EP0102923A1 - Detergent for washing fibre-reactive dyeings, and resultant washing process - Google Patents

Abstract

Aqueous detergent, characterized in that it is (A) an alkali aluminum silicate, (B) an anionic surfactant, (C) an aliphatic monoalcohol with 5 to 18 carbon atoms, a fatty acid / alkanolamine reaction product or an alkylene oxide adduct from the monoalcohols or fatty acid / alkanolamine mentioned Reaction products or from fatty acids having 8 to 22 carbon atoms, trihydric to hexavalent aliphatic alcohols or optionally substituted phenols and (D) an aqueous solution or dispersion of carboxyl-containing polymers. This detergent is used when washing prints or dyeings with reactive dyes on cellulosic fiber materials.

Description

The present invention relates to an aqueous detergent which can be used when washing prints or dyeings with reactive dyes on cellulose-containing textile materials, and to a corresponding washing process. The detergent according to the invention is particularly suitable if the after-washing is carried out with mineral-rich, "hard" water.

• (A) ein Alkalialuminiumsilikat,
• (B) ein anionisches Tensid,
• (C) einen aliphatischen Monoalkohol mit 5 bis 18 Kohlenstoffatomen oder ein Fettsäure/Alkanolamin-Umsetzungsprodukt oder deren AlkylenoxidAddukte,oder Addukte aus Fettsäuren mit 8 bis 22 Kohlenstoffatomen, drei- bis sechswertigen aliphatischen Alkoholen oder gegebenenfalls substituierten Phenolen und Alkylenoxiden und
• (D) eine wässerige Lösung oder Dispersion von carboxylgruppenhaltigen Polymerisaten

enthält.The detergent according to the invention is characterized in that it

• (A) an alkali aluminum silicate,
• (B) an anionic surfactant,
• (C) an aliphatic monoalcohol with 5 to 18 carbon atoms or a fatty acid / alkanolamine reaction product or its alkylene oxide adducts, or adducts from fatty acids with 8 to 22 carbon atoms, trihydric to hexavalent aliphatic alcohols or optionally substituted phenols and alkylene oxides and
• (D) an aqueous solution or dispersion of carboxyl-containing polymers

contains.

In addition to the components (A), (B), (C) and (D) mentioned, the detergent according to the invention may also contain additives and auxiliaries.

Components (A), (B), (C) and (D) can be present as individual compounds or as mixtures with one another.

• (A) 20 bis 60 Gewichtsprozent des Alkalialuminiumsilikates,
• (B) 0,5 bis 20 Gewichtsprozent des anionischen Tensides,
• (C) 1 bis 20 Gewichtsprozent der Komponente (C) und
• (D) 2 bis 30 Gewichtsprozent der wässerigen Komponente (D).

The aqueous detergent contains, based on the total detergent, in particular

• (A) 20 to 60 percent by weight of the alkali aluminum silicate,
• (B) 0.5 to 20 percent by weight of the anionic surfactant,
• (C) 1 to 20 percent by weight of component (C) and
• (D) 2 to 30 percent by weight of the aqueous component (D).

in der Me ein n-wertiges Alkalimetallion, vorzugsweise das Natriumion,

• n 1 oder 2,
• Y₁ eine Zahl von 0,7 bis 1,5 und
• Y₂ eine Zahl von 0,8 bis 6, vorzugsweise 1,3 bis 4 bedeuten, in Betracht.

As component (A), which is the actual active substance of the new post-washing agent, there are advantageously finely divided water-insoluble alkali aluminum silicates of the formula

in the Me an n-valent alkali metal ion, preferably the sodium ion,

• n 1 or 2,
• Y _{1 is} a number from 0.7 to 1.5 and
• Y _{2 is} a number from 0.8 to 6, preferably 1.3 to 4, into consideration.

Such aluminosilicates necessarily have a particle size of 1 to 12μ, preferably 2 to 8μ. As a rule, they have a calcium binding capacity of 100 to 200 mg CaO per gram of anhydrous active substance.

The alkali aluminum silicates used as component (A) can be prepared synthetically in a simple manner, for example by reaction of water-soluble silicates with water-soluble ones Aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials are mixed with one another or a component present in the solid state is reacted with the other component present as an aqueous solution. Mixing the two components in the solid state also gives the desired aluminum silicates in the presence of water. Alkali aluminum silicates can also be prepared from _A1 (OH) ₃ , A1 ₂ 0 ₃ or SiO ₂ by reaction with alkali silicate or aluminate solutions. Finally, such substances can also form from the melt.

The alkali aluminum silicates prepared by precipitation or converted into aqueous suspension in a finely divided state by other processes can be converted from the amorphous to the aged or to the crystalline state by heating to temperatures of 50 to 200 ° C. The amorphous or crystalline alkali aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and, if desired, at temperatures of e.g. Dry 50 to 800 ° C. As a rule, however, moist filter cakes or free-flowing suspensions of the alkali aluminum silicates are used.

Precipitation conditions can already contribute to the formation of the small particle sizes of 1-12µ, whereby the mixed aluminate and silicate solutions - which can also be fed into the reaction vessel at the same time - are exposed to strong shear forces, e.g. the suspension is stirred intensively. If crystallized alkali aluminum silicates are produced - these are preferably used according to the invention - the formation of large, possibly penetrating crystals is prevented by slowly stirring the crystallizing mass.

Nevertheless, undesirable agglomeration of crystal particles can occur during drying, so that it is advisable to use these secondary particles in a suitable manner, e.g. to remove by air sighting. Alkaline aluminum silicates obtained in the coarser state, which have been ground to the desired grain size, can also be used. For this, e.g. Mills and / or air classifiers or their combinations.

Further details on the nature of the alkali aluminum silicates which are suitable as component (A), including their preparation and preparation, are described in DE-OS 27 14 954.

The anionic surfactants of component (B) are preferably acidic derivatives of nonionic or cationic alkylene oxide adducts, such as e.g. addition products containing acidic ether groups or preferably ester groups of inorganic or organic acids of 2 to 100 mol of alkylene oxides, especially ethylene oxide and / or propylene oxide or also styrene oxide onto aliphatic hydrocarbon radicals with a total of at least 4, preferably 12, organic hydroxyl, carboxyl, amino having carbon atoms and / or amido compounds or mixtures of these substances. These acidic ethers or esters can be used as free acids or as salts, e.g. Alkali metal, alkaline earth metal, ammonium or amine salts are present.

These anionic surfactants are prepared by known methods, for example by adding at least 2 moles, preferably more than 2 moles, for example 10 to 100 moles, of ethylene oxide or propylene oxide or, alternately, in any sequence to ethylene oxide or propylene oxide and then adding the addition products etherified or esterified and, if appropriate, the ethers or the esters converted into their salts. The basic materials are higher fatty alcohols, ie alkanols or alkenols each having 8 to 22 carbon atoms, di- to hexavalent aliphatic alcohols enzylphenole of 2 to 9 carbon atoms, alicyclic alcohols, phenylphenols, _B, alkylphenols having one or more alkyl substituents, have the, or together contain at least 4 carbon atoms, fatty acids having 8 to 22 carbon atoms, amines, aliphatic and / or cycloaliphatic hydrocarbon radicals of at least 8 carbon atoms, especially fatty amines, hydroxyalkylamines, hydroxyalkylamides and aminoalkyl esters of fatty acids or dicarboxylic acids and higher alkylated aryloxycarboxylic acids.

Highly suitable anionic polyalkylene oxide adducts are acidic esters or their salts of a polyadduct of 2 to 100 mol, preferably up to 50 mol, of ethylene oxide with 1 mol of fatty alcohol with 8 to 22 carbon atoms or with 1 mol of a phenol which has at least one benzyl group, one phenyl group or preferably one Has alkyl group with at least 4 carbon atoms, such as Benzylphenol, Dibenzylphenol, Dibenzyl- (nonyl) -phenol, o-Phenylphenol, Butylphenol, Tributylphenol, Octylphenol, Nonylphenol, Dodecylphenol or Pentadecylphenol, whereby these acidic esters can be used individually or as a mixture.

worin Y Alkyl oder Alkenyl je mit 8 bis 22 Kohlenstoffatomen, Alkylphenyl mit 4 bis 16 Kohlenstoffatomen im Alkylteil oder o-Phenylphenyl, X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure wiez.B. Schwefelsäure oder Phosphorsäure oder auch den Rest einer organischen Säure und m 2 bis 40, vorzugsweise 2 bis 15 bedeuten. Der Alkylrest im Alkylphenyl befindet sich vorzugsweise in para-Stellung. Die Alkylreste im Alkylphenyl können Butyl, Hexyl, n-Octyl, iso-Octyl, p-tert.-Octyl, n-Nonyl, iso-Nonyl, Decyl oder Dodecyl sein. Bevorzugt sind die Alkylreste mit 8 bis 12 Kohlenstoffatomen, insbesondere die Octyl- oder Nonylreste.Preferred anionic polyalkylene oxide adducts correspond to the formula

where Y is alkyl or alkenyl each with 8 to 22 carbon atoms, alkylphenyl with 4 to 16 carbon atoms in the alkyl part or o-phenylphenyl, X is the acid residue of an inorganic, oxygen-containing acid such as e.g. Sulfuric acid or phosphoric acid or the rest of an organic acid and m is 2 to 40, preferably 2 to 15. The alkyl radical in the alkylphenyl is preferably in the para position. The alkyl radicals in the alkylphenyl can be butyl, hexyl, n-octyl, iso-octyl, p-tert-octyl, n-nonyl, iso-nonyl, decyl or dodecyl. The alkyl radicals having 8 to 12 carbon atoms are preferred, in particular the octyl or nonyl radicals.

The fatty alcohols for the preparation of the anionic surfactants of formula (2) are e.g. those with 8 to 22, in particular 8 to 18, carbon atoms, such as octyl, decyl, lauryl, tridecyl, myristyl, cetyl, stearyl, oleyl, arachidyl or behenyl alcohol.

The acid radical X is derived for example from low molecular weight dicarboxylic acids, for example of maleic acid, succinic acid or sulfo _'succinic acid, and is connected via a Esterbrücke with the Ethylenoxyteil of the molecule. In particular, however, X is derived from inorganic polybasic acids, such as sulfuric acid or orthophosphoric acid.

Acid residue X can be in the form of free acid or in salt form, i.e. e.g. as an alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.

worin Y' Octyl oder Nonyl bedeutet, m₁ 2 bis 15 ist und X' ein Säurerest ist, der sich von Schwefelsäure oder von o-Phosphorsäure ableitet, und die Tenside als freie Säuren, Natrium- oder Ammoniumsalze vorliegen. Von besonderem Interesse ist der saure Schwefelsäureester des Anlagerungsproduktes von 2 bis 12 Mol Ethylenoxid an 1 Mol p-Nonylphenol. Die anionischen Alkylenoxidaddukte können zur Herstellung des neuen Nachwaschmittels einzeln oder als Mischungen untereinander eingesetzt werden.Anionic surfactants of the formula are particularly preferred

wherein Y 'is octyl or nonyl, m _{1 is} 2 to 15 and X' is an acid residue derived from sulfuric acid or from o-phosphoric acid, and the surfactants are present as free acids, sodium or ammonium salts. Of particular interest is the acidic sulfuric acid ester of the adduct of 2 to 12 moles of ethylene oxide with 1 mole of p-nonylphenol. The anionic alkylene oxide adducts can be used individually or as mixtures with one another to produce the new post-washing agent.

For example, aliphatic monoalcohols having at least 5, preferably 8 to 18, carbon atoms are used as component (C). These alcohols can be saturated or unsaturated and branched or straight-chain and can be used alone or in a mixture. It can Natural alcohols such as, for example, amyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol or synthetic alcohols, for example oxo alcohols such as in particular 2-ethyl butanol, 2-ethyl hexanol, isooctyl alcohol, trimethyl hexanol, trimethyl nonyl alcohol or alfadole alcohol.

dargestellt, in der R einen gesättigten oder ungesättigten aliphatischen Rest, vorzugsweise Alkyl oder Alkenyl jeweils mit 8 bis 18 Kohlenstoffatomen und s 1 bis 10, vorzugsweise 1 bis 3 bedeuten.The alkylene oxide addition products from the water-insoluble monoalcohols mentioned, such as, for example, 1,2-propylene oxide addition products, for example those which contain 1 to 15 mol of propylene oxide, but preferably the ethylene oxide addition products of these alcohols can also be used as component (C). Preferred ethylene oxide addition products are exemplified by the following formula

represented in which R is a saturated or unsaturated aliphatic radical, preferably alkyl or alkenyl each having 8 to 18 carbon atoms and s 1 to 10, preferably 1 to 3.

Also suitable as component (C) are fatty acid-alkanolamine reaction products which are advantageously derived from fatty acids with 8 to 22 carbon atoms and from alkanolamines with 2 or 3 carbon atoms per alkanol radical.

The reaction products of fatty acids having 12 to 18 carbon atoms are preferred. As alkanolamine one can e.g. Use ethanolamine, diethanolamine, propanolamine, isopropanolamine or di-isopropanolamine. Dialkanolamines, especially diethanolamine, are preferred. The molar ratio between fatty acid and dialkanolamine can be 1: 1 to 1: 2. Examples of fatty acids are: decenic acid, lauric acid, coconut oil fatty acid, myristic acid, palmitic acid, tallow fatty acid, oil acid, ricinoleic acid, linoleic acid, linolenic acid, stearic acid, arachic acid or behenic acid.

Mixtures of these acids can also be used, such as those obtained from the cleavage of natural oils or fats. Palmitic / stearic acid mixtures and especially coconut fatty acid are particularly preferred. These reaction products of component (C) and processes for their preparation are known, for example, from US Pat. No. 2,089,212.

Also suitable as component (C) are alkylene oxide, in particular ethylene oxide, adducts from the above-mentioned fatty acid-alkanolamine reaction products, it being possible for individual ethylene oxide units to be replaced by substituted epoxides, such as propylene oxide. The number of alkylene oxide groups in these glycol ethers can be 1 to 8 and preferably 1 to 4. Addition products of 1 to 4 moles of ethylene oxide with 1 mole of reaction product of 1 mole of coconut fatty acid, stearic acid and / or palmitic acid with 1 mole of diethanolamine are preferred.

Further reaction products which are suitable as component (C) are addition products of preferably 2 to 15 mol of alkylene oxide, e.g. Ethylene oxide and / or propylene oxide, on optionally substituted phenols, trihydric to hexavalent aliphatic alcohols of 3 to 9 carbon atoms or on the aforementioned fatty acids.

Suitable optionally substituted phenols are, for example, phenol, benzylphenol, o-phenylphenol or alkylphenols, the alkyl radical of which may have a total of 4 to 16, preferably 4 to 12, carbon atoms. Examples of these alkylphenols are butylphenol, tributylphenol, octylphenol and in particular nonylphenol.

The trihydric to hexavalent alcohols preferably contain 3 to 6 carbon atoms and are in particular glycerol, trimethylolpropane, erythritol, mannitol, pentaerythritol or sorbitol. The three to hexavalent alcohols are preferably reacted with ethylene oxide or preferably with propylene oxide or mixtures of these alkylene oxides.

The fatty acids preferably have 8 to 22 carbon atoms and can be saturated or unsaturated, e.g. capric, lauric, myristic, palmitic or stearic acid or decenic, dodecenic, tetradecenic, hexadecenic, oleic, linoleic, linolenic or preferably ricinoleic acid.

Preferred components (C) consist of an aliphatic monoalcohol of 8 to 18 carbon atoms, an above-mentioned fatty acid / alkanolamine reaction product or in particular a mixture of these substances. If desired, the mixture can also contain an adduct of 5 to 12 moles of ethylene oxide with a C ₄ -C ₁₂ alkylphenol.

The amounts in which component (C) is present alone or as a mixture of two, three or more components in the detergent range from 1 to 20 percent by weight, preferably 1 to 5 percent by weight, based on the total detergent.

The polymers containing carboxyl groups present as component (D) in the detergent according to the invention are expediently used in the form of 0.5 to 35%, preferably 0.5 to 5% aqueous solutions or dispersions, based on the solution or dispersion. These polymers are advantageously polymerized ethylenically unsaturated mono- or dicarboxylic acids of 3 to 5 carbon atoms, such as, for example, polyacrylic acid or polymers of methacrylic acid, crotonic acid, itaconic acid, teraconic acid, maleic acid or their anhydride, fumaric acid, citraconic acid or mesaconic acid, copolymers of olefins, for example ethylene or Propylene, diketenes, acrylic acid esters, methacrylic acid esters or acrylamides and the aforementioned monomers including acrylic acid or copolymers of acrylic acid with methacrylic acid, methacrylonitrile or vinyl monomers, such as vinyl phosphoric acid, copolymers of maleic acid and styrene, maleic acid and a vinyl ether or maleic acid and a vinyl ester, for example vinyl acetate. Furthermore, as component (D) poly (N, N-bis- carboxymethyl) vinylamine, poly (N, N-bis-carboxymethyl) acrylamide, poly (N-carboxymethyl) ethylene diamine or polyhydroxycarboxylic acids can be used. The polymers containing carboxyl groups present as component (D) in the detergent according to the invention can at the same time also be used as thickeners. The aqueous solutions or dispersions of the abovementioned polymers, insofar as they form usable thickenings, can be used as such, ie in the acidic pH range, or can be converted into the corresponding salts by adding alkalis or ammonia and used in this form as a thickening. They are preferably adjusted to a pH of 6.5 to 7. Furthermore, they have a viscosity which is advantageously at least 5000 centipoise, preferably 8000 to 35,000 centipoise at 20 ° C. If desired, these thickeners can also be pseudoplastic. The carboxyl-containing polymers which form thickeners can have a molecular weight of 1/2 to 6 million.

• (a) Makromolekulare Copolymerisate aus Ethylen und Maleinsäureanhydrid (Mol-Verhältnis 1:1), insbesondere solche, die ein Molekulargewicht von 0,01 bis 2 Millionen haben und deren 1,5 bis 3Zige wässrige Lösungen, bezogen auf das Copolymerisat, bei 20°C eine Viskosität von 8000 bis 100 000 vorzugsweise bis 20 000 Centipoise aufweisen;
• (b) Vernetzte Carboxymethylenpolymerisate mit einem Molekulargewicht von 1 bis 5 Millionen, insbesondere solche, deren 1,5 bis 3Zige wässrige Lösungen, bezogen auf das Copolymerisat, bei 20°C eine Viskosität von 20 000 bis 32 000 Centipoise aufweisen;
• (c) Polyacrylsäure oder Copolymerisate aus Acrylsäure und Acrylamid, wobei das entsprechende Molekulargewicht von 1/2 bis 6 Millionen schwanken kann. Die Copolymerisate weisen vorteilhafterweise ein Molverhältnis Acrylsäure:Acrylamid von 1:0,8 bis 1:1,2 auf. Die bevorzugten 1,5 bis 3Zigen wässrigen Lösungen dieser Polymerisate (c) besitzen bei 20°C eine Viskosität von 15 000 Centipoise.

The solutions of the following polymers used as component (D) have proven to be particularly useful thickeners:

• (a) Macromolecular copolymers of ethylene and maleic anhydride (molar ratio 1: 1), in particular those which have a molecular weight of 0.01 to 2 million and whose 1.5 to 3% aqueous solutions, based on the copolymer, at 20 ° C have a viscosity of 8,000 to 100,000, preferably up to 20,000 centipoise;
• (b) Crosslinked carboxymethylene polymers with a molecular weight of 1 to 5 million, in particular those whose 1.5 to 3% aqueous solutions, based on the copolymer, have a viscosity of 20,000 to 32,000 centipoise at 20 ° C.;
• (c) Polyacrylic acid or copolymers of acrylic acid and acrylamide, where the corresponding molecular weight can vary from 1/2 to 6 million. The copolymers advantageously have a molar ratio of acrylic acid: acrylamide of 1: 0.8 to 1: 1.2. The preferred 1.5 to 3% aqueous solutions of these polymers (c) have a viscosity of 15,000 centipoise at 20 ° C.

In the detergent according to the invention, a partially hydrolyzed polymaleic anhydride is particularly preferred as component (D). This is usually partly in the form of a water-soluble salt and has a molecular weight that is preferably between 300 and 5000.

Polymaleic anhydride is a homopolymer of maleic anhydride and can be hydrolyzed very easily, for example by heating in water, to form a polymeric product which contains free carboxylic acid groups and optionally still intact anhydride groups on a main carbon chain. The product is not a pure polymaleic acid. The exact constitution of the product is not known. In the present specification, however, this polymeric product formed by hydrolysis of polymaleic anhydride is referred to as hydrolyzed polymaleic anhydride. This can be prepared by addition polymerization of a starting monomer consisting essentially of maleic anhydride under bulk polymerization conditions or by solution polymerization. Maleic anhydride is preferably polymerized in an inert organic solvent, such as, for example, toluene or xylene, in the presence of a polymerization catalyst, in particular a radical initiator, such as, for example, benzoyl peroxide, di-tertiary-butyl peroxide or mono-butyl hydroperoxide, at temperatures up to 150 ° C., preferably 120 ° to 145 ° C. The main chain of the primary polymer is essentially formed by non-hydrolyzable bonds. The unhydrolyzed polymer product is then hydrolyzed after separation of the unreacted monomer and by-products with water or an aqueous base and then used in this form. If necessary, it can also be used in non-hydrolyzed form.

During the polymerization or the subsequent hydrolysis, a decarboxylation of the polymer can occur, so that the acid number found of the hydrolyzed polymaleic anhydride is lower than the theoretical value of 1143 mg KOH / g. However, such a decarboxylation does not go so far that the acid number falls below 350 mg KOH / g.

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

Further details about hydrolyzed polymaleic anhydride are e.g. in GB 1 369 429, GB 1 411 063, GB 1 491 978 and CH 624 256.

By adding bases to the hydrolyzed polymaleic anhydride, some of its carboxyl groups are present, for example, as alkali metal or ammonium carboxylate groups. Particularly suitable as alkali metal salts are the sodium or potassium salt and preferably ammonium (NH ₄ ⁺ ), alkylammonium or alkanolammonium salts, such as, for example, the trimethylammonium, monoethanolammonium, diethanolammonium or triethanolammonium salt as ammonium salts. The sodium and ammonium (NH4) salts are particularly suitable.

As a rule, the hydrolyzed polymaleic anhydride is used as component (D) in the form of an aqueous 40 to 60 percent by weight solution, based on the solution. The detergent according to the invention preferably contains as component (D) 1.5 to 10 percent by weight of this aqueous solution, based on the total detergent. When using hydrolyzed polymaleic anhydride as a component (D) the detergent according to the invention preferably additionally contains a thickener to increase the stability.

In this case, suitable thickeners are, for example, polysaccharides, e.g. Carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, locust bean gum ether or starch ether, as well as alginates or metal stearates, such as e.g. Aluminum, calcium or zinc stearate or finely divided silica.

The amounts of these additional ingredients are generally between 0.1 to 5 percent by weight, preferably 0.3 to 2 percent by weight, based on the total detergent.

In addition to components (A), (B), (C) and (D), the new detergent may also contain a silicone oil or a mixture of the silicone oils as component (E).

wiedergegeben werden, worin R_lfür Methyl oder Methoxy steht und x eine ganze Zahl grösser als 1, vorzugsweise 50 bis 1200 oder mehr, bedeutet. Es handelt sich in der Regel um bekannte Handelsprodukte, die neben dem Siliconöl gegebenenfalls noch übliche Zusätze, wie z.B. kolloidale Kieselsäure oder Emulgatoren auf Polyäthylenglykolbasis enthalten können. Bevorzugt sind die höhermolekularen Siliconöle. Man setzt sie vorzugsweise in verhältnismässig kleinen Mengen ein, um z.B. Eigeneffekte der Silikonöle (Hydrophobie) zu vermeiden.The silicone oils of component (E) are used in the agents according to the invention in particular in order to strive for an extremely foam-suppressing effect. However, silicone oils can also further improve the kneading effect of the agents used. The silicone oils can be present in amounts of up to 15, for example 1 to 15, in particular up to 5, and in some cases only up to 2 percent by weight, based on the detergent. Silicone oils are understood to mean organopolysiloxanes (optionally blocked with hydroxyl at the ends) such as, for example, polydimethylsiloxanes, polymethylphenylsiloxanes and polymethylhydrogen siloxanes with average molecular weights of about 1000 to 100000, preferably 5000 to 40,000. Alkyl polysiloxanes which have a viscosity of at least 0.7 centipoise at 25 ° C. are particularly suitable. The alkyl radical can contain 1 to 6 carbon atoms. Preferred are, for example, the methylsiloxanes which have a viscosity of 50 to 15,000, preferably 100 to 1000 centipoise at 25 ° C. Suitable methylpolysioxanes can by the formula

are reproduced, wherein R _{l is} methyl or methoxy and x is an integer greater than 1, preferably 50 to 1200 or more. As a rule, these are known commercial products which, in addition to the silicone oil, may also contain conventional additives, such as colloidal silica or emulsifiers based on polyethylene glycol. The higher molecular weight silicone oils are preferred. They are preferably used in relatively small amounts, for example in order to avoid the silicone oils having their own effects (hydrophobicity).

The amounts in which component (E) may be present alone or as a mixture in the detergent advantageously range from 0 to 5 percent by weight, preferably from 0 to 3 percent by weight, based on the detergent as a whole.

• (Aa) ein Natriumaluminiumsilikat,
• (Bb) ein anionisches Tensid der Formel (3),
• (Cc) einen aliphatischen Monoalkohol von 8 bis 18 Kohlenstoffatomen, ein Fettsäure/Alkanolamin-Umsetzungsprodukt oder insbesondere deren Gemische und als Komponente (D),
• (Dd_l)eine wässrige Lösung als Verdickungsmittel einer polymerisierten ethylenisch ungesättigten Mono- oder Dicarbonsäure von 3 bis 5 Kohlenstoffatomen oder eines Copolymerisates aus einer dieser Säuren und Ethylen oder Acrylamid, insbesondere eines Copolymerisates aus Ethylen und Maleinsäureanhydrid oder vorzugsweise
• (Dd₂)ein hydrolysiertes Polymaleinsäureanhydrid zusammen mit einem Verdickungsmittel, z.B. einem Polysaccharid.

Particularly preferred aqueous detergents according to the invention contain at least the following components

• (Aa) a sodium aluminum silicate,
• (Bb) an anionic surfactant of the formula (3),
• (Cc) an aliphatic monoalcohol of 8 to 18 carbon atoms, a fatty acid / alkanolamine reaction product or in particular mixtures thereof and as component (D),
• (Dd ₁ ) an aqueous solution as a thickener of a polymerized ethylenically unsaturated mono- or dicarboxylic acid of 3 to 5 carbon atoms or a copolymer of one of these acids and ethylene or acrylamide, in particular a copolymer of ethylene and maleic anhydride or preferably
• (Dd ₂ ) a hydrolyzed polymaleic anhydride together with a thickening agent, for example a polysaccharide.

The after-washing agents according to the invention can be prepared by simply stirring the above-mentioned components (A), (B), (C), (D) and optionally (E) and / or thickening agents in water. Homogeneous, clear mixtures are obtained which are very stable in storage and free of sedimentation at room temperature.

• 35 bis 50 Gewichtsprozent der Komponente (A),
• 0,5 bis 10 Gewichtsprozent der Komponente (B),
• 1 bis 15 Gewichtsprozent der Komponente (C),
• 2 bis 20 Gewichtsprozent der wässrigen Komponente (D), vorzugsweise, bezogen auf das Polymerisat, in Form einer 1,5 bis 3OZigen wässrigen Lösung,
• 0 bis 3 Gewichtsprozent der Komponente (E),
• 0 bis 2 Gewichtsprozent Verdickungsmittel

und mindestens 25 Gewichtsprozent Wasser.These agents preferably contain, based in each case on the mixture,

• 35 to 50 percent by weight of component (A),
• 0.5 to 10 percent by weight of component (B),
• 1 to 15 percent by weight of component (C),
• 2 to 20 percent by weight of the aqueous component (D), preferably, based on the polymer, in the form of a 1.5 to 30% aqueous solution,
• 0 to 3 percent by weight of component (E),
• 0 to 2 weight percent thickener

and at least 25 weight percent water.

If desired, such mixtures can additionally contain neopentyl glycol, benzyl alcohol, furfuryl alcohol, acetic acid esters, malonic acid diesters, succinic acid diesters, adipic acid diesters, tetralin, decalin, alkylbenzenes and in particular paraffin oils, and also fatty amine-alkylene oxide adducts.

The detergents according to the invention are used, in particular, for washing dyeings or prints on cellulose fibers or mixed fabrics made of cellulose and synthetic organic material, for example linear polyesters or modified cellulose (cellulose esters), cellulose material being those made from natural or regenerated cellulose, such as hemp, Linen, jute, viscose silk, cellulose or especially cotton and any polyester content, if necessary, before or after the cellulose is dyed. Cellulose dyeings or cellulose prints are understood here to mean the dyeings or prints produced by any process with reactive dyes, the detergents according to the invention being used as aftertreatment. The dyeing material can be in any processing stages, for example as a loose material (flake), as a doubled, pre-stretched staple fiber tape or in the form of threads, yarns, but especially woven or knitted fabrics. Reactive dyes are understood to be the customary anionic dyes which form a chemical bond with the cellulose, for example the "Reactive Dyes" listed on pages 3391-3562 in the Color Index, 3rd Edition (1971) Vol. 3.

The detergent according to the invention makes it possible to carry out the usual washing operations of the abovementioned prints or dyeings produced with reactive dyes with hard water (process water), as is directly available from the water pipe, with good success. As a result, the water hardness is reduced without the usual addition of electrolytes, ion exchangers and / or complexing agents and, above all, without the use of phosphorus-containing compounds, e.g. Phosphonic acids or inorganic phosphates eliminated, which have recently been increasingly restricted by the ecological and legislative requirements for phosphorus-free products.

The invention thus further relates to a method for washing prints or dyeings produced with reactive dyes on cellulose-containing textile materials using the detergents according to the invention. This process consists in treating the printed or dyed textiles at a temperature of 60 to 100 ° C. in an aqueous washing liquor which contains the detergent according to the invention, preferably in amounts of 1-10 g / l. The textiles are then removed from the wash liquor and rinsed with fresh water until the wash liquor components have been completely removed. This gives printing dyeings, the white base of which is not stained, and dyeings from the exhaust process, which have the desired wet fastness properties, especially fastness to washing.

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

The following products are examples of the anionic surfactants or alkylene oxide adducts used as components (B) and (D).

B. Anionic surfactants

• B ₁ ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of alfol (1014);
• B ₂ ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of stearyl alcohol;
• B ₃ ammonium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of 2-ethyl-hexanol;
• B ammonium salt of the acid sulfuric acid ester of the adduct of 15 moles of ethylene oxide and 1 mole of stearyl alcohol;
• B ₅ ammonium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of tridecyl alcohol;
• B ₆ ammonium salt of the acid sulfuric acid ester of the adduct of 4 moles of ethylene oxide and 1 mole of hydroabietyl alcohol;
• B ₇ ammonium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of Alfol (2022);
• B ₈ ammonium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of lauryl alcohol;
• B ₉ di- (β-hydroxy-ethyl) amine salt of the acidic sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of lauryl alcohol;
• B ₁₀ sodium salt of the acidic sulfuric acid ester of the additive of 2 moles of ethylene oxide and 1 mole of lauryl alcohol;
• B ₁₁ sodium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of lauryl alcohol;
• B ₁₂ acidic phosphoric acid ester of the adduct of 5 moles of ethylene oxide and 1 mole of 2-ethyl-n-hexanol;
• B ₁₃ ammonium salt of the acid sulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of butylphenol;
• B ₁₄ ammonium salt of the acid sulfuric acid ester of the adduct of 5 moles of ethylene oxide and 1 mole of tributylphenol;
• B ₁₅ ammonium salt of the acid sulfuric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of nonylphenol;
• B ₁₆ ammonium salt of the acid sulfuric acid ester of the adduct of 10 moles of propylene oxide and 10 moles of ethylene oxide and 1 mole of nonylphenol;
• B ₁₇ ammonium salt of the acid sulfuric acid ester of the adduct of 35 moles of ethylene oxide and 1 mole of nonylphenol;
• B ₁₈ ammonium salt of the acid sulfuric acid ester of the adduct of 50 moles of ethylene oxide and 1 mole of nonylphenol;
• B ₁₉ ammonium salt of the acid sulfuric acid ester of the adduct of 15 moles of propylene oxide with 1 mole of nonylphenol;
• B ₂₀ ammonium salt of the acidic sulfuric acid ester of the adduct of 6 moles of ethylene oxide and 1 mole of dodecylphenol;
• B ₂₁ ammonium salt of the acidic sulfuric acid ester of the adduct of 6 moles of ethylene oxide and 1 mole of pentadecylphenol;
• B ₂₂ ammonium salt of the acid sulfuric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of o-phenylphenol;
• B ₂₃ sodium salt of the acidic maleic acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-nonylphenol;
• B ₂₄ sodium salt of the acidic monosulfosuccinic acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of p-noylphenol;
• B ₂₅ ammonium salt of the acidic phosphoric acid ester of the adduct of 2 moles of ethylene oxide and 1 mole of nonylphenol;
• B ₂₆ sodium salt of the acid sulfuric acid ester of the adduct of 12 moles of ethylene oxide and 1 mole of dibenzylphenol;
• B ₂₇ sodium salt of the acidic sulfuric acid ester of the adduct of 15 moles of ethylene oxide and 1 mole of dibenzyl- (nonyl) phenol;
• B ₂₈ acidic phosphoric acid ester of the adduct of 10 moles of ethylene oxide with 1 mole of p-nonylphenol;
• B ₂₉ ammonium salt of the acidic sulfuric acid ester of the adduct of 15 moles of ethylene oxide and 1 mole of stearic acid-β-hydroxyethylamide;
• B ₃₀ ammonium salt of the acidic disulfuric acid ester of the adduct of 3 moles of ethylene oxide and 1 mole of tallow fatty amine;
• B ₃₁ ammonium salt of the acidic disulfuric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of tallow fatty amine;
• B ₃₂ ammonium salt of the acidic disulfuric acid ester of the adduct of 3 moles of propylene oxide and 5 moles of ethylene oxide and 1 mole of tallow fatty amine;
• B ₃₃ ammonium salt of the acidic diphosphoric acid ester of the adduct of 8 moles of ethylene oxide and 1 mole of tallow fatty amine;
• B ₃₄ ammonium salt of the acidic disulfuric acid ester of the adduct of 1 mol of styrene oxide and 8 mol of ethylene oxide and 1 mol of dodecylamine;
• B ₃₅ sodium salt of the acidic sulfosuccinic acid half ester of the adduct of 8 moles of ethylene oxide and 1 mole of tallow fatty amine
• B ₃₆ ammonium salt of the acidic disulfuric ester of the adduct of 2 moles of ethylene oxide and 1 mole of stearylamine;
• _B37 mixture of the mono- and di-phosphoric acid ester (1: 2) of the adduct of 8 moles of ethylene oxide and 1 mole of dodecylamine;
• B ₃₈ mixture of the mono- and di-phosphoric acid ester (1: 2) of the adduct of 4 moles of ethylene oxide and 1 mole of laurylamine;

C. Alkylene oxide adducts which can be used as component (C)

• C _l . Adduct of 6 moles of ethylene oxide with 1 mole of 2-ethylhexanol;
• C ₂ adduct of 5 moles of ethylene oxide with 1 mole of 2-ethylhexanol;
• C ₃ adduct of 15 moles of ethylene oxide with 1 mole of stearyl alcohol;
• C ₄ adduct of 3 moles of ethylene oxide with 1 mole of alfol (8-10);
• C ₅ adduct of 5 moles of ethylene oxide with 1 mole of hexadecyl alcohol;
• C ₆ adduct of 15 moles of ethylene oxide with 1 mole of oleyl alcohol;
• C ₇ adduct of 6 moles of ethylene oxide with 2 moles of butyl phenol;
• C ₈ adduct of 4 moles of ethylene oxide with 2 moles of p-cresol;
• C ₉ adduct of 5 moles of ethylene oxide with 1 mole of tributylphenol;
• C ₁₀ adduct of 8 moles of ethylene oxide with 1 mole of octylphenol;
• C ₁₁ adduct of 2 moles of ethylene oxide with 1 mole of nonylphenol;
• _C12 adduct of 10 _{moles of} ethylene oxide with 1 mole of nonylphenol;
• C ₁₃ adduct of 10 moles of ethylene oxide and 10 moles of propylene oxide with 1 mole of nonylphenol;
• _C14 adduct of 10 moles of ethylene oxide with 1 mole of oleyl alcohol;
• C ₁₅ adduct of 12 moles of ethylene oxide with 1 mole of oleic acid;
• C ₁₆ adduct of 8 moles of ethylene oxide with 1 mole of o-phenylphenol;
• C ₁₇ adduct of 5 moles of ethylene oxide and 5 moles of propylene oxide with 1 mole of Alfol 12-14;
• C ₁₈ adduct of 15 moles of ethylene oxide with 1 mole of castor oil;
• C ₁₉ adduct of 8 moles of propylene oxide with 1 mole of pentaerythritol;
• C ₂₀ adduct of 15 moles of ethylene oxide and 15 moles of propylene oxide with 1 mole of glycerol;
• C ₂₁ adduct of 7 moles of ethylene oxide with 1 mole of C ₉ -C ₁₁ oxo alcohol;
• C ₂₂ adduct of 15 moles of ethylene oxide with 1 mole of p-nonylphenol;
• C ₂₃ adduct of 2 moles of ethylene oxide with 1 mole of coconut oil fatty acid (N, N-bis-ß-hydroxyethyl) amide
• C ₂₄ adduct of 5 moles of ethylene oxide with 1 mole of p-nonylphenol;
• C ₂₅ adduct of 15 moles of propylene oxide with 1 mole of glycerol.

Manufacturing instructions A

• 100 g Maleinsäureanhydrid in 100 g Xylol werden auf 120°C erhitzt und im Verlauf von 15 Minuten mit der Lösung von 20 g Di-tertiär-butylperoxid in 50 g Xylol versetzt. Die Temperatur des Reaktionsgemisches wird auf 130°C gesteigert und 5 Stunden dort gehalten. Man bricht sowohl das Erhitzen als auch das Rühren ab und lässt das Polymerisat sich abscheiden. Nach Abkühlen des Reaktionsgemisches auf 85°C wird die untere Polymerschicht von der oberen Xylolschicht abgetrennt. Man erhält 81 g Polymerisat.

The hydrolyzed polymaleic anhydride which can be used as component (D) is prepared as follows:

• 100 g of maleic anhydride in 100 g of xylene are heated to 120 ° C. and a solution of 20 g of di-tertiary-butyl peroxide in 50 g of xylene is added in the course of 15 minutes. The temperature of the reaction mixture is raised to 130 ° C. and held there for 5 hours. Both the heating and the stirring are stopped and the polymer is allowed to separate. After the reaction mixture has cooled to 85 ° C., the lower polymer layer is separated from the upper xylene layer. 81 g of polymer are obtained.

The polymer is mixed with 15 g of 2-butanone or 1,4-dioxane as a diluent and further purified as follows. The polymer is precipitated by adding the polymer solution to 430 g of toluene in a rapid homogenizer. After filtering off and drying in vacuo at 50 ° C., 78 g of powdery polymer are obtained.

When measured in 2-butanone using a vapor pressure osmometer, the polymaleic anhydride obtained has a molecular weight of 580.

20 g of the polymaleic anhydride are heated in 20 g of water at 90 ° C. for 30 minutes, after which the solution obtained is cooled to 30 ° C. and filtered. A solution with a solids content of 53% is obtained. The potentiometric titration of the hydrolyzed polymer against potassium hydroxide gives an acid value of 560 mg KOH / g.

The hydrolyzed polymaleic acid hydride solution is then mixed with 4.5 g of a 25% aqueous ammonia solution and enough water to form a 50% aqueous solution of the hydrolyzed polymaleic anhydride, which is partially present as the ammonium salt.

Example 1: A stable, homogeneous liquid detergent of the following composition is obtained by stirring at room temperature

Example 2: Stirring at room temperature produces a stable, homogeneous detergent of the following composition

Example 3: A stable, homogeneous detergent of the following composition is obtained by stirring at room temperature

Example 4: A stable, homogeneous detergent of the following composition is obtained by stirring at room temperature

Example 5: A stable, homogeneous detergent of the following composition is obtained by stirring at room temperature

Example 6: A stable, homogeneous detergent of the following composition is obtained by stirring at room temperature

Example 7:

• 400 g Alginatverdickungsmittel 5%ig
• 100 g Harnstoff
• 50 g eines Farbstoffes der Formel
  
• 10 g m-Nitrobenzolsulfonsäure (Natriumsalz)
• 60 g Natriumcarbonatlösung 30%ig und
• 380 g Wasser

_A ) Bleached cotton terry is on a Rouleaux printing machine with 1 kg of printing paste of the composition

• 400 g 5% alginate thickener
• 100 g urea
• 50 g of a dye of the formula
  
• 10 g m-nitrobenzenesulfonic acid (sodium salt)
• 60 g sodium carbonate solution 30% and
• 380 g water

_s o printed that 3 cm printed strips result in addition to 3 cm unprinted strips. The goods are then dried and steamed at 101 ° C for 8 minutes.

• B) Es werden 3 Waschflotten von je 150 ml auf Kochtemperatur erhitzt:
  • 1, Wasser von Härte 20° deutsche Härte (dH)
  • 2. Wasser von Härte 20° dH + 4 ml/l der Zubereitung gemäss Beispiel 1
  • 3. Wasser von Härte 20° dH + 8 ml/l der Zubereitung gemäss Beispiel 1 In jede dieser Waschflotten werden bei einem Flottenverhältnis von 1:60 jeweils nacheinander 3 der gemäss (A) bedruckten Abschnitte während 5 Minuten bei Kochtemperatur behandelt, in kaltem Wasser gespült und an der Luft getrocknet.

The goods are then rolled up and used for the test described below:

• B) 3 washing liquors, each 150 ml, are heated to boiling temperature:
  • 1, water of hardness 20 ° German hardness (dH)
  • 2. Water with a hardness of 20 ° dH + 4 ml / l of the preparation according to Example 1
  • 3. Water with a hardness of 20 ° dH + 8 ml / l of the preparation according to Example 1 In each of these washing liquors, at a liquor ratio of 1:60, 3 of the sections printed according to (A) are treated in succession for 5 minutes at the boiling temperature, rinsed in cold water and air-dried.

With washing liquors 2 and 3, a product is obtained which has no staining on unprinted parts. In contrast, the white portion of the print treated with wash liquor 1 is strongly stained.

If, instead of the preparation according to Example 1, the same amount of one of the preparations according to Examples 2 to 6 is used in the washing liquors 2 and 3, a product is also obtained which shows no coloring on unprinted parts.

Example 8:

• 32 kg Natriumchlorid und
• 800 g m-Nitrobenzolsulfonsäure, Natriumsalz

eingenetzt. Alsdann wird die Färbeflotte auf 95°C erhitzt, worauf das Färbebad 30 Minuten bei 85°C gehalten wird. Hierauf gibt man zur Färbeflotte

• 8 kg Natriumcarbonat und
• 1,2 1 Natriumhydroxydlösung (30%ig)

zu und färbt das Tricot noch 60 Minuten bei 85°C. Danach wird die Flotte abgekühlt und die gefärbte Ware gespült und getrocknet.A) On a closed reel runner, 10 kg of tricot made from bleached and mercerized cotton in 400 liters of water with the addition of 400 g of a dye of the formula

• 32 kg sodium chloride and
• 800 g m-nitrobenzenesulfonic acid, sodium salt

networked. The dyebath is then heated to 95 ° C., after which the dyebath is kept at 85 ° C. for 30 minutes. Then add to the dye liquor

• 8 kg sodium carbonate and
• 1.2 1 sodium hydroxide solution (30%)

and dye the tricot for 60 minutes at 85 ° C. The liquor is then cooled and the dyed goods are rinsed and dried.

• 1. Wasser von Härte 20° dH
• 2. Wasser von Härte 20° dH + 4 ml/1 der Zubereitung gemäss Beispiel 1
• 3. Wasser von Härte 20° dH + 8 ml/1 der Zubereitung gemäss Beispiel 1

B) A cotton tricot section dyed according to A) is treated in an Ahiba dyeing machine at a liquor ratio of 1:50 for 10 minutes at the boiling temperature with the following three wash liquors:

• 1. Water with a hardness of 20 ° dH
• 2. Water with a hardness of 20 ° dH + 4 ml / 1 of the preparation according to Example 1
• 3. Water with a hardness of 20 ° dH + 8 ml / 1 of the preparation according to Example 1

The individual wash samples are then rinsed together in cold permutite water for 10 minutes.

The treated colored samples are spun onto 1007 water absorption and tested for wet ironing in accordance with SNV standard 19832. A white section of cotton is wetted in distilled water and spun to 100% water absorption. The damp colored tricot section is placed on a dry white section of cotton and covered with the moist white section. The washing samples are then pressed together for 2 minutes in an ironing press set at 180 ° C. The white, pre-wetted accompanying fabric is then assessed for fastness to ironing.

The dyed sections obtained according to washing tests 2 and 3 do not stain the white section when testing the fastness to ironing, while the white cotton is strongly stained by the section obtained according to washing test 1.

If the same amount of one of the preparations according to Examples 2 to 6 is used in each of the washing liquors 2 and 3 instead of the preparation according to Example 1, then iron-fastened colored sections are also obtained.

Claims (18)

1. Aqueous detergent, characterized in that it (A) an alkali aluminum silicate, (B) an anionic surfactant, (C) an aliphatic monoalcohol with 5 to 18 carbon atoms or a fatty acid / alkanolimine reaction product or its alkylene oxide adducts or adducts from fatty acids with 8 to 22 carbon atoms, trihydric to hexavalent aliphatic alcohols or optionally substituted phenols and alkylene oxides and (D) an aqueous solution or dispersion of carboxyl-containing polymers
contains. 2. Detergent according to claim 1, characterized in that it additionally contains a silicone oil as component (E). 3. Detergent according to one of claims 1 and 2, characterized in that it, based on the total detergent, (A) 20 to 60 percent by weight of the alkali aluminum silicate, (B) 0.5 to 20 percent by weight of the anionic surfactant, (C) 1 to 20 percent by weight of component (C) and (D) 2 to 30 percent by weight of the aqueous component (D)
contains. 4. Detergent according to one of claims 1 to 3, characterized in that component (A) is a water-insoluble alkali aluminum silicate of the formula

in which Me is an n-valent alkali metal ion, preferably the sodium ion, n 1 or 2, Y _{1 is} a number from 0.7 to 1.5 and Y _{2 is} a number from 0.8 to 6, preferably 1.3 to 4. 5. Detergent according to one of claims 1 to 4, characterized in that component (B) is an anionic polyalkylene oxide adduct of the formula

in which Y is alkyl or alkenyl each having 8 to 22 carbon atoms, alkylphenyl having 4 to 16 carbon atoms in the alkyl part or o-phenylphenyl, X is the acid residue of an inorganic, oxygen-containing acid or the residue of an organic acid and m 2 to 40, preferably 2 to 15, and the acid residue X is present as a free acid or in salt form. 6. Detergent according to claim 5, characterized in that component (B) is an anionic surfactant of the formula

is where Y 'is octyl or nonyl, m _{1 is} 2 to 15 and X' is an acid residue derived from sulfuric acid or from o-phosphoric acid, and the surfactant is present as a free acid or as a sodium or ammonium salt. 7. Detergent according to one of claims 1 to 6, characterized in that component (C) is an aliphatic monoalcohol of 8 to 18 carbon atoms, a fatty acid / alkanolamine reaction product or a mixture of these substances. 8. Detergent according to one of claims 1 to 7, characterized in that component (D) is a 0.5 to 35% aqueous solution or dispersion of a polymerized ethylenically unsaturated mono- or dicarboxylic acid of 3 to 5 carbon atoms or a copolymer of one Olefin, an acrylic acid ester or acrylamide and one of the acids mentioned, based on the polymer. 9. Detergent according to one of claims 1 to 8, characterized in that component (D) is present as a thickener. 10. Detergent according to one of claims 8 and 9, characterized in that component (D) is a 1.5 to 3% aqueous solution of a macromolecular copolymer of ethylene and maleic anhydride (molar ratio 1: 1), based on the copolymer . 11. Detergent according to one of claims 1 to 8, characterized in that the polymer of component (D) is a hydrolyzed polymaleic anhydride. 12. Detergent according to claim 11, characterized in that the hydrolyzed polymaleic anhydride is present as an alkali metal, ammonium, alkylammonium or alkanolammonium salt. 13. Detergent according to one of claims 11 and 12, characterized in that the hydrolyzed polymaleic anhydride is present in combination with a polysaccharide as a thickener. 14. Detergent according to claim 1, characterized in that it (Aa) is a sodium aluminum silicate, (Bb) an anionic surfactant of the formula (3)

wherein Y 'is octyl or nonyl, m is 2 to 15 and X' is an acid residue which is derived from sulfuric acid or from o-phosphoric acid, (Cc) an aliphatic monoalcohol of 8 to 18 carbon atoms, a fatty acid / alkanolamine reaction product or a mixture thereof and (Dd ₁ ) an aqueous solution as a thickener of a polymerized ethylenically unsaturated mono- or dicarboxylic acid of 3 to 5 carbon atoms or a copolymer of one of these acids and ethylene or acrylamide or (Dd ₂ ) a hydrolyzed polymaleic anhydride together with a thickener
contains. 15. Detergent according to one of claims 1 to 14, characterized in that the fatty acid-alkanolamine reaction product of component (C) is derived from a fatty acid with 8 to 22 carbon atoms and from an alkanolamine with 2 or 3 carbon atoms per alkanol radical. 16. Use of the detergent according to any one of claims 1 to 15 when washing in hard water from printing or dyeing with reactive dyes on cellulose-containing textile materials. 17. A method for washing prints or dyeings produced with reactive dyes on cellulose-containing textile materials, characterized in that the printed or dyed textiles are treated at a temperature of 60 to 100 ° C with an aqueous washing liquor which contains the detergent as defined in claim 1. 18. The method according to claim 17, characterized in that the washing liquor contains the detergent in amounts of 1-10 g / l.