EP0246184A2 - Process for printing or dyeing cellulosic textiles - Google Patents

Abstract

Textile cellulose material is printed or dyed with the help of foam with reactive dyes. The foam is applied by applying a foamed, aqueous preparation to the cellulose material which, in addition to the dye and fixing alkalis, (1) a foaming agent, (2) a homopolymer or copolymer of the acrylamide or methacrylamide or preferably a graft polymer, which preferably consists of an adduct of an alkylene oxide Propylene oxide to an at least trihydric aliphatic alcohol, such as Glycerol, and acrylamide or methacrylamide is obtained, and (3) contains a betaine-like quaternary ammonium salt, which by condensation (A) a sulfonated, asymmetric succinic acid diester, which has an ester group, a halogenohyd ring group and an etherified polyalkylene glycol group, with (B) a tertiary amine-substituted N -Alkylamide an ethylenically unsaturated aliphatic mono- or dicarboxylic acid is available. The cellulosic material thus treated is then subjected to heat treatment, e.g. by steaming. With this very stable preparation, a strong, level and sharp color print is obtained without using thickeners, especially alginates, which at the same time has an excellent handle.

Description

The present invention relates to a method for printing or dyeing cellulose-containing textile reactive dyes and using foam.

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, especially alginates, are required. The disadvantage of using the alginates is that they have to be washed out again after printing and fixing the dye. This post-wash requires considerable mechanical effort and increases the consumption of energy, water and various chemicals.

EP-A-151091 or US-A-4 604 099 propose a foam printing ink which is used with the exclusion of thickeners and gives good stability. This foam printing ink, which in addition to the dye and the foamer, homopolymers, copolymers or graft polymers based on acrylamide or methacrylic contains amide, generally has sufficient foam stability. However, due to certain dye formulations, high shear forces and long residence times in the application system, the foam stability is in some cases not sufficient.

It has now been found that foam stability can be significantly improved if cellulose-containing textile material is printed or dyed using the process set out below.

The present invention accordingly relates to a process for printing or dyeing cellulose-containing textile material with reactive dyes by printing or dyeing the textile material with a foamed, aqueous preparation and fixation of the dyes by the action of heat, the preparation comprising reactive dyes, foaming agents, fixing alkalis, homopolymers or copolymers of acrylamide or Methacrylamides or graft polymers which are obtainable from an adduct of an alkylene oxide with an at least trihydric aliphatic alcohol having 3 to 10 carbon atoms and acrylamide or methacrylamide, characterized in that the preparation additionally obtains a quaternary ammonium salt by condensation (A) of a sulfonated, asymmetric succinic acid diester, which has a halohydrin group and an etherified polyalkylene glycol group as ester groups, with (B) a tertiary amine-substituted N-alkylamide e contains in ethylenically unsaturated aliphatic mono- or dicarboxylic acid.

The condensation of components (A) and (B) is advantageously carried out at a temperature of 50 to 100 ° C, with spontaneous polymerization sometimes being able to occur.

The succinic diester (A) is prepared by first reacting maleic acid or maleic anhydride with a mono-etherified polyalkylene glycol and then with an epihalohydrin, such as epibromohydrin, β-methylepichlorohydrin or before preferably epichlorohydrin condensed to the mixed ester. The malonic diester is then sulfited with alkali disulfites, alkali pyrosulfites or alkali hydrogen sulfites to give the sulfosuccinate.

R
durchgeführt, worin
R den Rest eines alilphatischen Monoalkohols mit 4 bis 24 Kohlen­stoffatomen, vorzugsweise 8 bis 22 Kohlenstoffatomen darstellt und m 4 bis 120, vorzugsweise 8 bis 60, bedeutet.The monoesterification of maleic acid is expediently carried out using monoetherified diols of the formula
(1) HO- (CH₂CH₂O

R
carried out in which
R represents the residue of an aliphatic monoalcohol with 4 to 24 carbon atoms, preferably 8 to 22 carbon atoms and m represents 4 to 120, preferably 8 to 60.

The mono alcohol residues can be straight-chain or branched-chain. They are derived, for example, from butanols, amyl alcohols, neopentyl alcohol, hexanol, 2-ethylbutanol, 2-methylpentanol, 2-ethylhexanol, heptanol, 5-methylheptan-3-ol, octan-2-ol, caprylic alcohol, trimethylnony alcohol, decanol, lauryl alcohol , Myristyl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, arachidyl alcohol or behenyl alcohol.

Unsaturated aliphatic monoalcohols, such as e.g. Crotyl alcohol, dodecenyl alcohol, hexadecenyl alcohol or oleyl alcohol.

The mono alcohols can be used individually or as mixtures.

R in formula (1) preferably denotes alkyl having 12 to 22 carbon atoms.

Unetherified, the polyethylene glycols required for the esterification preferably have an average molecular weight of 350 to 2600, especially 660 to 2300.

worin
R₁ und R₂ je einen Alkylrest mit 1 bis 5 Kohlenstoffatomen, wie z.B. Methyl, Ethyl, Propyl, Isoproyl, n-Butyl, Isobutyl, sek.-Butyl, n-Amyl oder Isoamyl,
Q Ethylen oder vorzugsweise Propylen und
Z-CO- den Säurerest einer ethylenisch ungesättigten aliphatischen Mono- oder Dicarbonsäure mit höchstens 10 Kohlenstoffatomen bedeu­ten.The tertiary amine-substituted N-alkylamides which are suitable as component (B) for the preparation of the quaternary ammonium salts advantageously correspond to the formula

wherein
R₁ and R₂ each have an alkyl radical with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isoproyl, n-butyl, isobutyl, sec-butyl, n-amyl or isoamyl,
Q is ethylene or preferably propylene and
Z-CO means the acid residue of an ethylenically unsaturated aliphatic mono- or dicarboxylic acid with at most 10 carbon atoms.

The ethylenically unsaturated monocarboxylic acids are e.g. acrylic acid, methacrylic acid, α-haloacrylic acid, 2-hydroxyethylacrylic acid, 2-cyanoacrylic acid, crotonic acid, vinyl acetic acid, vinyl propionic acid, allyl acetic acid or allyl hydroxypropionic acid.

Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid, furthermore mesaconic acid, citraconic acid, glutaconic acid or methylene malonic acid.

worin
R₃ und R₄ jeweils Methyl, Ethyl oder Propyl und
R₅ Wasserstoff oder Methyl
bedeuten.Particularly preferred components (B) correspond to the formula

wherein
R₃ and R₄ are each methyl, ethyl or propyl and
R₅ is hydrogen or methyl
mean.

Component (B) can be prepared in a conventional manner by reacting an N, N-disubstituted alkylenediamine with a halide of an ethylenically unsaturated aliphatic mono- or dicarboxylic acid, for example with acryloyl chloride or methacryloyl chloride.

The amounts in which such quaternary ammonium salts are added to the preparations to be foamed, alone or as a mixture, can range from 1 to 30 g / l in the form of 10 to 25% strength aqueous solutions, depending on the printing or dyeing process. Quantities of 3 to 15 g in the form of 20% aqueous solutions per liter of non-foamed preparation have proven to be advantageous.

The acrylamide or methacrylamide-based polymers used according to the invention are preferably the acrylamide graft polymers as defined.

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 acrylamide 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 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. Details on the preparation of the acrylamide graft polymers are e.g. in European Patent Publication 151091 or in US-A-4,494,4956.

The amounts used in which the required acrylamide polymers are added to the preparations to be foamed, alone or as a mixture, can, depending on the printing or dyeing process, move between 0.5 to 30 g / l in the form of aqueous solutions. 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 non-foamed preparation have proven to be advantageous.

Instead of the acrylamide graft polymers mentioned, linear or branched polymers of acrylic acid amide or methacrylic acid amide as well as copolymers of acrylic acid amide or methacrylic acid amide and other ethylenically unsaturated monomers, such as e.g. Acrylic acid, methacrylic acid, α-haloacrylic acid, 2-hydroxyethylacrylic acid, α-cyanoacrylic acid, crotonic acid, vinyl acetic acid, maleic acid, acrylonitrile, methacrylonitrile, vinyl alkyl ether, (methyl vinyl ether, isopropyl vinyl ether), vinyl ester (vinyl acetate), styrene, vinyl toluene, vinyl sulfido acid, 2-acrylamido acid, 2-acrylic acid -methylpropanesulfonic acid or esters of the above-mentioned α, β-unsaturated carboxylic acids and especially half-esters of maleic acid with adducts of 2 to 15 moles of ethylene oxide with monoalcohols with 8 to 22 carbon atoms. The weight ratio of the acrylic acid amide to the other monomers is preferably from 9: 1 to 1: 1.

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:
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;
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, mol, 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. 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.

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 oxide, 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 of a fatty acid having 8 to 22 carbon atoms and a primary or secondary amine or alkylene oxide addition products containing these hydroxyalkyl group-containing reaction products, which have at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, the reaction taking place in such a way that the molecular quantitative ratio between hydroxyalkylamine and fatty acid is 1: 1 and can be greater than 1, for example 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 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, insbesondere das Anlagerungs­produkt von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol;
• (6) Fettsäurealkanolamide 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 having 8 to 22 carbon atoms or with 1 mole of alkylphenol with a total of 4 to 12 carbon atoms in the alkyl part, in particular the adduct of 2 moles of ethylene oxide with 1 mole of cetyl alcohol;
• (6) Fatty acid alkanolamides with 8 to 22 carbon atoms in the fatty acid residue and 2 to 6 carbon atoms in the alkanol part.

worin Rʹ Wasserstoff, Alkyl oder Alkenyl mit höchstens 22 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 und die Summe von n₁ + n₂ 3 bis 50, vorzugsweise 3 bis 30 und von y₁ + 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

wherein Rʹ is hydrogen, alkyl or alkenyl with at most 22 carbon atoms, preferably 8 to 16 carbon atoms, o-phenylphenyl or alkylphenyl with 4 to 12 carbon atoms in the alkyl part, of Z₁ and Z₂ a hydrogen and the other methyl, y 1 to 75, preferably 3 to 50 and x is 1 to 30 and the sum of n₁ + n₂ is 3 to 50, preferably 3 to 30 and y₁ + y₂ is 2 to 30, preferably 4 to 20 and n₂ and y₂ can also be 0.

Preferred block polymers of the formula (4) are those in which Rʹ is alkyl or alkenyl of 4 to 18, preferably 8 to 16 carbon atoms, y 1 to 30, preferably 3 to 15, n₁ 3 to 30 and n₂ 0.

Particularly advantageous block polymers are fatty alcohol polyglycol mixed ethers, in particular addition products of 3 to 30 moles of ethylene oxide and 3 to 30 moles of propylene oxide with aliphatic monoalcohols of 8 to 22 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 300 to 7000, in particular 350 to 3500.

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 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 cation-active quaternary ammonium salts. The latter can e.g. by reacting aliphatic fatty amines whose alkyl or alkenyl radicals have 8 to 24 carbon atoms, e.g. Dodecylamine, hexadecylamine, heptadecylamine, octadecylamine, tallow fatty amine, behenylamine or oleylamine or di- and triamines, e.g. Dodecylpropylenediamine, octadecylethylenediamine and octadecyldiethylenetriamine with 1 to 35 equivalents of an alkylene oxide, e.g. 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 e.g. Methyl, ethyl or benzyl halide, diethyl sulfate and especially dimethyl sulfate, halohydrins, halocarboxamides, such as e.g. Chloroacetamide.

Mixtures of these cationic auxiliaries can also be used.

Particularly suitable cationic auxiliaries have been found with dimethyl sulfate, diethyl sulfate or C₁-C₂ alkyl halides, e.g. 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 with 12 to 24 carbon atoms or a mixture thereof have been proven.

• (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 und 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 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 1 Mol 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 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) adducts of 1 to 15 moles of ethylene oxide with 1 mole of fatty alcohol with 12 to 22 carbon atoms and 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- C₁₇-C₁₈-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 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 in which the foaming agents, preferably in the form of mixtures, are added to the preparations vary, depending on the printing or dyeing process, between 5 and 200 g, preferably between 10 and 100 g, per liter of treatment preparation 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 the dyes generally depends on the desired color strength and is expediently 1 to 400 g per liter of preparation, advantageously 5 to 300 and preferably 10 to 200 g / l of preparation (printing ink or dye liquor).

The preparations generally contain alkalis to fix the reactive dyes. Examples of alkaline compounds are sodium carbonate, 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 preparations containing alkali is generally 7.5 to 13.2, preferably 8.5 to 11.5.

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

Suitable cellulose material is regenerated or, in particular, natural cellulose, such as Cellulose, viscose silk, cellulose acetate, hemp, linen, jute or preferably cotton, as well as fiber mixtures e.g. those made of polyamide / cotton or in particular polyester / cotton, it being possible for the polyester portion to be printed or dyed 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 or dyeing liquors to be foamed are expediently prepared by dissolving the dye and by adding the betaine-like quaternary ammonium salts, the acrylamide polymers, the foaming agents and alkali. Depending on the dye used, the printing inks or dyeing liquors can contain other conventional additives, such as Electrolytes, glycerin, urea, oxidizing agents e.g. Contain nitrobenzenesulfonate or sodium chlorate, sequestering agents or, depending on the printing ink or dye liquor, 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, foams which have a liter weight of 65 to 350 g, preferably 150 to 250 g, have proven to be suitable.

The foams used according to the invention are distinguished by the fact that they are thick, dense and stable, ie they are durable and usable over a long period of time. They preferably have according to the invention foams used a drop exit time (TAZ) of 30 minutes to 100 hours, preferably 1 to 50 hours. The bubble diameters in the foams are approximately 1 to 150 µ.

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. Film or rotary printing machines. The foam is advantageously applied by means of a screen printing machine, preferably in a closed system. Such systems are described for example in DE-OS -en 3 034 802 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 foaming the treatment preparation in a suitable device in a closed system, for example under pressure, and transporting the generated foam to the application device by means of pipelines. Then the foam, preferably through a Sieve or a sieve-like intermediate carrier, applied to the textile fabric, whereupon the foam is sucked into the goods by mechanical pressing in, pressing in or doctoring. 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 or dyed textile material is preferably dried and then subjected to a heat treatment process in order to complete the dyeings (or to fix the dye).

The heat treatment 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 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 100 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 prints or dyeings can be finished by means of the so-called thermal insulation process after or without intermediate drying, for example 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 an 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. 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. 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 distinguished by improved sharpness, a good handle and an excellent product appearance. Furthermore, the fastness to use of the colored goods, such as Light fastness, fastness to rubbing and wet fastness are not negatively influenced by the use of the defined betaine-like quaternary ammonium salts and acrylamide polymers.

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. When using the defined betaine-like quaternary ammonium salts with the acrylamide polymers, good foam stability is achieved, which lasts at least 24 hours.

In the following regulations, manufacturing examples and application examples, parts and percentages, unless stated otherwise, each relate to the weight.

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

Instructions 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 3 Heated at this temperature for hours. 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. This gel, measured at 25 ° C, has a viscosity of 112957 mPas.

Instructions 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 initially introduced and with stirring and passing nitrogen over to 50 ° C warmed and held 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 to, cools to room temperature with stirring, and receives 1794 g of a free-flowing gel with a polymer content of 4.3%. Measured at 25 ° C, this gel has a viscosity of 64202 mPas.

Rule 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 kept 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 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 75300 mPas.

Rule 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 kept at this temperature for 3 hours. 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 96750 mPas.

Instructions 5: If the addition product specified in instruction 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. This gel, measured at 25 ° C, has a viscosity of 19500 mPas.

Instructions 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 passing over nitrogen and at 4 hours kept at this temperature. 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 25750 mPas.

Instructions 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. with stirring and passing over nitrogen and at 3 hours kept at this temperature. 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 16300 mPas.

Instructions 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 peroxydisulfate in 150 g of water is heated to 50 ° C. with stirring and passing over nitrogen and at this temperature for 4 hours held. 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 chloroacet is added to the gel amide and 0.4 g of hydroquinone monomethyl ether in 347 g of water and receives 519 g of a gel with a polymer content of 4.2%. Measured at 25 ° C, this gel has a viscosity of 15582 mPas.

Manufacturing examples:

Example 1: 488 g of the adduct of 50 moles of ethylene oxide and 1 mole of stearyl alcohol (molecular weight 2440) and 19.6 g of maleic anhydride are melted and mixed with 0.01 ml of tri-n-butylamine. The reaction mixture is then stirred at 80 ° C. for 2 hours. Then 20 g of epichlorohydrin are added dropwise, after which the mixture is stirred at 80 ° C. for a further 1 1/2 hours. The excess epichlorohydrin is then removed in a water jet vacuum and the reaction product is cooled to room temperature. Then 100 ml of water are added and 18 g of sodium pyrosulfite in 30 ml of water are added dropwise. The new mixture is heated to 80 ° C., kept at this temperature for 1 hour, 34.5 g of N- (dimethylaminopropyl) methacrylamide are also added dropwise, and the mixture is rinsed with 10 ml of water. The reaction mixture is kept at 80 ° C. for 2 hours, a viscous resin being formed. 2180 g of water are added, the mixture is stirred at 50 ° C. for 24 hours and a clear, highly viscous solution having a solids content of 20% is obtained. Yield: 2900 g, reduced viscosity: 0.09 dl / g.

If, instead of the adduct of 50 moles of ethylene oxide with stearyl alcohol, an adduct of 8 moles or 15 moles of ethylene oxide with 1 mole of stearyl alcohol and instead of N- (dimethylaminopropyl) methacrylamide N- (dimethylyaminopropyl) acrylamide, two further betaine-like quaternary ammonium salts are obtained, which are based on acrylamide derivatives.

Example 2: 45.8 g of the adduct of 15 moles of ethylene oxide with 1 mole of a linear C₁₆-C₁₈ alcohol (Alfol) (molecular weight 917.3), 4.9 g of maleic anhydride, and 0.01 ml of tril-n-butylamine heated to 70 ° C, whereupon a melt is formed which is kept at 70 ° C for 1 1/2 hours. Then leave 5.0 g Add epichlorohydrin dropwise and stir the mixture for a further 3 hours at 70 ° C. The excess epichlorohydrin is then removed in a water jet vacuum. Then 8.5 g of N- (dimethylaminopropyl) methacrylamide are added dropwise and the mixture is stirred at 70 ° C. for 30 minutes. The temperature is reduced to 60 ° C., the resin formed is dissolved in 213 g of water and then a solution of 5.2 g of sodium pyrosulfite in 64.5 g of water is added dropwise. The mixture is stirred for 30 minutes, cooled to room temperature, 0.2 g of 2,2′-azobis- (2-amidinopropane) hydrochloride is added, the mixture is heated again to 60 ° C. and kept at this temperature for 1 hour. 386.5 g of a clear yellow solution with a solids content of 20.5% are obtained. Reduced viscosity: 0.04 dl / g.

Examples of use Example 1:

200 g einer wässerigen Mischung, die 30 g eines Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,1 g Natrium­laurylsulfat enthält,
20 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
5 g des 20%igen, gemäss Beispiel 1 hergestellten quaternären Ammo­niumsalzes,
10 g des Natriumsalzes von m-Nitrobenzolsulfonsäure,
100 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:
90 g of a dye of the formula

200 g of an aqueous mixture which contains 30 g of an adduct of 2 moles of ethylene oxide with 1 mole of cetyl alcohol and 0.1 g of sodium lauryl sulfate,
20 g of the graft polymer prepared according to regulation 2,
5 g of the 20% quaternary ammonium salt prepared according to Example 1,
10 g of the sodium salt of m-nitrobenzenesulfonic acid,
100 g of a 25% aqueous sodium carbonate solution and
100 g urea
contains.

The printing ink is then foamed in a closed system using a foam unit. The foam has a liter weight of 192 g and a drop exit time of over 48 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 2.5 bar. The printed fabric is then dried, 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 and of polyacrylamide in the form of a 4% aqueous solution with a viscosity of 28,000 cps, measured at 25% C, be used.

Example 2

5 g eines Farbstoffes der Formel

200 g einer wässerigen Mischung, die 30,0 g eines Anlagerungsproduk­tes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,1 g Natriumlaurylsulfat enthält,
20 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
10 g des Natriumsalzes von m-Nitrobenzolsulfonsäure,
5 g des 20%igen, gemäss Beispiel 1 hergestellten quaternären Ammoniumsalzes,
100 g einer 25%igen wässerigen Natriumcarbonatlösung und
100 g Harnstoff
enthältA printing ink is produced which contains the following additives in 1 liter of water:
75 g of a dye of the formula

5 g of a dye of the formula

200 g of an aqueous mixture containing 30.0 g of an adduct of 2 moles of ethylene oxide with 1 mole of cetyl alcohol and 0.1 g of sodium lauryl sulfate,
20 g of the graft polymer prepared according to regulation 2,
10 g of the sodium salt of m-nitrobenzenesulfonic acid,
5 g of the 20% quaternary ammonium salt prepared according to Example 1,
100 g of a 25% aqueous sodium carbonate solution and
100 g urea
contains

The printing ink is then foamed in a closed system using a foam unit. The foam has a weight of 175 g. Drop exit time: 48 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 2.5 bar. The printed fabric is then dried, steamed at 101 ° C. for 8 minutes, then rinsed as usual and dried again.

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

Example 3

10 g eines Farbstoffes der Formel (15)

5 g des 20%igen, gemäss Beispiel 1 hergestellten quaternären Ammo­niumsalzes,
200 g einer wässerigen Mischung, die 30 g eines Anlagerungsproduktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,1 g Natrium­laurylsulfat enthält,
20 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
10 g m-Nitrobenzolsulfonsäure-Natriumsalz,
100 g einer 25%igen wässerigen Natriumcarbonatlösung und
100 g Harnstoff
enthältA printing ink is produced which contains the following additives in 1 liter of water:
100 g of a dye of the formula

10 g of a dye of the formula (15)

5 g of the 20% quaternary ammonium salt prepared according to Example 1,
200 g of an aqueous mixture which contains 30 g of an adduct of 2 moles of ethylene oxide with 1 mole of cetyl alcohol and 0.1 g of sodium lauryl sulfate,
20 g of the graft polymer prepared according to regulation 2,
10 g m-nitrobenzenesulfonic acid sodium salt,
100 g of a 25% aqueous sodium carbonate solution and
100 g urea
contains

The printing ink is then foamed in a closed system using a foam unit. The foam has a liter weight of 238 g. Drop exit time: 50 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 2.5 bar. The printed fabric is then dried, steamed at 101 ° C. for 8 minutes, then soaped as usual and dried again.

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

Example 4:

Two separate printing inks are produced, each containing the following additives in 1 liter of water:

Printing ink (A)

66 g of the yellow dye of the formula (13)
150 g of an aqueous mixture which contains 30 g of an adduct of 2 moles of ethylene oxide and 1 mole of cetyl alcohol and 0.1 g of sodium lauryl sulfate,
50 g of the graft polymer prepared according to regulation 2,
5 g of the 20% quaternary ammonium salt prepared according to Example 1,
10 g of the sodium salt of m-nitrobenzenesulfonic acid,
100 g of a 25% aqueous sodium carbonate solution and
100 g urea.

Printing ink (B)

150 g einer wässerigen Mischung, die 30 g eines Anlagerungspro­duktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,1 g Natriumlaurylsulfat enthält,
50 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
5 g des 20%igen, gemäss Beispiel 1 hergestellten quaternären Ammoniumsalzes,
10 g des Natriumsalzes von m-Nitrobenzolsulfonsäure,
100 g einer 25%igen Natriumcarbonatlösung und
100 g Harnstoff60 g of the blue dye of the formula

150 g of an aqueous mixture which contains 30 g of an adduct of 2 moles of ethylene oxide and 1 mole of cetyl alcohol and 0.1 g of sodium lauryl sulfate,
50 g of the graft polymer prepared according to regulation 2,
5 g of the 20% quaternary ammonium salt prepared according to Example 1,
10 g of the sodium salt of m-nitrobenzenesulfonic acid,
100 g of a 25% sodium carbonate solution and
100 g urea

Both printing inks are then foamed separately in a closed system using a foam unit. The foam of the printing ink (A) has a liter weight of 130 g and a drop exit time (TAZ) of 48 hours. With the printing ink (B), the foam has a liter weight of 115 g and TAZ is 48 hours.

Using a duplex system, both foams are pressed onto a cotton fabric with a pressure of 2.5 bar using a suitable screen template, printing ink (A) on the front and printing ink (B) on the back of the same fabric. The fabric printed on both sides is then dried, steamed at 101 ° C. for 8 minutes, then soaped and dried as usual. The two-sided printing is also completed without intermediate drying.

You get a strong, level and sharp yellow and blue print with a good grip on both sides and good fastness to use.

in 50 %iger flüssiger Form,
150 g einer wässerigen Mischung, die 22,5 g eines Anlagerungspro­duktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,11 g Natriumlaurylsulfat enthält,
20 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
3 g des 20%igen gemäss Beispiel 1 hergestellten quaternären Ammo­niumsalzes,
10 g des Natriumsalzes von m-Nitrobenzolsulfonsäure,
100 g einer 25%igen wässerigen Natriumcarbonatlösung und
100 g Harnstoff
enthält Example 5: A printing ink is produced which contains the following additives in 1 liter of water:
150 g of a dye of the formula

in 50% liquid form,
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 0.11 g of sodium lauryl sulfate,
20 g of the graft polymer prepared according to regulation 2,
3 g of the 20% quaternary ammonium salt prepared according to Example 1,
10 g of the sodium salt of m-nitrobenzenesulfonic acid,
100 g of a 25% aqueous sodium carbonate solution and
100 g urea
contains

The printing ink is then foamed in a closed system using a foam unit. The foam has a liter weight of 192 g and a drop exit time of over 48 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 2.5 bar. The printed fabric is then dried, steamed at 102 ° C. for 8 minutes, then soaped and dried as usual.

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

Similar good color prints are achieved when instead of sodium lauryl sulfate
0.15 g of the adduct of 1 mol of 1-p-tert-octylphenol and 8 mol of ethylene oxide or
0.18 g of sodium dodecylbenzenesulfonate or
0.2 g coconut fatty acid diethanolamide
be used.

jeweils in 40 % flüssiger Form und im Mischungsverhältnis 1:1:1,
150 g einer wässerigen Mischung, die 22,5 g eines Anlagerungspro­duktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,11 g Natriumlaurylsulfat enthält,
20 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
7,5 g des gemäss Beispiel 2 hergestellten quaternären Ammonium­salzes,
10 g des Natriumsalzes von m-Nitrobenzolsulfonsäure,
100 g einer 25%igen wässerigen Natriumcarbonatlösung und
100 g Harnstoff
enthält Example 6: A printing ink is produced which contains the following additives in 1 liter of water:
400 g of a dye mixture from the dyes of the formulas (14), (17) and (18)

each in 40% liquid form and in a mixing ratio of 1: 1: 1,
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 0.11 g of sodium lauryl sulfate,
20 g of the graft polymer prepared according to regulation 2,
7.5 g of the quaternary ammonium salt prepared according to Example 2,
10 g of the sodium salt of m-nitrobenzenesulfonic acid,
100 g of a 25% aqueous sodium carbonate solution and
100 g urea
contains

The printing ink is then foamed in a closed system using a foaming unit. The foam has a liter weight of 192 g and a drop exit time of over 48 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 2.5 bar. The printed fabric is then dried, steamed at 102 ° C. for 8 minutes, then soaped and dried as usual.

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

in 50 % flüssiger Form,
150 g einer wässerigen Mischung, die 22,5 g eines Anlagerungspro­duktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,11 g Natriumlaurylsulfat enthält,
20 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
3 g des gemäss Beispiel 1 hergestellten quaternären Ammonium­salzes und
50 g Harnstoff
enthält Example 7: A printing ink is produced which contains the following additives in 1 liter of water:
240 g of a dye of the formula

in 50% liquid form,
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 0.11 g of sodium lauryl sulfate,
20 g of the graft polymer prepared according to regulation 2,
3 g of the quaternary ammonium salt prepared according to Example 1 and
50 g urea
contains

The printing ink is then foamed in a closed system using a foam unit. The foam has a liter weight of 169 g and a drop exit time of over 48 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 2.5 bar, printed and dried. Then the printed fabric is placed in a foulard with a liquor in liters
100 g of table salt
150 g soda
70 g potash and
Contains 50 g NaOH 36 ° Bé,
treated (liquor absorption 80%) and then steamed at 102 ° C for 8 minutes, soaped and dried as usual.

You get a bright, level yellow print with an excellent handle and good fastness to use.

in 50 % flüssiger Form,
150 g einer wässerigen Mischung, die 22,5 g eines Anlagerungspro­duktes von 2 Mol Ethylenoxid an 1 Mol Cetylalkohol und 0,11 g Natriumlaurylsulfat enthält,
20 g des gemäss Vorschrift 2 hergestellten Pfropfpolymerisates,
3 g des gemäss Beispiel 1 hergestellten quaternären Ammonium­salzes und
50 g Harnstoff
enthält. Example 8: A printing ink is produced which contains the following additives in 1 liter of water:
40 g of a dye of the formula

in 50% liquid form,
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 0.11 g of sodium lauryl sulfate,
20 g of the graft polymer prepared according to regulation 2,
3 g of the quaternary ammonium salt prepared according to Example 1 and
50 g urea
contains.

The printing ink is then foamed in a closed system using a foam unit. The foam has a liter weight of 200 g and a drop exit time of over 48 hours.

This foam is pressed through pipes through a screen template onto a cotton fabric with a pressure of 2.5 bar. The printed fabric is then dried, 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.

Claims (18)

1. Process for printing or dyeing cellulose-containing textile material with reactive dyes by printing or dyeing the textile material with a foamed, aqueous preparation and fixing the dyes by exposure to heat, the preparation comprising reactive dyes, foaming agents, fixing alkalis, homopolymers or copolymers of acrylamide or methacrylamide or graft polymer, or graft. which is obtainable from an adduct of an alkylene oxide with an at least trihydric aliphatic alcohol having 3 to 10 carbon atoms and acrylamide or methacrylamide, characterized in that the preparation additionally contains a quaternary ammonium salt by condensation
(A) a sulfonated, asymmetric succinic diester which has a halohydrin group and an etherified polyalkylene glycol group as ester groups
(B) contains a tertiary amine-substituted N-alkyl amide of an ethylenically unsaturated aliphatic mono- or dicarboxylic acid. 2. The method according to claim 1, characterized in that the succinic diester (A) with a mono-etherified diol of the formula
(1) HO- (CH₂CH₂O

R
wherein R is the residue of an aliphatic monoalcohol having 4 to 24 carbon atoms, preferably 8 to 22 carbon atoms and m 4 to 120, has been obtained. 3. The method according to any one of claims 1 and 2, characterized in that component (B) is a tertiary amine-substituted N-alkyl amide of the formula

wherein
R₁ and R₂ each represent an alkyl radical with 1 to 5 carbon atoms,
Q ethylene or propylene and
Z-CO- is the acid residue of an ethylenically unsaturated aliphatic mono- or dicarboxylic acid with at most 10 carbon atoms. 4. The method according to any one of claims 1 to 3, characterized in that component (B) is a tertiary amine-substituted N-alkyl amide of the formula (3)

wherein
R₃ and R₄ are each methyl, ethyl or propyl and
R₅ is hydrogen or methyl
mean is 5. The method according to any one of claims 1 to 4, characterized in that the preparation is a graft polymer which is obtainable by graft polymerization of acrylamide or methacrylamide onto an adduct of 40 to 80 mol of propylene oxide with a trihydric to hexavalent alkanol having 6 to 6 carbon atoms , contains. 6. The method according to claim 5, characterized in that the graft polymer contains 4 to 20 wt .-% of the adduct of 40 to 80 mol propylene oxide with 1 mol glycerol and 80 to 96 wt .-% grafted acrylamide, based on the graft polymer. 7. The method according to any one of claims 1 to 6, characterized in that the preparation as a foaming agent contains a mixture of alkyl sulfonates with 8 to 10 carbon atoms and fatty alcohols with 12 to 22 carbon atoms or addition products of 1 to 4 moles of ethylene oxide with 1 mole of these fatty alcohols. 8. The method according to any one of claims 1 to 6, characterized in that the preparation contains a mixture of addition products of 1 to 15 moles of ethylene oxide and 1 mole of fatty alcohol with 12 to 22 carbon atoms and fatty acid diethanolamides with 8 to 18 carbon atoms in the fatty acid residue as a foaming agent. 9. The method according to any one of claims 1 to 8, characterized in that the printing is carried out by means of a screen printing machine. 10. The method according to claim 9, characterized in that the preparation is applied to a sieve or sieve-like intermediate carrier and is pressed through the sieve or sieve-like intermediate carrier. 11. The method according to any one of claims 1 to 10, characterized in that the fixation of the dyes is carried out by steaming. 12. The method according to any one of claims 1 to 11, characterized in that the fixing of the dyes is carried out by the thermosol process. 13. Quaternary ammonium salt, which by condensation
(A) a sulfonated, asymmetric succinic diester which has a halohydrin group and an etherified polyalkylene glycol group as ester groups
(B) a tertiary amine-substituted N-alkyl amide of an ethylenically unsaturated aliphatic mono- or dicarboxylic acid is available. 14. Ammonium salt according to claim 13, characterized in that the succinic diester (A) has an etherified polyalkylene glycol group, which is derived from a mono-etherified diol of the formula
(1) HO- (CH₂CH₂O

R
wherein R derives the residue of an aliphatic monoalcohol having 4 to 24 carbon atoms, preferably 8 to 22 carbon atoms and m 4 to 120. 15. ammonium salt according to claim 16, characterized in that in formula (1) R is an alkyl radical having 12 to 22 carbon atoms. 16. Ammonium salt according to one of claims 13 to 15, characterized in that component (B) is an N-substituted amide of the formula

wherein
R₁ and R₂ each represent an alkyl radical with 1 to 5 carbon atoms,
Q ethylene or propylene and
Z-CO- is the acid residue of an ethylenically unsaturated aliphatic mono- or dicarboxylic acid with at most 10 carbon atoms. 17. Ammonium salt according to one of claims 13 to 16, characterized in that component (B) is an N-substituted amide of the formula

wherein
R₃ and R₄ are each methyl, ethyl or propyl and
R₅ is hydrogen or methyl
mean is. 18. Ammonium salt according to one of claims 13 to 17, characterized in that it is the condensation product of a sulfonated succinic diester, which is esterified with an adduct of 50 moles of ethylene oxide with 1 mole of stearyl alcohol and epichlorohydrin, and N- (dimethylaminopropyl) methacrylamide.