EP0162018B1 - Process for dyeing or printing fabrics containing cellulose with vat dyes - Google Patents

Description

EP-A-009 721, Example X describes a two-stage process for dyeing cotton, in which the dyeing is carried out with a foamed composition which contains a sulfur dye. GB-A-871 193 discloses a process for dyeing cellulose-containing textile goods, polyacrylamide polymers being used as migration inhibitors.

The present invention relates to a process for dyeing or printing cellulose-containing textile material with vat dyes and with the aid of foam which contains graft polymers. The process is characterized in that, with the exclusion of air, a foamed, aqueous preparation is used which contains dyes, foaming agents, reducing agents, alkalis and a graft polymer which consists of an adduct of an alkylene oxide with an at least trihydric aliphatic alcohol having 3 to 10 carbon atoms and acrylamide or Methacrylamide is available contains. The preparation can also contain mixtures of the polymers mentioned.

The amounts used in which the acrylic acid amide graft polymers are added to the preparations to be foamed, alone or as a mixture, can range from 0.5 to 20 g / l in the form of aqueous solutions, depending on the process. Quantities of 0.5 to 10 g, preferably 1 to 5 g in the form of 2 to 10% aqueous solutions, per liter of non-foamed preparation 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 propylene oxide with 3 to 6 carbon atoms having trivalent to hexavalent alkanols. 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 the parent chain and 50 to 97.5% by weight of grafted methacrylamide or preferably acrylamide as the 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, suitably 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. B. 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. B. carried out in a nitrogen atmosphere.

The graft polymers are obtained as a very viscous mass. By dissolving and diluting with water, gel-like products with a dry content of e.g. B. 0.5 to 20 wt .-%, preferably 2 to 20 wt .-%. To preserve and / or improve the storage stability of the aqueous graft polymer solutions obtained, preservatives, such as. B. chloroacetamide, N-hydroxymethylchloroacetamide, pentachlorophenolates, alkali metal nitrites, triethanolamine or preferably hydroquinone monomethyl ether or antibacterial agents, such as. B. sodium azide or surface-active quaternary ammonium compounds, which have one or two fatty alkyl radicals, 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 at 25 ° C (milli Pascal second). The polyalkylene oxide adducts used to prepare the graft polymers generally have a molecular weight of 400 to 6000, preferably 3000 to 4500.

• - 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 Oele, 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 Oelsäure, 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.

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. 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 such fatty acids containing oils, e.g. B. castor oil;
• - Alkyl sulfonates whose alkyl chain contains 8 to 20 carbon atoms, e.g. B. dodecyl sulfonate or pentadecyl sulfonate;
• - Alkylarylsulfonate with one or two straight-chain or branched alkyl chains with a total of at least 6 carbon atoms, for. B. 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, 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. B. o-phosphoric acid or in particular sulfuric acid adducts converted from 1 to 60, preferably 2 to 30 mol, ethylene oxide and / or propylene oxide onto fatty amines, fatty amides, fatty acids or fatty alcohols each having 8 to 22 carbon atoms, to alkylphenols having 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. B. 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 whose alkyl chain contains 8 to 20 carbon atoms e.g. B. 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 addition product of 1 to 100 moles of alkylene oxide, e.g. As 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 Alkylenoxyden, 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 1800, 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, in particular ethylene oxide, where individual ethylene oxide units can be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, with higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty amides with 8 to 22 carbon atoms or at Phenylphenol or alkylphenols, the alkyl radicals of which 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 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.

• (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.
  Weitere gut geeignete nichtionogene Tenside sind Blockpolymerisate der Formel
  
  oder der Formel
  
  worin R Wasserstoff, Alkyl oder Alkenyl mit höchstens 18 Kohlenstoffatomen, vorzugsweise 8 bis 16 Kohlenstoffatomen, o-Phenylphenyl oder Alkylphenyl mit 4 bis 12 Kohlenstoffatomen im Alkylteil, von Z₁ und Z₂ eines Wasserstoff und das andere Methyl, y 1 bis 75, vorzugsweise 3 bis 50 und x 1 bis 30 bedeuten und die Summe von n₁ + n₂ 3 bis 30, vorzugsweise 3 bis 15 und von _Y1 + y₂ 2 bis 30, vorzugsweise 4 bis 20 beträgt und n₂ und y₂ auch 0 sein können.

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

• (5) Addition products 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.
  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 ₁ 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 ₁ + n _{2 is} 3 to 30, preferably 3 to 15 and of _Y1 + y _{2 is} 2 to 30, preferably 4 to 20 and n ₂ and y _{2 are} also 0 can.

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 ₁ 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 monoalcohol 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 6000, in particular 350 to 3000.

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. B. polyethylene or polypropylene glycols. Such connections are e.g. B. described in European Patent 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. B. determined according to DIN 53 917.

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 e.g. B. by reacting aliphatic fatty amines whose alkyl or alkenyl radicals have 8 to 24 carbon atoms, such as. B. dodecylamine, hexadecylamine, heptadecylamine, octadecylamine, tallow fatty amine, behenylamine or oleylamine or di- and triamines, such as. B. dodecylpropylenediamine, octadecylethylenediamine and octadecyldiethylenetriamine with 1 to 35 equivalents of an alkylene oxide, e.g. B. 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 by subsequent reaction with conventional quaternizing agents, such as. As methyl, ethyl or benzyl halide, diethyl sulfate and especially dimethyl sulfate, halohydrins, halocarboxamides, such as. B. chloroacetamide.

Mixtures of these cationic auxiliaries can also be used.

As particularly suitable cationic auxiliaries with dimethyl sulfate, diethyl sulfate or C ₁ -C ₂ alkyl halides z. B. 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 to alkylamines or alkenylamines having 12 to 24 carbon atoms or mixtures thereof.

• (A) Alkylsulfonaten mit 8 bis 20 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 22 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 bis 4 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-C₁₇-C₁₈-Alkylbenzimidazoldisulfonsäure,
• (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 - 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 1 Mol Fettamin mit 12 bis 22 Kohlenstoffatomen.

Preferred mixtures of foaming agents are e.g. B. combinations of components (1), (2), (3), (4), (5) and (6) and especially those

• (A) alkyl sulfonates with 8 to 20 carbon atoms and fatty alcohols with 12 to 22 carbon atoms or addition products of 1 to 4 mol of ethylene oxide onto these fatty alcohols,
• (B) adducts 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 22 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 moles of ethylene oxide with C12-C22 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 ₁₇ -C ₁₈ 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 in 1 mole of an aliphatic monoalcohol with 8-16 carbon atoms, or
• (G) a sulfuric acid ester or its salts (especially diethanolamine 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, 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 having 12 to 22 carbon atoms and / or an adduct quaternized with dimethyl sulfate of 1 mol of styrene oxide and 10 to 30 mol of ethylene oxide with 1 mol of 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 used, in which the foaming agents, preferably in the form of mixtures, are added to the treatment liquors, vary between 2 and 50 g, preferably between 2.5 and 20 g, per liter of treatment liquor to be foamed, depending on the printing process.

Suitable dyes which can be used in the process according to the invention are the vat dyes usually used for dyeing or printing cellulose textile materials.

The vat dyes are e.g. B. to higher fused and heterocyclic benzoquinones or naphthoquinones, to sulfur dyes and in particular anthraquinone or indigoid dyes. Examples of vat dyes which can be used according to the invention are listed in the Color Index 3rd Edition (1971) Vol. 3 on pages 3649 to 3837 under the names "Sulfur Dyes" and "Vat Dyes".

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

Sodium dithionite (sodium hydrosulfite), for example, is used as a reducing agent for converting the vat dyes into the fiber-fine form of the leuco compound (vatting). The vatting takes place in an alkaline medium. Examples of alkaline compounds are sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, borax, aqueous ammonia or alkali donors, such as. B. sodium trichloroacetate is used.

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

As cellulose material comes from regenerated or in particular natural cellulose, such as. B. cellulose, viscose silk, cellulose acetate, hemp, linen, jute or preferably cotton, and fiber mixtures such. B. those made of polyamide / cotton or in particular polyester / cotton, wherein the polyester portion can be printed with disperse dyes at the same time.

The textile material can be in any form, such as. B. as yarn, skein, woven fabric, knitted fabric, felt, preferably in the form of textile fabrics such as woven or knitted fabric, which consist entirely or partially of native, regenerated or modified cellulose.

The preparations to be foamed are expediently prepared by dissolving the dye and adding the acrylamide polymer, the foaming agent, the alkalis and reducing agents. The preparations can contain other conventional additives, e.g. B. electrolytes such as sodium chloride or sodium sulfate, glucose, urea, reduction catalysts, fixation accelerators, protective colloids, sulfobetaines, sequestering agents or, depending on the printing ink, also leveling agents and wetting agents. The addition of thickeners is not necessary.

The pH of the printing inks is usually 8 to 13.5, preferably 9 to 13.

The foams can be produced on the commercially available foaming devices, the foams being excluded from the air by means of non-oxidizing blowing agents, for. B. using nitrogen, if desired also continuously.

According to the invention, degrees of foaming, i.e. Volume ratios of unfoamed to foamed preparation from 1: 2 to 1: 100, advantageously 1: 3 to 1: 30, 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 1 minute to 6 hours, preferably 10 minutes to 1 hour.

The foams can be applied evenly to the fiber materials using a wide variety of application techniques. Examples of some possibilities are: sucking in, blowing in, Press in or print. The foam color can be applied using the machines suitable for textile printing. 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 3,034,802 and 3,034,803.

The foams can be applied at a temperature of 10 to 105 ° C. It is preferably carried out at room temperature, i.e. approximately at 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 is drained immediately upon contact with the tissue. If desired, the foam application can be repeated on the back of the fabric. It is also possible to apply different pressure foams to the front and back of the textile material.

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. B. under pressure, and in an inert atmosphere z. B. in a nitrogen atmosphere, foamed and transported the foam generated by means of pipes to the applicator. 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, pressed into or pressed into the goods. 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 application, the printed textile material is subjected to a heat treatment process if necessary, then oxidized, soaped and finished in the usual way.

The heat treatment is usually carried out by steaming and in the absence of air. It can also be carried out using microwaves. After impregnation with the pressure foam, the goods are treated in a chamber with the exclusion of air using microwaves.

In the steaming process, the textile materials printed with the dyeing foam are subjected to a treatment in a steamer with possibly superheated steam, expediently at a temperature of 60 to 120 ° C., preferably 100 to 106 ° C. Depending on the temperature, steaming can take 15 to 120 seconds.

The microwave treatment can take about 15 seconds to 30 minutes. Preferably 1 to 15 minutes will suffice. Microwaves are electromagnetic waves (radio waves) in the frequency range from 300 to 100,000 M Hz, preferably 1000 to 30,000 M Hz.

Following the dyeing process, the dyed cellulose-containing textile material can be washed out in a conventional manner in order to remove unfixed dye and to finally develop the color of the dyeing. For this purpose, the substrate is treated, for example, at from 40 ° C. to cooking temperature in a solution which contains soap or synthetic detergent.

With the method according to the invention, level and vivid color prints are obtained, which are characterized by sharpness and a good handle. Furthermore, the fastness to use of the colored goods, such as. B. Light fastness, fastness to rubbing and wet fastness are not adversely 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 vat dyes on cellulose-containing textiles, with the exclusion of the usual thickeners such as B. alginates, cellulose derivatives, starch ether or core meal ether such as locust bean meal, which are usually used in large quantities. 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.1.) Refer to the 3rd edition of the Color Index.

Manufacturing regulations Regulation 1:

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. while stirring and passing over nitrogen and 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 4200 and 0.09 g of potassium peroxydisulfate in 600 g of water is 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 1794 g of a free-flowing gel with a polymer content of 4.3% are obtained. Measured at 25 ° C, this gel has a viscosity of 64 202 mPas.

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 3350 and 0.09 g of potassium peroxydisulfate in 600 g of water is heated to 50 ° C. with stirring and passing over nitrogen and for 3 hours kept at 50 ° C. 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 increased 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 are obtained , 2%. 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 mPas.

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 with stirring and nitrogen sparge and 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 mPas.

Example 1:

• 30 g eines handelsüblichen Farbstoffes der Formel
  
• 2,7 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-ß-hydroxylethylamid (1 : 1)
• 1,2 g einer Mischung aus 13 Teilen des mit Dimethylsulfat quaternisierten Anlagerungs produktes 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,
• 3 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates, 100 ml einer 30 %-igen wässerigen Natriumhydroxidlösung und 20 g Natriumsulfat.
• Hierauf wird die Druckfarbe mit 50 g Natriumhydrosulfit versetzt und in einem geschlossenen System über ein Schaumaggregat mit Stickstoff verschäumt. Der Verschäumungsgrad beträgt 1 : 10.
• Dieser Schaum wird unter Druck (0,60 bar) durch Rohrleitungen über eine Siebschablone auf ein Baumwollgewebe gepresst. Alsdann wird das bedruckte Gewebe 30 Sekunden bei 102°C gedämpft, an der Luft oxidiert und anschliessend wie üblich gespült, geseift, wieder gespült und getrocknet. Man erhält somit auf rationelle Arbeitsweise einen egalen und scharfstehenden roten Druck mit ausgezeichneten Gebrauchsechtheiten.
• Ähnliche gute Farbdrucke werden erzielt, wenn anstelle des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates gleiche Mengen der gemäss Vorschriften 1 und 3 bis 8 hergestellten Pfropfpolymerisate eingesetzt werden.

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

• 30 g of a commercially available dye of the formula
  
• 2.7 g of a mixture of the di- (β-hydroxyethyl) amine salt of the acidic sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of lauryl alcohol and
• Coconut fatty acid-N-di-ß-hydroxylethylamide (1: 1)
• 1.2 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 and 1 mol of oleylamine,
• 13 parts of dibutylnaphthalenesulfonic acid and 7 parts of the adduct of 80 moles of ethylene oxide and 1 mole of oleyl alcohol,
• 3 g of the graft polymer prepared according to regulation 2, 100 ml of a 30% aqueous sodium hydroxide solution and 20 g of sodium sulfate.
• Then the printing ink is mixed with 50 g of sodium hydrosulfite and foamed with nitrogen in a closed system using a foam unit. The degree of foaming is 1:10.
• This foam is pressed under pressure (0.60 bar) through pipelines over a screen template onto a cotton fabric. The printed fabric is then steamed at 102 ° C. for 30 seconds, oxidized in air and then rinsed, soaped, rinsed and dried as usual. In a rational way of working, a level and sharp red print with excellent fastness properties is obtained.
• 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:

• 10 g des Farbstoffes Vat Blau 43 C. I. 53 630
• 2,7 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-ß-hydroxylethylamid (1 : 1)
• 1,2 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,
• 3 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates, 1,5 g einer Mischung aus
• 20 Teilen einer 50 %-igen wässerigen Lösung von Polymaleinsäureanhydrid (MG 600)
• 9 Teilen Dinatriumsalz des Di-(6-sulphonaphthyl-2-)-methans
• 15 Teilen Natriumsalz eines sauren Phosphorsäureesters eines Fettalkoholpolyethoxylates
• 30 ml einer 30 %-igen wässerigen Natriumhydroxidlösung und 20 g Natriumsulfat
• Hierauf wird die Druckfarbe mit 10 g Natriumhydrosulfit verküpt und in einem geschlossenen System über ein Schaumaggregat mit Stickstoff verschäumt. Der Verschäumungsgrad beträgt 1 : 23.
• Dieser Schaum wird unter Durck durch Rohrleitungen über eine Siebschablone auf ein Baumwollgewebe gepresst. Alsdann wird das Gewebe an der Luft oxidiert und anschliessend gespült, geseift, wieder gespült und getrocknet.
• Man erhält einen scharfstehenden hellen blauen Druck mit guten Gebrauchsechtheiten.

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

• 10 g of the dye Vat Blau 43 CI 53 630
• 2.7 g of a mixture of the di- (β-hydroxyethyl) amine salt of the acidic sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of lauryl alcohol and
• Coconut fatty acid-N-di-ß-hydroxylethylamide (1: 1)
• 1.2 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 and 1 mol of oleylamine,
• 13 parts of dibutylnaphthalenesulfonic acid and 7 parts of the adduct of 80 moles of ethylene oxide and 1 mole of oleyl alcohol,
• 3 g of the graft polymer prepared according to regulation 2, 1.5 g of a mixture of
• 20 parts of a 50% aqueous solution of polymaleic anhydride (MW 600)
• 9 parts of disodium salt of di- (6-sulphonaphthyl-2 -) - methane
• 15 parts of sodium salt of an acidic phosphoric acid ester of a fatty alcohol polyethoxylate
• 30 ml of a 30% aqueous sodium hydroxide solution and 20 g of sodium sulfate
• The printing ink is then coated with 10 g of sodium hydrosulfite and foamed with nitrogen in a closed system using a foam unit. The degree of foaming is 1:23.
• This foam is pressed under pressure through pipelines over a screen template onto a cotton fabric. The tissue is then oxidized in air and then rinsed, soaped, rinsed and dried.
• A sharp, bright blue print with good fastness properties is obtained.

Example 3:

• 10 g des Farbstoffes Vat Green 1 C. I. 59 825
• 100 g einer wässerigen Mischung, die 7,5 g eines Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,025 g Natriumlaürylsulfat enthält.
• 15 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates
• 5 g einer Mischung aus 20 Teilen einer 50 %-igen wässerigen Lösung von Polymaleinsäureanhydrid (MG 600), 9 Teilen Dinatriumsalz des Bi-(6-sulphonaphthyl-2)-methans und 15 Teilen Natriumsalz eines sauren Phosphorsäureesters eines Fettalkoholpolyethoxylates und
• 40 ml einer 30 %-igen wässerigen Natriumhydroxidlösung.
• Hierauf wird die Druckfarbe mit 16 g Natriumhydrosulfit verküpt und in einem geschlossenen System über ein Schaumaggregat mit Stickstoff verschäumt. Der Verschäumungsgrad beträgt 1 : 8.
• Dieser Schaum wird unter Druck durch Rohrleitungen über eine Siebschablone auf ein Baumwollgewebe gepresst. Alsdann wird das Gewebe an der Luft oxidiert und anschliessend gespült, geseift, wieder gespült und getrocknet.
• Man erhält einen scharfstehenden hellen grünen Druck mit guten Gebrauchsechtheiten.
• Ähnlich gute Farbdrucke erhält man, wenn an Stelle des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates gleiche Mengen der gemäss Vorschriften 1 und 4 hergestellten Pfopfpolymerisaten eingesetzt werden.

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

• 10 g of the Vat Green 1 CI 59 825 dye
• 100 g of an aqueous mixture containing 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.
• 15 g of the graft polymer prepared according to regulation 2
• 5 g of a mixture of 20 parts of a 50% aqueous solution of polymaleic anhydride (MW 600), 9 parts of disodium salt of bi- (6-sulphonaphthyl-2) methane and 15 parts of sodium salt of an acidic phosphoric acid ester of a fatty alcohol polyethoxylate and
• 40 ml of a 30% aqueous sodium hydroxide solution.
• The printing ink is then coated with 16 g of sodium hydrosulfite and foamed with nitrogen in a closed system using a foam unit. The degree of foaming is 1: 8.
• This foam is pressed under pressure through pipelines over a screen template onto a cotton fabric. The tissue is then oxidized in air and then rinsed, soaped, rinsed and dried.
• A sharp, bright green print with good fastness properties is obtained.
• Color prints of similar quality are obtained if, instead of the graft polymer prepared according to regulation 2, the same amounts of the graft polymers prepared according to regulations 1 and 4 are used.

Example 4:

• 25 g des Vat green 1 C. I. 59 825,
• 5 g einer Mischung aus dem Di-(ß-hydroxyethyl-)aminsalz des sauren Schwefelsäureesters des Anlagerungsproduktes von 3 Mol Ethylenoxid an 1 Mol Laurylalkoho und
• Kokosfettsäure-N-di-ß-hydroxylethylamid (1 : 1)
• 5 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,
• 5 g einer Mischung aus
• Teilen einer 50 %-igen wässerigen Lösung von Polymaleinsäureanhydrid (MG 600),
• 9 Teilen Dinatriumsalz des Di-(6-sulphonaphthyl-2)-methans und 15 Teilen Natriumsalz eines sauren Phosphorsäureesters eines Fettalkoholpolyethoxylates und
• 50 ml einer 30 %-igen wässerigen Natriumhydroxidlösung.
• Hierauf wird die Druckf arbe mit 25 g Natriumhydrosulfit verküpt und in einem geschlossenen System über ein Schaumaggregat mit Stickstoff verschäumt. Der Verschäumungsgrad beträgt 1 : 13.
• Dieser Schaum wird unter Druck durch Rohrleitungen über eine Siebschablone auf ein Baumwollgewebe gepresst. Alsdann wird das Gewebe 30 Sekunden bei 102°C gedämpft, an der Luft oxidiert und anschliessend gespült, geseift, wieder gespült und getrocknet.
• Man erhält einen egalen grünen Druck mit guten Gebrauchsechtheiten.

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

• 25 g of Vat green 1 CI 59 825,
• 5 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-ß-hydroxylethylamide (1: 1)
• 5 g of a mixture of
• 13 parts of the addition product quaternized with dimethyl sulfate of 1 mol of styrene oxide and 15 mol of ethylene oxide and 1 mol of oleylamine,
• 13 parts of dibutylnaphthalenesulfonic acid and 7 parts of the adduct of 80 moles of ethylene oxide and 1 mole of oleyl alcohol,
• 5 g of a mixture of
• Dividing a 50% aqueous solution of polymaleic anhydride (MW 600),
• 9 parts of disodium salt of di- (6-sulphonaphthyl-2) methane and 15 parts of sodium salt of an acidic phosphoric acid ester of a fatty alcohol polyethoxylate and
• 50 ml of a 30% aqueous sodium hydroxide solution.
• The printing ink is then coated with 25 g of sodium hydrosulfite and foamed with nitrogen in a closed system using a foam unit. The degree of foaming is 1:13.
• This foam is pressed under pressure through pipelines over a screen template onto a cotton fabric. The fabric is then steamed at 102 ° C for 30 seconds, oxidized in air and then rinsed, soaped, rinsed again and dried.
• You get a level green print with good fastness properties.

Claims (20)

1. A process for dyeing or printing cellulose-containing textile material with vat dyes, which comprises using in the absence of air a foamed aqueous preparation which contains dye, foam-forming agent, alkalis, reducing agent and 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 in the form of an aqueous solution per litre of unfoamed preparation.

3. A process according to either of Claims 1 and 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 which is obtainable by graft polymerisation of acrylamide or methacrylamide on an adduct of 4 to 100 mol, preferably 40 to 80 mol, 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 mol of propylene oxide on 1 mol 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 mol of propylene oxide on 1 mol 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 the foam-forming 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 mol of ethylene oxide on 1 mol of these fatty alcohols.

10. A process according to any one of Claims 1 to 8, wherein the preparation contains as the foam-forming agent a mixture of adducts of 2 to 12 mol of ethylene oxide on 1 mol of alkylphenol having 4 to 12 carbon atoms in the alkyl moiety, sodium salts of sulfate 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.

11. A process according to any one of Claims 1 to 8, wherein the preparation contains as the foam-forming agent a mixture of adducts of 1 to 15 mol of ethylene oxide on 1 mol 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 the foam-forming agent a mixture of sodium salts of sulfate 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 if desired adducts of 1 to 4 mol of ethylene oxide on C₁₂-C₂₂-fatty alcohols.

13. A process according to any one of Claims 1 to 8, wherein the preparation contains as the foam-forming agent a mixture of sodium salts of sulfate 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 if desired in addition the disodium salt of 1-benzyl-2-C₁₇-C₁₈-alkylbenzimidazoledisulfonic acid.

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

15. A process according to any one of Claims 1 to 8, wherein the preparation contains as the foam-forming agent a mixture of a sulfate ester or its salts of an adduct of 2 to 15 mol of ethylene oxide on 1 mol 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 if desired an adduct of 2 to 80 mol of ethylene oxide on 1 mol of fatty alcohol having 12 to 22 carbon atoms and/or an adduct, quaternised with dimethyl sulfate, of 1 mol of styrene oxide and 10 to 30 mol of ethylene oxide on one mol of fatty amine having 12 to 22 carbon atoms.

16. A process according to any one of Claims 1 to 15, wherein the foamed preparation is used in a nitrogen atmosphere.

17. A process according to any one of Claims 1 to 16, wherein printing is effected by means of a screenprinting machine.

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

19. An aqueous preparation for dyeing or printing cellulose-containing textile material with vat dyes, which contains dye, foam-forming agent, reducing agent, alkalis and 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.

20. An aqueous preparation according to claim 19, in foamed form.