WO1996016150A1

WO1996016150A1 - Soil-repellent detergent with specific combination of surfactants

Info

Publication number: WO1996016150A1
Application number: PCT/EP1995/004398
Authority: WO
Inventors: Fred Schambil; Peter Krings; Georg Meine; Eduard Smulders; Horst Upadek
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-11-17
Filing date: 1995-11-08
Publication date: 1996-05-30
Also published as: DE4440956A1

Abstract

The aim of the invention is to improve the cleaning power of detergents and cleaners that contain soil-removing polymers and surfactants of the ether sulfate type. This is achieved essentially by incorporating a combination of active agents consisting of soil-removing polyester, anionic surfactant of the ether sulfate type as per the general formula R1-(OCH2CH2)n-O-SO3X, in which R1 is an alkyl or alkenyl group with 10-22 C atoms, X is an alkali, ammonium or alkyl/hydroxyalkyl substituted ammonium ion and n is a number from 0.5 to 3, and nonionic surfactant as per the general formula R2-(OCH2CH2)m-OH, in which R2 is an alkyl or alkenyl radical with 10-22 C atoms and m a number from 6.5 to 8.5.

Description

Dirt-repellent detergent with a specific combination of surfactants

The invention relates to detergents and cleaning agents which contain dirt-repellent polymer and a combination of certain anionic surfactant of the ether sulfate type and certain nonionic surfactant of the alkyl polyethoxylate type.

In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain further constituents, which can be summarized under the term washing auxiliaries and which contain different active ingredient groups such as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors include. Such auxiliary substances also include substances which impart dirt-repellent properties to the laundry fiber and which, if present during the washing process, support the dirt-removing ability of the other detergent components. The same applies analogously to cleaning agents for hard surfaces. Such dirt-releasing substances are often referred to as “soil release” active ingredients or because of their ability to make the treated surface, for example the fiber, dirt-repellent, “soil repellents”. Because of their chemical similarity to polyester fibers, particularly effective dirt-releasing active ingredients, but which can also have the desired effect on fabrics made from other materials, are copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-removing copolyesters of the type mentioned and their use in detergents have been known for a long time. For example, German Offenlegungsschrift DT 16 17 14 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. The German Offenlegungsschrift DT 22 00911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. German laid-open specification DT 22 53063 mentions acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. Polymers with a molecular weight of 15,000 to 50,000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1,000 to 10,000 and since the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: to 6: 1 can, according to the German patent application DE 3324258 in Detergents are used. The European patent EP 066944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulphonated aromatic dicarboxylic acid in certain molar ratios. European patent EP 185427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil-release poly. European patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units. From the European patent EP 241 985 polyesters are known which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units C \ - to C4 ~ alkyl groups are end groups closed. The European patent EP 253 567 relates to soil release polymers with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide -terephthalate is 0.6 to 0.95. European patent application EP 272033 discloses at least a proportion of polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are end-capped by C4-alkyl or acyl radicals. European patent EP 274907 describes Sulphoethyl end-capped terephthalate-containing soil release polyesters. In European patent application EP 357280, sulfonation of unsaturated end groups produces soil-release polyesters with terephthalate, alkylene glycol and poly-C2-4-glycol units. Polymers made from ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents is in the German patent DE 2857292 described. This document shows that when low-ethoxylated alkyl sulfates (hereinafter referred to as ether sulfates) are used, there is no additional cleaning effect due to the polymer or only significantly less pronounced compared to other surfactants. However, these ether sulfates have good washing performance as individual substances and are therefore particularly interesting.

Against the background of this extensive state of the art, the applicant had set itself the task of further improving the cleaning performance of detergents by the interaction of such dirt-removing polymers with surfactants of the ether sulfate type.

This object was essentially achieved by the presence of a surfactant combination of ether sulfates with low average degrees of ethoxylation and alkyl oligoethoxylates with average degrees of ethoxylation in the range from 6.5 to 8.5.

The invention accordingly relates to a washing or cleaning agent which contains a combination of active ingredients comprising dirt-releasing polyester, anionic surfactant of the ether sulfate type according to the general formula

Rl- (0CH ₂ CH ₂ ) _n -0-S03X (I)

in which R ^{1 is} an alkyl or alkenyl radical having 10 to 22, in particular 12 to 18, carbon atoms, X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion and n is a number from 0.5 to 3, in particular of 1 to 2 mean and nonionic surfactant according to the general formula

in which R2 is an alkyl or alkenyl radical having 10 to 22, in particular 1 to 18, carbon atoms and m is a number from 6.5 to 8.5, in particular from 6.8 to 7.5.

Another object of the invention is the use of such a combination of active ingredients of dirt-releasing polyester, ether sulfate according to formula I and nonionic surfactant according to formula II in detergents and cleaning agents, in particular to increase their cleaning performance compared to greasy soiling.

In the active ingredient combination on which the invention is based, the weight ratio of dirt-releasing polyester to ether sulfate according to formula I is preferably 1:25 to 1: 3, in particular 1:20 to 1: 5. The weight ratio of ether sulfate according to formula I to nonionic surfactant according to formula II is preferably 3: 1 to 1: 2, in particular 2: 1 to 1: 1.5.

Suitable dirt-releasing polyesters are known from the documents cited above and are commercially available, for example, under the names Sokalan (R) HC 9798X from BASF or Velvetol (R) 251C from Rhone-Poulenc. The preferred dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol H0- (CHR ³ -) _a 0H, which is also known as polymeric diol H- (0- (CHR3-) _a ) [ _j OH may be present. Therein, Ph represents an o-, m- or p-phenylene radical, which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R3 is hydrogen, an alkyl radical having 1 to 22 carbon atoms and their mixtures, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, both monodiol units -0- (CHR3-) _a 0- and poly er are in the polyesters which can be prepared from these - diol units - (0- (CHR3-) _a ) _D 0- before. The molar ratio of monomer diol units to poly erdiol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. The degree of polymerization b in the polymer diol units is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred dirt-releasing polyesters is preferably in the range from 250 to 100,000, in particular from 500 to 50,000. The acid underlying the rest of Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small amounts, in particular not more than 10 mol%, based on the amount of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the dirt-releasing polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols H0- (CHR3-) _a 0H include those in which R3 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R3 is hydrogen and the alkyl radicals having 1 to 10 , in particular 1 to 3 carbon atoms is selected. Among the latter diols, those of the formula H0-CH2-CHR3-0H, in which R3 has the abovementioned meaning, are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octahediol, 1,2-decanediol diol, 1,2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol with an average molecular weight in the range from 1000 to 6000. If desired, the polyesters composed as described above can also be end group-closed, alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, linoleic acid, linoleic acid, oleic linaidic acid, oleic acid, linoleic acid, oleic acid, linoleic acid, oleic acid, linoleic acid, oleic acid, linoleic acid, oleic acid, linoleic acid, oleic acid, linoleic acid, oleic acid, linoleic acid, oleic acid, linoleic acid, oleic acid, oleic acid - Nolenic acid, eläostearic acid, arachic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms , for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, - and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can in turn be connected to one another via their hydroxyl group and their carboxyl group and can therefore be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10.

In a preferred embodiment of the invention, the washing or cleaning agent contains polymers of ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10 is.

Detergents or cleaning agents which contain the active ingredient combination according to the invention can contain all the usual other constituents of such agents which do not interact undesirably with the soil-release polymer or the surfactants. The active ingredient combination according to the invention is preferably used in amounts of 5% by weight to 50% by weight, in particular 8% to 25% by weight incorporated into washing or cleaning agents.

Surprisingly, it was found that the combination of active ingredients according to the invention can synergistically influence the action of certain other detergents and cleaning agents and that, conversely, the performance of the active ingredient combination according to the invention is synergistically enhanced by certain other detergent ingredients. These effects occur particularly in the case of enzymatic active ingredients, in particular proteases and lipases, in water-insoluble inorganic builders, in water-soluble inorganic and organic builders, in particular based on oxidized carbohydrates, in bleaching agents based on peroxygen, in particular in alkali percarbonate, and in synthetic anionic surfactants of the sulfate and sulfonate type , but not or only slightly so with alkylbenzenesulfonates, which is why the use of the above-mentioned ingredients together with polymers according to the invention is preferred.

In a preferred embodiment, such an agent contains, in addition to the nonionic surfactant according to formula II introduced with the active ingredient combination according to the invention, further nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or or propoxylation products of fatty alkyl amines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.

A further embodiment of such agents comprises the presence of additional synthetic anionic surfactants of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, which does not correspond to formula I, sulfofatty acid esters and / or sulfofatty acid disalts, in particular in an amount in the range from 2% by weight. % to 25% by weight. The anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms. The nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is generally between 1 and 6 or between 9 and 20, preferably between 3 and 6. Like the nonionic surfactant of the formula II contained in the active compound combination according to the invention, they can be prepared in a known manner by reacting the corresponding alcohols can be prepared with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or ocadecyl radicals, and mixtures thereof, can be used. In addition, 1 to 20 times, in particular 3 to 10 times, alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, can be used. In addition, there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, such as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as are used, for example, in accordance with the processes of the US Pat US 1 985424, US 2016962 and US 2 703 798 and the international patent application WO 92/06984 can be produced. So-called alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) n-OR ^ in which R ^ is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and p is a number between 1 and 10 mean. Such compounds and their preparation are described, for example, in European patent applications EP 92355, EP 301 298, EP 357 969 and EP 362 671 or the US Pat. No. 3,547,828. The glycoside component (G) p is oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allos, idose, ribose , Arabinose, xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of olergization. The degree of oligomerization p generally takes broken numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl part R ^{4 of} the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl glycosides contain a coconut fatty alkyl radical, that is to say mixtures with essentially R ⁴ = dodecyl and R ⁴ = tetradecyl.

Additional nonionic surfactant is in agents which contain the combination of active ingredients on which the invention is based, preferably in amounts of up to 30% by weight, in particular of 1% by weight to 25% by weight, in each case based on the total agent , contain.

Agents according to the invention can instead or in addition further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight, in each case based on the total mean. Synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl substituted ammonium ion as countercation . The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali metal, ammonium or alkyl or hydroxyalkyl substituted ammonium bases can be produced. Such alkyl and / or alkenyl sulfates are preferably present in amounts from 0.1% by weight to 20% by weight, in particular from 0.5% by weight to 18% by weight. Suitable anionic surfactants of the sulfonate type include the .alpha.-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, as well as the sulfofatty acids resulting from these by formal saponification.

Soaps are considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated Ci2-Ci8 fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. However, in particular in liquid agents according to the invention, higher amounts of soap of generally up to 20% by weight can also be present.

In a further embodiment, an agent according to the invention contains water-soluble and / or water-insoluble builders, in particular selected from alkali alumosilicate, crystalline alkali silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range from 2.5% by weight. % to 60% by weight.

An agent which has the active ingredient combination on which the invention is based preferably contains 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110, which are accessible by oxidation of polysaccharides Acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl ethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 1 -C 6 -carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C4-C8 dicarboxylic acid, preferably a C4-C8 dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, vinyl alcohol derivatives are preferred which are an ester of short-chain carboxylic acids, for example C 1 -C 4 -carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, are very particularly preferred. 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, is preferably substituted with a C 1 -C 4 -alkyl radical, or an aromatic radical, which is preferably derived from benzene or benzene derivatives. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight .-%, preferably 15% by weight to 25% by weight of methylailsulfonic acid or methylailsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers can be produced in particular by processes which are described in German patent DE 4221 381 and German patent application DE 43 00 772 and generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3,000 and 10,000. They can be used, in particular for the preparation of liquid compositions, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents which contain the active ingredient combination on which the invention is based.

The water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% .-%, used. Among these, the crystalline aluminum silicates in detergent quality, in particular zeolite A, zeolite P and optionally zeolite X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent specification DE 24 12837, is generally in the range from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline or amorphous alkali silicates, which can be present alone or as a mixture with one another. The alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: Si O 2 molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil ( ^R ). Those with a molar Na2θ: Siθ2 ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0425427. In the course of production, they are preferably added as a solid, not in the form of a solution. The crystalline silicates used are preferably crystalline sheet silicates of the general formula a2Si _x θ2χ ₊ i'.yH2θ in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and J-sodium disilicate (Na2Si2θ5'yH2θ) are preferred, whereby β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. fr sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238809 or JP 04/260610. Also practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can be prepared from amorphous alkali silicates, as in European patent applications EP 0548599, EP 0502325 and EP 0425428 can be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0436835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent specifications EP 0 164552 and / or EP 0294753, are used in a further preferred embodiment of the washing or ripening according to the invention detergent used. The content of alkali silicates which can be used as a builder is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on the anhydrous active substance. If alkali alumosilicate, in particular zeolite, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance . The weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

In addition to the inorganic builder mentioned, further water-soluble or water-insoluble inorganic substances can be used in the agents according to the invention. In this context, the alkali carbonates, alkali hydrogen carbonates and alkali sulfates and mixtures thereof are suitable. Such additional inorganic material can be present in amounts up to 70% by weight, but is preferably absent entirely.

In addition, the agents can contain further constituents customary in washing and cleaning agents. These optional components include, in particular, enzymes, enzyme stabilizers, bleaching agents, bleach activators, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, graying inhibitors, for example cellulose ethers, color transfer or vinyl inhibitors, for example polyvinyl pyrrolidone, vinylpyrdin-N-oxide, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4'-bis- (2, 4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, up to 3% by weight, in particular 0.5% by weight to 2% by weight, of graying inhibitors and up to 2% by weight, in particular 0.1% by weight to 1% by weight Contain foam inhibitors, the weight percentages each referring to the entire average.

In addition to water, solvents which are used in particular in the case of liquid agents according to the invention are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, iso-propanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the classes of compounds mentioned. In such liquid agents, the dirt-releasing polyesters are usually dissolved or in suspended form.

Any enzyme present is preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures of these. Protease obtained from microorganisms, such as bacteria or fungi, is primarily suitable. It can be obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German patent applications DE 1940488, DE 2044 161, DE 2201 803 and DE 21 21 397, the US patents US 3632957 and US 4264 738, European patent application EP 006638 and international patent application WO 91/02792. Proteases are commercially available, for example, under the names BLAP ( ^R ), Savinase ( ^R ), Esperase ( ^R ), Maxatase ( ^R ), 0ptimase ( ^R ), Alcalase ( ^R ), Durazym ( ^R ) or Maxapem ( ^R ) . The lipase that can be used can be obtained from Humicola lanuginosa, for example in European patent applications EP 258068 and EP 305216 and EP 341 947, from Bacillus species, as described for example in international patent application WO 91/16422 or European patent application EP 384717, from Pseudomonas species, as for example in European patent applications EP 468102, EP 385401, EP 375102, EP 334462, EP 331 376, EP 330641, EP 214761, EP 218272 or EP 204284 or the international patent application WO 90/10695, from Fusariu species, as described for example in the European patent application EP 130064, from Rhizopus species, as described for example in European patent application EP 117 553, or from Aspergillus species, as described for example in European patent application EP 167 309. Suitable lipases are, for example, under the names Lipolase ( ^R ), Lipozym ( ^R ), Lipomaχ (), Amano ( ^R ) Lipase, Toyo-Jozo ( ^R ) Lipase, Meito ( ^R ) Lipase and Diosynth ( ^R ) lipase commercially available. Suitable amylases are commercially available, for example, under the names Maxamyl ( ^R ) and Termamyl ( ^R ). The cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5. Such cellulases are known, for example, from German laid-open publications DE 31 17250, DE 3207825, DE 3207847, DE 3322950 or European patent applications EP 265832, EP 269977, EP 270974, EP 273 125 and EP 339550.

The customary enzyme stabilizers which are optionally present, in particular in liquid agents according to the invention, include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and their mixtures, lower carboxylic acids, for example from European patent applications EP 376705 and EP 378261 known, boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from. European patent application EP 451 921 known, boric acid esters, as known for example from international patent application WO 93/11215 or European patent application EP 511 456, boronic acid derivatives, as known for example from European patent application EP 583536, calcium salts, for example those from European Patent EP 28865 known Ca-formic acid combination, magnesium salts, such as from the European patent application EP 378262 known, and / or sulfur-containing reducing agents, such as known from European patent applications EP 080 748 or EP 080223.

Suitable foam inhibitors include long-chain soaps, in particular beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate compositions, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309931 or European patent EP 150386.

Furthermore, an agent according to the invention can contain graying inhibitors. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying of the fibers. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example partially hydrolyzed starch. Na carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used.

A further embodiment of an agent according to the invention contains bleaching agents based on peroxygen, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight. . These bleaches that come into consideration are the per compounds generally used in detergents, such as hydrogen peroxide, perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts Such bleaching agents are found in detergents which Contain polymer according to the invention, preferably in amounts up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably of

5% by weight to 15% by weight, based in each case on the total average. The optional component of the bleach activators comprises the N- or O-acyl compounds normally used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazipamides, sulfikurylamides, sulfikuryls, dikuricoles Cyanurates, moreover carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose. In order to avoid the interaction with the compounds during storage, the bleach activators can be coated or granulated with Hü11 substances in a known manner, with tetraacetylethylenediamine granulated with average grain sizes of 0.01 mm to 0.8 mm using carboxyethyl cellulose. as can be produced, for example, by the process described in European Patent EP 37 026, and / or granulated l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine, as described in the German patent Process described DD DD 884 can be produced, is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.

In a preferred embodiment, an agent according to the invention is particulate and, in addition to the active ingredient combination according to the invention, contains 20% by weight to 55% by weight of inorganic builders, up to 15% by weight, in particular 2% by weight to 12% by weight. % water-soluble organic builder, 2.5% by weight to 20% by weight of synthetic anionic surfactant, 0.5% by weight to 20% by weight of nonionic surfactant, up to 25% by weight, in particular 1% by weight up to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight of

6% by weight of bleach activator and up to 20% by weight, in particular 0.1% by weight to 15% by weight, of inorganic salts, in particular alkali carbonate and / or sulfate. In a further preferred embodiment, such a powdery composition, in particular for use as a mild detergent, contains 20% by weight to 55% by weight of inorganic builder, up to 15% by weight, in particular 2% by weight to 12% by weight of water-soluble organic builder, 4% by weight to 24% by weight of nonionic surfactant, up to 15% by weight, in particular 1% by weight to 10% by weight of synthetic anionic surfactant, to 65% by weight, in particular 1% by weight to 30% by weight, of inorganic salts, in particular alkali carbonate and / or sulfate, and neither bleaching agent nor bleach activator.

A further preferred embodiment comprises a liquid agent containing 5% by weight to 35% by weight of water-soluble organic builder, up to 15% by weight, in particular 0.1% by weight to 5% by weight of water-insoluble inorganic builder, up to 15% by weight, in particular 0.5% by weight to 10% by weight of synthetic anionic surfactant, 1% by weight to 25% by weight of nonionic surfactant, up to 15% by weight %, in particular 4% by weight to 12% by weight of soap and up to 30% by weight, in particular 1% by weight to 25% by weight of water and / or water-miscible solvent.

Examples

Example 1: Production of hydroxyl group-terminated soil release Polvester

In a heatable reaction vessel with stirrer, 12.8 kg of terephthalic acid, 19.1 kg of ethylene glycol and 0.1 kg of acidic catalyst (Swedcat ( ^R ) 3) were heated to 200 ° C. under N2 and water was separated until a clear one Melt developed (duration about 3 hours). The poly (ethylene terephthalate) thus obtained was then partially transesterified with polyethylene glycol without working up. 85.0 kg of polyethylene glycol (average molecular weight 3000) and 0.1 kg of acidic catalyst (Swedcat ( ^R ) 5) were added, vacuum (17 mbar) was applied and 14 was reached by heating to 220 ° C , 4 kg of ethylene glycol continuously deposited. The product (SP1) had an OH number of 23 and a softening point in the range from 50 ° C to 60 ° C.

Example 2:

Powdery detergents of the composition given in Table 2 below were tested for their washing performance against greasy soiling. For this purpose, the standardized test soils on cotton listed in Table 2 were washed in a Miele ( ^R ) W 933 washing machine in a 1-cycle process together with 3.5 kg of normally soiled household laundry at 40 ° C or 60 ° C (water hardness 16 ° dH , Detergent dosage 98 g). The test fabrics were then dried and their cleanliness was determined by reflectance measurement (at 460 nm). The reflectance values are also shown in Table 2. It can be seen that agents with the active ingredient combination according to the invention (agents M1 and M2) have significantly better soil release properties than agents which lack a component of the active ingredient combination. Table 1: Composition [% by weight]

Nl M2 VI V2

Na-Ci2 ~ alkylbenzenesulfonate 4 4 2 8

Na ether sulfate ^a ) 4 - 6 -

Na ether sulfate ^D ) - 4 - -

Nonionic surfactant ^c ) 5 5 - 5

Niotensidd) 1 1 6 1

Soap 1 1 1 1

SP1 1 1 1 1

Zeolite NaA 25 25 25 25

Polycarboxylate ^e ) 6 6 6 6

Na ₂ C03 25 25 25 25

Na silicate 1 1 1 1

Na perborate (tetrahydrate) 20 20 20 20

TAED 6 6 6 6

Enzymes ^) 1 1 1 1

a) 1-fold ethoxylated and then sulfated Ciö / ig fatty alcohol b) 2-fold ethoxylated and then sulfated Ci5 / ιg fatty alcohol c) 7-fold ethoxylated d) 5-fold ethoxylated

e) Sokalan ( ^R ) CP5, manufacturer BASF f) Protease / lipase / cellulase combination Table 2: Remission values [%]

Soiling detergent

Ml M2 VI V2

A 57.7 62.1 54.3 55.1

B 62.3 63.1 60.4 59.5

C 71.3 70.8 67.1 68.2

D 68.0 68.7 65.0 66.3

Soiling: A dust / wool fat; 40 degree wash

B dust / skin fat; 40 degree wash

C dust / wool fat; 60 degree wash

D dust / skin fat; 60 degree wash

Claims

claims

1. washing or cleaning agent, which is an active ingredient combination of dirt-releasing polyester, anionic surfactant of the ether sulfate type according to the general formula

R ¹ - (0CH ₂ CH2) n-0-S0 ₃ X (I)

in which R ^{1 is} an alkyl or alkenyl radical having 10 to 22 carbon atoms,

X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion and n is a number from 0.5 to 3, and nonionic surfactant according to the general formula

R ² - (0CH ₂ CH ₂ ) _m -0H (II)

in which R2 is an alkyl or alkenyl radical having 10 to 22 and a number from 6.5 to 8.5.

2. Composition according to claim 1, characterized in that the ratio by weight of dirt-releasing polyester to ether sulfate according to formula I is 1:25 to 1: 3, in particular 1:20 to 1: 5.

3. Composition according to claim 1 or 2, characterized in that the weight ratio of ether sulfate according to formula I to nonionic surfactant according to formula II is 3: 1 to 1: 2, in particular 2: 1 to 1: 1.5.

4. Agent according to one of claims 1 to 3, characterized in that the dirt-releasing polyester is a polymer of ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate Polyethylene oxide terephthalate is 50:50 to 90:10.

5. Composition according to one of claims 1 to 4, characterized in that the active ingredient combination of dirt-releasing polyester, ether sulfate according to formula I and nonionic surfactant according to formula II in amounts of 5 wt .-% to 50 wt .-%, especially 8 wt. -% to 25 wt .-% is included.

6. Agent according to one of claims 1 to 5, characterized in that Rl is an alkyl or alkenyl radical having 12 to 16 carbon atoms, R is an alkyl or alkenyl radical having 12 to 16 carbon atoms, n is a number from 1 to 2 and / or m is a number from 6.8 to 7.5.

7. Composition according to one of claims 1 to 6, characterized in that it is particulate and in addition 20 wt .-% to 55 wt .-% inorganic builder, up to 15 wt .-%, in particular 2 wt .-% up to 12% by weight of water-soluble organic builder, 2.5% by weight to 20% by weight of synthetic anionic surfactant, 0.5% by weight to 20% by weight of nonionic surfactant, up to 25% by weight %, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight to 6% by weight of bleach activator and up to 20% by weight, in particular 0 , 1 wt .-% to 15 wt .-% inorganic salts, in particular alkali carbonate and / or sulfate.

8. Composition according to one of claims 1 to 6, characterized in that it is particulate and in addition 20 wt .-% to 55 wt .-% inorganic builder, up to 15 wt .-%, in particular 2 wt .-% up to 12% by weight of water-soluble organic builder, 4% by weight to 24% by weight of nonionic surfactant, up to 15% by weight, in particular 1% by weight to 10% by weight of synthetic anionic surfactant, to 65% by weight, in particular 1% by weight to 30% by weight, of inorganic salts, in particular alkali carbonate and / or sulfate, and contains neither bleaching agent nor bleach activator.

9. Composition according to one of claims 1 to 6, characterized in that it is liquid and in addition 85 wt .-% to 35 wt .-% water-soluble organic builder, up to 15 wt .-%, in particular 0.1 wt .-% % to 5% by weight of water-insoluble inorganic builders, up to 15% by weight, in particular 0.5% by weight to 10% by weight of synthetic anionic surfactant, 1% by weight to 25% by weight of nonionic surfactant, up to 15% by weight, contains in particular 4% by weight to 12% by weight of soap and up to 30% by weight, in particular 1% by weight to 25% by weight of water and / or water-miscible solvent.

10. Use of an active ingredient combination of dirt-releasing polyester, ether sulfate according to the general formula

R ¹ - (OCH ₂ CH ₂ ) n-0-Sθ3X (I)

in which R ^{1 is} an alkyl or alkenyl radical having 10 to 22, in particular 12 to 18, carbon atoms, X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion and n is a number from 0.5 to 3, in particular of 1 to 2 mean, and nonionic surfactant according to the general formula

R ² - (0CH2CH ₂ ) _m -0H (II)

in which R2 is an alkyl or alkenyl radical having 10 to 22, in particular 12 to 18, carbon atoms and m is a number from 6.5 to 8.5, in particular from 6.8 to 7.5, in washing and Detergents, in particular to increase their cleaning performance compared to greasy soiling.