood to be the usual dyes that form a chemical bond with the cellulose, e.g. the “Reactive Dyes” listed in Color Index, Volume 3 (3rd edition, 1971) on pages 3391-3560 and Volume 6 (revised 3rd edition, 1975) on Pages 6268-6345.

The amount of dyes generally depends on the desired color strength and is expediently 0.1 to 300 g per liter of printing ink, advantageously 0.1 to 100 and preferably 5 to 60 g / l of printing ink.

When using reactive dyes, the preparations usually contain fixing alkalis. Examples of alkaline compounds for fixing the reactive dyes are sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, borax, aqueous ammonia or alkali donors, such as e.g. Sodium trichloroacetate or sodium formate used. A mixture of water glass and a 25% aqueous sodium carbonate solution can also be used as the alkali.

The pH of the printing inks containing alkali is generally 7.5 to 13.2, preferably 8.5 to 11.5.

The method according to the invention is suitable for printing on textiles which consist of or contain cellulose.

Suitable cellulose materials are those made from regenerated or, in particular, natural cellulose, such as, for example, cellulose, viscose silk, hemp, linen, jute or preferably tree wool, as well as fiber blends, for example those made of polyamide / cotton or in particular polyester / cotton, it being possible for the polyester portion to be printed simultaneously with disperse dyes.

The textile can be used in any form, e.g. Yarns, skeins of yarn, woven fabrics, knitted fabrics, felts, preferably in the form of textile fabrics such as woven fabrics or knitted fabrics, which consist wholly or partly of native, regenerated or modified cellulose.

The printing inks to be foamed are expediently prepared by dissolving the dye and adding the acrylamide polymer, the foaming agent and, if necessary, alkali. Depending on the dye used, the printing inks can contain other common additives such as Electrolytes, glycerin, urea, oxidizing agents e.g. Nitrobenzenesulfonate or sodium chlorate, sequestering agents or, depending on the printing ink, also contain wetting agents. The addition of thickeners is not necessary.

The foams can be produced on the commercially available foaming devices, and the foams can also be produced continuously.

According to the invention, degrees of foaming, i.e. Volume ratios of unfoamed to foamed preparation from 1: 2 to 1: 100, preferably 1: 4 to 1:20, have been found to be suitable.

The foams used according to the invention are distinguished by the fact that they are thick, dense and stable, i.e. are durable and usable for a long time. The foams used according to the invention preferably have half-lives of 5 minutes to 24 hours, preferably 30 minutes to 6 hours. The bubble diameters in the foams are about 1 to 100 g.

The foams can be applied evenly to the fiber materials using a wide variety of application techniques. Examples of some possibilities are: sucking in, doctor blades (one or both sides), blowing in, pressing in or printing. The application of the foam color can be done with the machines commonly used in textile printing, e.g. Rouleaux or rotary printing machines are used. The foam is advantageously applied by means of a screen printing machine, preferably in a closed system. Systems of this type are described, for example, in DE-OSs 3034802 and 3,034,803.

The foams are best applied at a temperature of 10 to 90 ° C, usually at room temperature, i.e. around 15 to 30 ° C. Based on the treated fabric, the foam application is generally 10 to 120, in particular 15 to 50 percent by weight.

The foam can be applied from a foam container, preferably with an adjustable doctor blade, to the front of the fabric via an application roller. The foam is drained immediately upon contact with the tissue. If desired, the foam application can be repeated on the back of the fabric. In this case, intermediate drying between the application on the front and that on the back is not necessary. It is also possible to apply different printing foams to the front and back of the textile.

The foam application according to the invention is preferably carried out by first treating the treatment liquor in a suitable device in a closed system, e.g. foamed under pressure and the foam produced is transported to the application device by means of pipes. The foam is then applied to the textile fabric, preferably through a sieve or a sieve-like intermediate carrier, whereupon the foam is sucked into the goods by mechanical pressing, pressing or knife-in. A perforated sheet, a latticework, network, wire mesh, screen drum or a screen template can be used as the screen or screen-like intermediate support.

The above-mentioned procedures destroy the foam structure with the foam bubbles bursting, whereupon the foam drains and the textile material is uniformly wetted.

After the foam has been applied and the foam has been dewatered, the printed textile material is subjected to a heat treatment process in order to fix the applied dyes.

The heat setting step can be carried out by a warm dwell process, a thermal insulation process or preferably by a steaming process.

In the steaming process, the textile materials printed with the dyeing foam for fixing the dyes are subjected to a treatment in a steamer with possibly superheated steam, advantageously at a temperature of 98 to 210 ° C., advantageously 100 to 180 ° C. and preferably 102 to 120 ° C.

In the warm dwell process, the goods are left moist, e.g. Linger for 5 to 120 minutes, advantageously at temperatures of 85 to 102 ° C. The printed goods can be preheated to 85 to 102 ° C by infrared treatment. The residence temperature is preferably 95 to 100.degree.

The fixation of the dyes by the so-called thermal insulation process can be done after or without intermediate drying e.g. at a temperature of 100 to 210 ° C. The thermal insulation is preferably carried out at a temperature of 120 to 210 ° C., preferably 140 to 180 ° C. and after intermediate drying at 80 to 120 ° C. of the printed goods. Depending on the temperature, the thermal insulation can take 20 seconds to 5 minutes, preferably 30 seconds to 4 minutes.

Following the dyeing process, the dyed cellulose-containing textile material can be washed out in the usual way in order to remove unfixed dye. To do this, the substrate is treated, for example, at from 40 ° C. to cooking temperature in one Solution containing soap or synthetic detergent. Treatment with a fixative can then be carried out to improve wet fastness.

With the method according to the invention, level and vivid color prints are obtained which are characterized by sharpness, a good handle and an excellent appearance. Furthermore, the fastness to use of the colored goods, such as Light fastness, rub fastness and wet fastness are not negatively affected by the use of the defined acrylic acid amide polymer.

In particular, by means of the foam application according to the invention, color prints with reactive dyes on cellulose-containing textiles, with the exclusion of the usual thickeners, such as e.g. Alginates, cellulose derivatives, starch ether or core meal ether such as locust bean meal, which are generally used in large quantities, can be achieved. According to the invention, color prints with excellent stability are obtained even with the addition of small amounts of the acrylic acid amide polymers according to the definition.

In the following manufacturing instructions and examples, parts and percentages are by weight unless otherwise specified.

The amounts of the dyes relate to commercial, i.e. coupé goods and with the aids on pure substance. The five-digit Color Index numbers (C.I.) refer to the 3rd edition of the Color Index.

Manufacturing regulations Regulation I:

A solution of 22.5 g of acrylamide, 2.5 g of an adduct of 52 moles of propylene oxide with 1 mole of glycerol and 0.04 g of potassium peroxydisulfate in 200 g of water is heated to 50 ° C. with stirring and passing over nitrogen and at this for 3 hours Temperature maintained. A solution of 0.03 g of potassium peroxydisulfate in 40 g of water is then added dropwise over the course of 60 minutes, and the very viscous solution is diluted with the addition of 300 ml of water over the course of 30 minutes. The reaction mixture is then kept at 50 ° C. for 5 hours, 0.6 g of hydroquinone monomethyl ether and 0.12 g of sodium azide are then added and the mixture is cooled to room temperature with stirring. 565 g of a gel with a polymer content of 4.4% are obtained. Measured at 25 ° C, this gel has a viscosity of 112,957 mPas.

Regulation 2:

A solution of 71.25 g of acrylamide, 3.75 g of an adduct of propylene oxide and glycerol with an average molecular weight of 4,200 and 0.09 g of potassium peroxydisulfate in 600 g of water is initially introduced and heated to 50 ° C with stirring and passing over nitrogen and Maintained at 50 ° C for 3 hours. The viscosity of the solution gradually increases. A solution of 0.06 g of potassium peroxydisulfate in 120 g of water is added dropwise over 60 minutes. About 10 minutes after the start of the dropping, the viscosity of the solution becomes so great that 600 g of water must be allowed to flow in over the next 20 minutes. After the dropwise addition of the potassium peroxydisulfate solution, the increasingly viscous solution is kept at 50 ° C. for a further 5 hours, with portions being diluted with an additional 400 g of water. 1.7 g of hydroquinone monomethyl ether are added, the mixture is cooled to room temperature with stirring, and 1,794 g of a free-flowing gel with a polymer content of 4.3% are obtained. This gel, measured at 25 ° C, has a viscosity of 64 202 m Pas.

Regulation 3:

A solution of 71.25 g of acrylamide, 3.75 g of an adduct of propylene oxide and pentaerythritol with an average molecular weight of 3,350 and 0.09 g of potassium peroxydisulfate in 600 g of water is heated to 50 ° C. while stirring and passing over nitrogen, and 3 Heated at 50 ° C for hours. The viscosity of the solution gradually increases. A solution of 0.06 g of potassium peroxydisulfate in 120 g of water is then added dropwise over 60 minutes. The viscosity of the solution increases approximately 30 minutes after the dropping has ended. 600 g of water are therefore allowed to flow in over the next 20 minutes. The solution, which becomes more viscous, is then kept at 50 ° C. for a further 4 hours, then diluted with an additional 400 g of water, 3.4 g of triethanolamine are added, the mixture is cooled to room temperature with stirring and 1793 g of a still flowing gel with a solids content of 4 are obtained , 0%. Measured at 25 ° C, this gel has a viscosity of 75,300 mPas.

Regulation 4:

A solution of 17.8 g of acrylamide, 0.94 g of an adduct of 70 moles of propylene oxide and 6 moles of ethylene oxide with 1 mole of glycerol and 0.025 g of potassium peroxydisulfate in 250 g of water is heated to 50 ° C. with stirring and passing over nitrogen and for 3 hours kept at this temperature. The temperature of the solution is raised to 60-63 ° C. in the course of 20 minutes until the viscosity increases significantly and then cooled to 55 ° C. The increasingly viscous solution is kept at 55 ° C. for 5 hours. A solution of 0.45 g of chloroacetamide and 0.45 g of hydroquinone monomethyl ether in 177 g of water is then added to the viscous solution, and 446 g of a gel with a graft polymer content of 4.2% are obtained. Measured at 25 ° C, this gel has a viscosity of 96 750 mPas.

Regulation 5:

If the addition product specified in regulation 4 is replaced by a further addition product of 53 mol of propylene oxide and 1 mol of trimethylolpropane, 446 g of a gel with a graft polymer content of 4.2% are obtained. Measured at 25 ° C, this gel has a viscosity of 19,500 m Pas.

Regulation 6:

A solution of 17.24 g of acrylamide, 4.31 g of an adduct of 70 moles of propylene oxide with 1 mole of glycerol and 0.035 g of potassium peroxydisulfate in 200 g of water is heated to 50 ° C. while stirring and passing over nitrogen and is kept at this temperature for 4 hours . The increasingly viscous solution is then heated to 55 ° C. for 5 hours. A solution of 0.4 g of chloroacetamide and 0.4 g of hydroquinone monomethyl ether in 291 g of water is added to the gel, and 513 g of a gel with a polymer content of 4.2% are obtained. Measured at 25 ° C, this gel has a viscosity of 25 750 mPas.

Regulation 7:

A mixture of 15.1 g of acrylamide, 6.5 g of an adduct of 70 moles of propylene oxide with 1 mole of glycerol and 0.025 g of potassium peroxydisulfate in 200 g of water is heated to 50 ° C. while stirring and passing over nitrogen and is kept at this temperature for 3 hours . The increasingly viscous solution is then heated to 55 ° C. for 5 hours. A solution of 0.4 g of chloroacetamide and 0.4 g of hydroquinone monomethyl ether in 291 g of water is added to the gel, and 512 g of a gel with a polymer content of 4.2% are obtained. Measured at 25 ° C, this gel has a viscosity of 16,300 mPas.

Regulation 8:

A mixture of 13 g of acrylamide, 8.7 g of an adduct of 70 moles of propylene oxide with 1 mole of glycerol and 0.015 g of potassium peroxide disulfate in 150 g of water is heated to 50 ° C. while stirring and passing over nitrogen and is kept at this temperature for 4 hours. The increasingly viscous solution is then heated to 65 ° C. for 2 hours and to 60 ° C. for a further 3 hours. A solution of 0.4 g of chloroacetamide and 0.4 g of hydroquinone monomethyl ether in 347 g of water is added to the gel, and 519 g of a gel with a polymer content of 4.2% are obtained. This gel, measured at 25 ° C, has a viscosity of 15,582 m Pas.

example 1

• 10 g eines Farbstoffes der Formel
  
• 50 g einer wässrigen Mischung, die 7,5 g eines Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0, 025 g Natriumlaurylsulfat enthält,
• 2 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
• 10 g des Natriumsalzes von m-Nitrobenzolsulfonsäure,
• 60 g einer 25%igen wässerigen Natriumcarbonatlösung und
• 150 g Harnstoff enthält.

A printing ink is produced which contains the following additives in 1 liter of water:

• 10 g of a dye of the formula
  
• 50 g of an aqueous mixture which contains 7.5 g of an adduct of 2 moles of ethylene oxide and 1 mole of cetyl alcohol and 0.025 g of sodium lauryl sulfate,
• 2 g of the graft polymer prepared according to regulation 2,
• 10 g of the sodium salt of m-nitrobenzenesulfonic acid,
• 60 g of a 25% aqueous sodium carbonate solution and
• Contains 150 g of urea.

The printing ink is then foamed in a closed system using a foam unit. The degree of foaming is 1: 8. The foam half-life is 90 minutes.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 0.40 bar. The printed fabric is then steamed at 102 ° C for 8 minutes, then soaped and dried as usual.

You get a strong, level, and sharp red print with an excellent handle and good fastness to use.

Similar good color prints are achieved if, instead of the graft polymer prepared according to regulation 2, the same amounts of the graft polymers prepared according to regulations 1 and 3 to 8 are used.

Example 2

• 1,8 g einer Mischung aus dem Di-(ß-hydroxyethyl)-aminsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol Laurylalkohol und Kokosfettsäure-N-di-ßhydroxylethylamid (1:1)
• 0,7 g einer Mischung aus 13 Teilen des mit Dimethylsulfat quaternisierten Anlagerungsproduktes von 1 Mol Styroloxid und 15 Mol Ethylenoxid an 1 Mol Oleylamin, 13 Teilen Dibutylnaphthalinsulfonsäure und 7 Teilen des Anlagerungsproduktes von 80 Mol Ethylenoxid an 1 Mol Oleylalkohol,
• 2 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
• 10 g des Natriumsalzes von m-Nitrobenzolsulfonsäure, und
• 70 g einer 25%igen wässerigen Natriumcarbonatlösung enthält.

A printing ink is prepared which contains the following additives in 1 liter of water: 20 g of a dye of the formula

• 1.8 g of a mixture of the di- (β-hydroxyethyl) amine salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of lauryl alcohol and coconut fatty acid-N-di-ßhydroxylethylamide (1: 1)
• 0.7 g of a mixture of 13 parts of the adduct quaternized with dimethyl sulfate of 1 mol of styrene oxide and 15 mol of ethylene oxide on 1 mol of oleylamine, 13 parts of dibutylnaphthalenesulfonic acid and 7 parts of the adduct of 80 mol of ethylene oxide on 1 mol of oleyl alcohol,
• 2 g of the graft polymer prepared according to regulation 2,
• 10 g of the sodium salt of m-nitrobenzenesulfonic acid, and
• Contains 70 g of a 25% aqueous sodium carbonate solution.

The printing ink is then foamed in a closed system using a foam unit. The degree of foaming is 1:40. The foam half-life is 2 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 0.40 bar. The printed fabric is then dried, steamed at 100 ° C. for 8 minutes, then soaped as usual and dried again.

You get a strong, level, and sharp red print with an excellent handle and good fastness to use.

Example 3

• 75 g eines Farbstoffes der Formel
  
• 100 g einer wässerigen Mischung, die 15,0 g eines Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,05 g Natriumlaurylsulfat enthält,
• 10 g des gemäss Vorschrift 4 hergestellten Pfropfpolymerisates,
• 80 g einer 25%igen wässerigen Natriumcarbonatlösung und
• 100 g Harnstoff enthält.

A printing ink is produced which contains the following additives in 1 liter of water:

• 75 g of a dye of the formula
  
• 100 g of an aqueous mixture which contains 15.0 g of an adduct of 2 moles of ethylene oxide and 1 mole of cetyl alcohol and 0.05 g of sodium lauryl sulfate,
• 10 g of the graft polymer prepared according to regulation 4,
• 80 g of a 25% aqueous sodium carbonate solution and
• Contains 100 g of urea.

The printing ink is then foamed in a closed system using a foam unit. The degree of foaming is 1: 8. The foam half-life is <2 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 0.20 bar. The printed fabric is then dried, steamed at 140 ° C. for 4 minutes, then rinsed as usual and dried again.

You get a level, brilliant turquoise blue print with good fastness properties.

Color prints of similar quality are achieved if, instead of the graft polymer prepared according to regulation 4, the same amount of the graft polymers prepared according to regulations 1 to 3 and 5 to 8 are used.

Example 4

• 10 g eines Farbstoffes der Formel
  
• 10 g des Farbstoffes der Formel (11 ),
• 150 g einer wässerigen Mischung, die 22,5 g eines Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,075 g Natriumlaurylsulfat enthält,
• 20 g des gemäss Vorschrift 2, hergestellten Pfropfpolymerisates,
• 10 g m-Nitrobenzolsulfonsäure-Natriumsalz,
• 8 g Natriumbicarbonat und
• 50 g Harnstoff enthält.

A printing ink is produced which contains the following additives in 1 liter of water:

• 10 g of a dye of the formula
  
• 10 g of the dye of the formula (11),
• 150 g of an aqueous mixture containing 22.5 g of an adduct of 2 moles of ethylene oxide with 1 mole of cetyl alcohol and 0.075 g of sodium lauryl sulfate,
• 20 g of the graft polymer prepared according to regulation 2,
• 10 g m-nitrobenzenesulfonic acid sodium salt,
• 8 g sodium bicarbonate and
• Contains 50 g of urea.

The printing ink is then foamed in a suitable foam unit, the degree of foaming being 1: 6. The foam is printed on a stencil on a mixed fabric made of cotton / polyester (33/67) with a squeegee. The printed fabric is then dried, steamed at 180 ° C. for 8 minutes, then rinsed, soaped and dried as usual. You get a level, brilliant red print with good fastness properties.

Example 5

• 100 g des Reaktivfarbstoffes Reactive Black 1 C. I. 17916,
• 100 g einer wässerigen Mischung, die 15,0 g eines Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,05 g Natriumlaurylsulfat enthält,
• 10 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
• 10 g m-Nitrobenzolsulfonsäure-Natriumsalz,
• 170 g einer 25%igen wässerigen Natriumcarbonatlösung und
• 200 g Harnstoff enthält.

A printing ink is produced which contains the following additives in 1 liter of water:

• 100 g of the reactive dye Reactive Black 1 CI 17916,
• 100 g of an aqueous mixture which contains 15.0 g of an adduct of 2 moles of ethylene oxide and 1 mole of cetyl alcohol and 0.05 g of sodium lauryl sulfate,
• 10 g of the graft polymer prepared according to regulation 2,
• 10 g m-nitrobenzenesulfonic acid sodium salt,
• 170 g of a 25% aqueous sodium carbonate solution and
• Contains 200 g of urea.

The printing ink is then foamed in a closed system using a foam unit. The degree of foaming is 1: 7. The foam half-life is <2 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 0.20 bar. The printed fabric is then dried, heat-set at 150 ° C. for 4 minutes, then rinsed as usual and dried again.

You get a level, gray print with good fastness properties.

Claims (20)

1. A process for printing cellulose-containing textile material with reactive dyes by printing the textile material with a foamed aqueous preparation and fixing the dyes through the action of heat, said preparation containing dyes and foaming agents in the absence or presence of further assistants, for example fixing alkalis, wherein the preparation additionally contains a graft polymer which is obtainable from an adduct of an alkylene oxide on an at least trihydric aliphatic alcohol having 3 to 10 carbon atoms and acrylamide or methacrylamide.

2. A process according to Claim 1 wherein the preparation contains the polymer in an amount of 0.1 to 20 g/I in the form of an aqueous solution per litre of unfoamed preparation.

3. A process according to either of Claims 1 or 2 wherein the preparation contains the polymer in an amount of 0.5 to 10 g, preferably 1 to 5 g, in the form of a 2 to 10% aqueous solution per litre of unfoamed preparation.

4. A process according to any one of Claims 1 to 3 wherein the preparation contains a graft polymer obtainable by graft polymerisation of acrylamide or methacrylamide onto an adduct of 4 to 100 moles, preferably 40 to 80 moles, of propylene oxide on a trihydric to hexahydric alkanol having 3 to 6 carbon atoms.

5. A process according to any one of Claims 1 to 4, wherein the graft polymer contains 2.5 to 50% by weight of the adduct and 50 to 97.5% by weight of the grafted-on acrylamide or methacrylamide based on the graft polymer.

6. A process according to Claim 5 wherein the graft polymer contains 2.5 to 30% by weight of the adduct and 70 to 97.5% by weight of the grafted-on acrylamide or methacrylamide based on the graft polymer.

7. A process according to any one of Claims 1 to 6, wherein the graft polymer has been prepared from acrylamide and an adduct of 40 to 80 moles of propylene oxide on 1 mole of glycerol.

8. A process according to Claim 7 wherein the graft polymer contains 4 to 20% by weight of the adduct of 40 to 80 moles of propylene oxide on 1 mole of glycerol and 80 to 96% by weight of grafted-on acrylamide, based on the graft polymer.

9. A process according to any one of Claims 1 to 8, wherein the preparation contains as foaming agent a mixture of alkylsulfonates having 8 to 10 carbon atoms and fatty alcohols having 12-22 carbon atoms or adducts of 1 to 4 moles of ethylene oxide or 1 mole of these fatty alcohols.

10. A process according to any one of Claims 1 to 8, wherein the preparation contains as foaming agents a mixture of adducts of 2 to 12 moles of ethylene oxide on the mole of alkylphenol having 4 to 12 carbon atoms in the alkyl moiety, sodium salts of sulfuric acid esters of fatty alcohol/ethylene oxide adducts having 10 to 12 carbon atoms in the alcohol moiety and 2 to 4 ethylene oxide units and the fatty acid diethanolamides having 8 to 18 carbon atoms in the fatty acid radical.

11. A process according to any one of Claims 1 to 8 wherein the preparation contains as foaming agent a mixture of adducts of 1 to 15 moles of ethylene oxide on 1 mole of fatty alcohol having 12 to 22 carbon atoms, and fatty acid diethanolamides having 8 to 18 carbon atoms in the fatty acid radical.

12. A process according to any one of Claims 1 to 8 wherein the preparation contains as foaming agent a mixture of sodium salts of sulfuric acid esters of fatty alcohol/ethylene oxide adducts having 10 to 22 carbon atoms in the alcohol moiety and 2 to 4 ethylene oxide units and fatty acid diethanolamides having 8 to 18 carbon atoms in the fatty acid radical and can, if desired, also contain adducts of 1 to 4 moles of ethylene oxide on C12-C22-alcohols.

13. A process according to any one of Claims 1 to 8 wherein the preparation contains as foaming agent a mixture of sodium salts of sulfuric acid esters of fatty alcohol/ethylene oxide adducts having 10 to 22 carbon atoms in the alcohol moiety and 2 to 4 ethylene oxide units, fatty acid diethanolamides having 8 to 18 carbon atoms in the fatty acid radical, alkylbenzenesulfonates having 8 to 12 carbon atoms in the alkyl moiety and can, if desired, also contain in addition the disodium salt of 1 -benzyl-2-C₁₇-C₁₈-aikylbenzimidazoledi- suifonicacid.

14. A process according to any one of Claims 1 to 8 wherein the preparation contains as foaming agent a mixture of a sulfuric acid ester or its salts of an adduct of 2 to 15 moles of ethylene oxide on 1 mole of an aliphatic monoalcohol having 8 to 18 carbon atoms or in particular on 1 mole of an alkylphenol having 4 to 12 carbon atoms in the alkyl radical and an adduct of 3 to 10 moles of ethylene oxide and 3 to 10 moles of propylene oxide on an aliphatic monoalcohol of 8 to 16 carbon atoms.

15. A process according to any one of Claims 1 to 8 wherein the preparation contains as foaming agent a mixture of a sulfuric acid ester or its salts of an adduct of 2 to 15 moles of ethylene oxide on 1 mole of an aliphatic monoalcohol having 8 to 18 carbon atoms, a fatty acid diethanolamide having 8 to 18 carbon atoms in the fatty acid radical, a dialkylnaphthalenesulfonate having 3 to 5 carbon atoms per alkyl radical and can, if desired, also contain an adduct of 2 to 80 moles of ethylene oxide on 1 mole of fatty alcohol having 12 to 22 carbon atoms and/or an adduct, quaternised with dimethyl sulfate, of 1 mole of styrene oxide and 10 to 30 moles of ethylene oxide on 1 mole of fatty amine having 12 to 22 carbon atoms.

16. A process according to any one of Claims 1 to 15 wherein printing takes place on a screenprinting machine.

17. A process according to Claim 16 wherein the preparation is applied to a sieve or sievelike intermediate carrier and is forced through the sieve or the sievelike intermediate carrier.

18. A process according to any one of Claims 1 to 17 wherein the dyes are fixed by steaming.

19. A process according to any one of Claims 1 to 17 wherein the dyes are fixed by thermosoling.