DE10151287A1 - Urethane based polymers obtained by polymerization of polyisocyanates with polymeric polyols useful for strengthening the dirt removal power of detergents in washing textiles, especially cotton or cotton containing textiles - Google Patents

Abstract

It has been found that urethane based polymers have good dirt removing properties, especially detergent washing of textiles consisting of or containing cotton . A dirt removing polymer obtained by polymerization of polyisocyanates with polymeric polyols, i.e. a polyurethane, of mean mol. wt. above 1000 D and water solubility at 20 deg C higher than 300 g polymer per liter and polyols of mean mol. wt. below 12000 D and water solubility at 20 deg C of 100 g per liter, and optionally other polyols and their mixtures for strengthening the cleaning action of detergents in washing textiles consisting or containing cotton, or which have already been washed in the presence of polymer before being contaminated with dirt, or a polyester active dirt removing polymer from dicarboxylic acid and optionally a polymeric diol for increasing the cleaning power of detergents in washing textiles (sic). Independent claims are included for: (1) A detergent containing the dirt removing polymer obtained by polymerization as described above; (2) production of the polymer in a first stage from a diisocyanate and a polymeric diol of formula (I). W((O-(CH2-)a)b-OH)c (I) (3) preparation of a prepolymer with excess diol which in a second stage is lengthened by reaction with further diisocyanate and a diol of formula (II), (III), (IV), or (V). a = 1-3; b = 3-800; c = 1-6, where b can vary inside the molecule; W = H when c = 1. -(CH2)d when c = 2, d =2-12, -(CH2)-(CH-)e-CH2 when c = e+2, and e = 1-4, -(CH2)e-CH(CH2)-(CH2)e when c = 3 and e = 1-4, aliphatic, alicyclic, or aromatic residue, or one which contains both aliphatic and aromatic groups. HO-X-CHY-OH (II) V((O-((CH2-)fCHR<1>-)g)hOH)i (III) HO((-HCR2(-CH2)m)n-O)o-Cy-C(R<3>)(R<4>)-Cy-(O-((CH2-)pCHR2-)q)rOH (IV) V(-O-C(O)-(C(R<7>)(R<8>))t-(CHOH)u-(CH2)w-H)i (V)

Description

The present invention relates to the use of certain Dirt-releasing polymers to enhance the cleaning performance of detergents Washing textiles, especially those made of cotton or cotton contain, as well as detergents, which such dirt-releasing polymers contain.

In addition to the ingredients that are essential for the washing process, detergents contain such as Surfactants and builder materials usually other components that can be found under the Term washing aids can summarize and so different Active ingredient groups such as foam regulators, graying inhibitors, bleach, Bleach activators and color transfer inhibitors include. To such additives also include substances that give the laundry fiber dirt-repellent properties lend and, if present during the washing process, the dirt-removing ability support the remaining detergent ingredients. The same applies analogously to Hard surface cleaner. Such dirt-releasing substances are often treated as "soil release" actives or because of their assets Surface, for example of the fiber, to be dirt-repellent, as "soil repellents" designated. Because of their chemical similarity to polyester fibers in textiles this material are particularly effective dirt-releasing active ingredients Copolyester, the dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units contain. 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 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. German laid-open specification DT 22 53 063 lists acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and, if appropriate, an alkylene or cycloalkylene glycol. Polymers made from ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights from 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 described in German patent DE 28 57 292. 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 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 2: 1 to 6: 1, can be according to the German published patent application DE 33 24 258 can be used in detergents. European patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European or European patent EP 185 427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer. 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 and with C ₁ - until C ₄ -alkyl groups are end group-capped. 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 0.6 to Is 0.95. European patent application EP 272 033 discloses polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are end-capped by C _1-4 alkyl or acyl radicals. European patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil-release polyesters. In European patent application EP 357 280, soil-release polyesters with terephthalate, alkylene glycol and poly-C _2-4 -glycol units are produced by sulfonation of unsaturated end groups. German patent application DE 26 55 551 describes the reaction of such polyesters with polymers containing isocyanate groups and the use of the polymers prepared in this way to prevent dirt from being re-absorbed when washing synthetic fibers. From the German patent DE 28 46 984, detergents are known which contain a reaction product of a polyester with a prepolymer containing terminal isocyanate groups, obtained from a diisocyanate and a hydrophilic nonionic macrodiol, as the dirt-removing polymer.

The polymers known from this extensive prior art have the Disadvantage on that in the case of textiles that are not or at least not predominantly consist of polyester, have no or insufficient effectiveness. A large Part of today's textiles is made of cotton or Cotton-polyester blended fabrics, so that there is a need for greasy soiling on such textiles better effective dirt-releasing polymers.

Surprisingly, it was found that this task was achieved by using certain urethane-based polymers can be solved.

The invention relates to the use of dirt-releasing polymers which are obtainable by polymerizing polyisocyanates with polymeric polyols an average molecular weight of over 1000 D and a water solubility at 20 ° C of over 300 g polymer per liter as well as polyols with an average molecular weight of less than 12000 D. and a water solubility at 20 ° C of less than 100 g per liter and optionally other polyols and their mixtures, to enhance the cleaning performance of Detergents for washing textiles made of cotton or cotton contain.

The washing performance-enhancing effect of the invention is particularly pronounced using polymers with multiple use, that is, in particular for Removal of soiling from appropriate textiles already at Presence of the polymer had been washed before being soiled were provided.

Preferred polymeric polyols with an average molecular weight of over 1000 D and a water solubility at 20 ° C. of over 300 g of polymer per liter can be described by the general formula I,

W [(O- (CH ₂ -) _a ) _b -OH] _c (I)

in which a is a number from 1 to 3, b is a number from 17 to 800 and c is a number from 1 to 6, where b can vary within one molecule;
W can stand for H- with c = 1,
- (CH ₂ ) _d - with c = 2, where d stands for a number from 2 to 12,
-CH ₂ - (CH-) _e -CH ₂ - with c = e + 2, where e stands for a number from 1 to 4,
- (CH ₂ ) _e -CH (CH ₂ -) - (CH ₂ ) _e with c = 3, where e represents a number from 1 to 4,
or for any aliphatic, alicyclic or aromatic radical or a radical which contains both aliphatic and aromatic groups.

A particularly preferred polymeric polyol with high water solubility is Polyethylene glycol, very particularly preferred is polyethylene glycol with a medium Molar mass between 3000 and 12000 D.

Preferred polyols with an average molecular weight of less than 12,000 D and a water solubility at 20 ° C. of less than 100 g per liter can be described by the general formulas II to IV

HO-X-CHY-OH (II),

in which X represents a linear or branched alkylene group having 1 to 48 carbon atoms and Y represents hydrogen or an alkyl group having 1 to 24 carbon atoms,

V [(O - ((CH ₂ -) _f CHR ¹ -) _g ) _h OH] _i (III)

in which R ^{1 is} hydrogen or an alkyl group having 1 to 6 carbon atoms, f is a number from 0 to 3, g is a number from 1 to 4 and h is a number from 5 to 300, where R ¹ , f and
h can vary within a molecule;
V can stand for H- with i = 1,
- (CH ₂ ) _k - with i = 2, where k is a number from 2 to 12,
-CH ₂ - (CH-) ₁ -CH ₂ - with i = 1 + 2, where 1 stands for a number from 1 to 4,
- (CH ₂ ) ₁ -CH (CH ₂ -) - (CH ₂ ) ₁ - with c = 3, where 1 stands for a number from 1 to 4,
or for any aliphatic, alicyclic or aromatic radical or a radical which contains both aliphatic and aromatic groups,

HO ((- CHR ² (-CH ₂ ) _m ) _n -O) _o -Cy-C (R ³ ) (R ⁴ ) -Cy- (O - ((CH ₂ -) _p CHR ² -) _q ) _r OH (IV)

in which Cy represents phenylene or cyclohexylidene, R ^{2 represents} hydrogen or an alkyl group having 1 to 6 C atoms, R ³ and R ⁴ independently of one another represent hydrogen or an alkyl group having 1 to 6 C atoms or together represent an aliphatic bridge (CR ⁵ R ⁶ ) _s form in which s can represent a number from 4 to 6 and R ⁵ and R ⁶ independently of one another H or an alkyl group having 1 to 6 C atoms or a double bond, R ⁵ and R ^{6 being} within a bridge can vary, m and p independently of one another represent a number from 0 to 3, n and q independently of one another represent a number from 1 to 4 and o and r independently of one another represent a number from 0 to 20, where R ² , m and p can vary within a molecule.

Polymeric polyols according to formula (III) are preferably derived from 1,2-propylene glycol, 1,2-butanediol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and / or Neopentyl glycol. Particularly preferred polymeric polyols according to formula (III) are Polypropylene oxide and polytetrahydrofuran with medium degrees of polymerization in Range from 3 to 70.

Polymeric diols according to formula (IV) are preferably derived from bisphenol A or Bisphenol F. Particularly preferred diols according to formula (IV) are propoxylated and ethoxylated bisphenol A.

Preferred further polyols are castor oil, partially hydrogenated castor oil, dimethylolpropionic acid and its salts, N-alkyldiethanolamine and its salts and water-soluble polymeric polyols with an average molecular weight of less than 1000 D and a water solubility at 20 ° C. of more than 500 g of polymer per liter, which is the general Correspond to formula I in which a is a number from 1 to 3, b is a number from 3 to 16 and c is a number from 1 to 6, where b can vary within one molecule. In these connections W can stand for H- with c = 1,
- (CH ₂ ) _d with c = 2, where d is a number from 2 to 12,
-CH ₂ - (CH-) _e -CH ₂ - with c = e + 2, where e stands for a number from 1 to 4,
- (CH ₂ ) _e -CH (CH ₂ -) - (CH ₂ ) _e with c = 3, where e represents a number from 1 to 4,
or for any aliphatic, alicyclic or aromatic radical or a radical which contains both aliphatic and aromatic groups.

The particularly preferred polyols also include polyethylene glycol with a medium one Molar mass from 300 D to 1000 D.

In a further preferred embodiment of the invention, polymers used, which are obtainable by using mixtures of at least two polymeric diols of various degrees of polymerization (b in formula I), the Degree of polymerization of the two polymer diol variants according to formula (I) is preferred differ by at least a factor of 10, for example when using a first polymeric diols with a degree of polymerization in the range of 8 to 15 and one second polymeric diol with a degree of polymerization in the range of 100 to 150.

The polyisocyanates are compounds of the general structure (O = C = N-) _t Z, where t is the number 2 or 3, Z is an aliphatic or aromatic radical or a radical which has both aliphatic and aromatic groups contains. Among these, compounds are preferred in which the isocyanate groups are bonded to an aromatic radical via alkylene groups, or in which the isocyanate groups are bonded to aromatic radicals which are bonded to one another directly or via an alkylene group. In a preferred embodiment of the invention, the polyisocyanate is a diisocyanate.

Examples of suitable diisocyanates are 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H ₁₂ MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and Tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, the isomers of tolylene diisocyanate (TDI), 1-methyl-2,4-diisocyanato-cyclohexane, 1,6-diisocyanato-2,2 , 4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (IPDI), chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, 4,4 ' -Diisocyanatophenylperfluoroethane, tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, phthalic acid bis-isocyanatoethyl ester, also diisocyanates with reactive halogen atoms, such as 1-chloromethylphenyl-2 , 4-diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate, 3,3-bis-chloromethyl ether-4,4'-diphenyl diisocyanate. Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxydihexyl sulfide. Other important diisocyanates are trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane and dimer fatty acid diisocyanate. Tetramethylene, hexamethylene, undecane, dodecamethylene, 2,2,4-trimethylhexane, 1,3-cyclohexane, 1,4-cyclohexane, 1,3- and 1,4-tetramethylxylene are particularly suitable. , Isophorone, 4,4-dicyclohexylmethane and lysine ester diisocyanate. 4,4'-Diphenylmethane diisocyanate and / or tetramethylxylene diisocyanate are very particularly preferred, especially the m-TMXDI.

The molar ratio of polyol - that is, the sum of polymeric polyols Formula (I) and polyol according to formulas (II) to (IV) - to polyisocyanate is preferably 1: 1 to 1.5: 1, in particular 1.05: 1 to 1.3: 1. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution preferred dirt-releasing polyurethane is in the range from 1500 to 2,000,000, especially from 8,000 to 150,000.

In the production known in principle, particularly preferably according to the invention Using polyurethanes is preferably carried out in such a way that first in a first stage from the polyisocyanate, preferably a diisocyanate, and polymer Polyol according to formula (I), which is preferably a diol (c = 2), prepolymers with Excess polyol produces in a second stage by reaction with another Polyisocyanate and a polyol according to formula (II), (III) or (IV), which is preferred is also a diol. It is possible to enter the second stage use different diisocyanate than in the first stage, for example the reaction of to conduct the first stage with MDI and the reaction of the second stage with TMXDI. If like Several polymeric polyols according to formula (I) with different Degrees of polymerization are to be used, it is preferred that with to use the lowest degree of polymerization in the first stage and that or those with higher degrees of polymerization in the second stage together with the Use polyol according to formula (II), (III) or (IV). So available polymers on Urethane bases are preferably used in the context of the present invention.

As described, the polyurethanes used according to the invention are simple producible and ecologically and toxicologically harmless. They lead to one significantly better detachment of grease and cosmetic stains in particular Cotton or cotton-containing fabrics than previously used known compounds for this purpose is the case. Alternatively, at Consistent fat removal ability saved significant amounts of surfactants become.

Another object of the invention is the use of a combination of such a cotton-active dirt-releasing polymer based on urethane a polyester active dirt release polymer from a dicarboxylic acid and an optionally polymeric diol to enhance the cleaning performance of Detergents when washing textiles.

The known polyester-active dirt-releasing polymers which can be used in addition to the urethane-based polymers essential to the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. 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 HO- (CHR ¹¹ -) _a OH, which is also used as a polymer Diol H- (O- (CHR ₁₁ -) _a ) _b 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, R ^{11 is} hydrogen, an alkyl radical having 1 to 22 carbon atoms and their mixtures, a a number from 2 to 6 and b a number from 1 to 300. Preferably, both monomer diol units -O- (CHR ₁₁ -) _a O- and polymer diol units - ( O- (CHR ¹¹ -) _a ) _b O- before. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b 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 in the range from 250 to 100,000, in particular from 500 to 50,000. The acid on which the rest Ph is based is preferably derived 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 them, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small proportions, in particular not more than 10 mol%, based on the proportion 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 HO- (CHR ¹¹ -) _a OH include those in which R ^{11 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ¹¹ is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -CHR ¹¹ -OH, in which R ^{11 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-octanediol, 1,2-decanediol, 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-capped, the end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids come into question. The one bound via ester bonds End groups can be alkyl, alkenyl and aryl monocarboxylic acids with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, Caproic acid, enanthic 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, petroselaidic acid, oleic acid, Linoleic acid, linolaidic acid, linolenic 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, the 1 to 5 substituents with a total can carry up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert. Butylbenzoic. The end groups can also be hydroxymonocarboxylic acids with 5 to 22 Underlying C atoms, for example hydroxyvaleric acid, Hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and include p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can in turn be connected to one another via their hydroxyl group and their carboxyl group and thus exist more than once in an end group. Preferably the number of Hydroxymonocarboxylic acid units per end group, that is their degree of oligomerization, in the range of 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention are polymers of ethylene terephthalate and polyethylene oxide terephthalate, in which the Polyethylene glycol units have molecular weights from 750 to 5000 and that Molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10 in combination with nitrogen-containing dirt-releasing polymers screw cap.

The soil release polymers to be used according to the invention are preferably water-soluble, the term "water-soluble" being a solubility of at least 0.01 g, preferably at least 0.1 g of the polymer per liter of water Room temperature and pH 8 should be understood. Polymers used with preference under these conditions, however, a solubility of at least 1 g per liter, in particular at least 10 g per liter.

The use according to the invention can be carried out in the course of a washing process take place that the urethane-based polymer of a detergent-containing liquor separately adds, or introduces the polymer as part of the detergent into the liquor. On Another object of the invention is therefore a detergent, the one described above Contains urethane-based polymer.

Detergent which is a urethane-based polymer to be used according to the invention contain, can contain all usual other ingredients of such means, which are not in undesirably with the soil-release polymer essential to the invention interact. The polymer is preferably used in amounts of 0.1% by weight to 5% by weight, in particular 0.5% to 2.5% by weight incorporated into detergent.

Surprisingly, it was found that such polymers with the above Properties the effect of certain other detergents and cleaning agents positively influence and that conversely the effect of the cotton-active soil release Polymer is reinforced by certain other detergent ingredients. These effects occur in particular in the case of enzymatic active substances, in particular proteases and lipases, in water-insoluble inorganic builders, in water-soluble inorganic and organic builders, especially based on oxidized carbohydrates, for bleaching agents based on peroxygen, especially with alkali percarbonate, and with synthetic Anionic surfactants of the sulfate and sulfonate type, which is why the use of the aforementioned ingredients together with polymers to be used according to the invention is preferred.

In a preferred embodiment, such an agent contains nonionic surfactant, selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular -ethoxylates and / or -propoxylates, fatty acid polyhydroxyamides and / or Ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, Fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, especially in one Amount in the range of 2% to 25% by weight.

Another embodiment of such agents involves the presence of synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, Fatty alkyl ether sulfate, sulfofatty acid esters and / or sulfofatty acid disalts, especially in an amount ranging from 2% by weight to 25% by weight. The anionic surfactant is preferred from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates selected in which the alkyl or alkenyl group 8 to 22, in particular 12 to 18 C- Owns 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 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols 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 octadecyl radicals, and mixtures thereof, can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used. In addition, there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as in accordance with the processes of US Pat. No. 1,985,424. US 2 016 962 and US 2 703 798 and international patent application WO 92/06984 can be considered. So-called alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) _n -OR ¹² , in which R ^{12 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. Such compounds and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828. The glycoside component (G) _n is an oligomer or polymer from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Xylose and Lyxose belong to. 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 oligomerization. The degree of oligomerization n generally takes fractional 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 ^{12 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, ie mixtures with essentially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is in agents which use one according to the invention Containing soil release active ingredient, preferably in amounts of 1% by weight to 30% by weight, Contain in particular from 1 wt .-% to 25 wt .-%, with amounts in the upper part of this Range are more likely to be found in liquid detergents and particulate Detergents preferably contain smaller amounts of up to 5% by weight.

Instead, or in addition, the agents can contain further surfactants, preferably synthetic ones Anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, in Amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18 wt .-%, each based on the total, included. As for use in Synthetic anionic surfactants which are particularly suitable for such agents are the alkyl and / or Alkenyl sulfates with 8 to 22 carbon atoms, which are an alkali, ammonium or alkyl or carry hydroxyalkyl-substituted ammonium ion as a counter cation call. The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms are preferred. Atoms and their branched chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding Alcohol component with a conventional sulfating reagent, especially sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or Alkyl- or hydroxyalkyl-substituted ammonium bases can be produced. Such alkyl and / or alkenyl sulfates are in the agents which a Contain urethane-based polymer according to the invention, preferably in amounts of Contain 0.1% by weight to 15% by weight, in particular from 0.5% by weight to 10% by weight.

The sulfate-type surfactants that can be used also include the sulfated ones Alkoxylation products of the alcohols mentioned, so-called ether sulfates. Preferably contain such ether sulfates 2 to 30, in particular 4 to 10 ethylene glycol groups per Molecule. Suitable sulfonate-type anionic surfactants include those by Implementation of fatty acid esters with sulfur trioxide and subsequent neutralization available α-sulfoesters, in particular those derived from fatty acids with 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, derivative sulfonation products, and those by formal Saponification from these emerging sulfo fatty acids.

Soaps are further optional surfactant ingredients, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, being suitable. Soap mixtures are particularly preferred which are composed of 50% by weight to 100% by weight of saturated C ₁₂ -C ₁₈ 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 compositions which contain a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present.

In a further embodiment, an agent which contains an agent according to the invention containing polymer contains, water-soluble and / or water-insoluble builder, especially selected from alkali alumosilicate, crystalline alkali silicate with modulus over 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 contains a polymer to be used according to the invention 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 also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality. The relative molecular weight 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 methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ 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. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ carboxylic acids, with vinyl alcohol are particularly preferred. 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% by weight to 40% by weight, preferably 10% by weight to 30% by weight of 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, in the 2-position, has an alkyl radical, preferably a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is substituted. 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 methallylsulfonic acid or methallylsulfonate 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 prepared in particular by processes which are described in German patent specification DE 42 21 381 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 3000 and 10,000. They can be used, in particular for the production of liquid agents, 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 in the form of their water-soluble salts, especially their alkali salts used.

Organic builder substances of this type 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 contain. Amounts close to the upper limit mentioned are preferably in paste-like or liquid, in particular water-containing, agents used, in which the polymer according to the invention is contained.

In particular, crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, 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% by weight. used. Among these, the crystalline aluminosilicates in detergent quality, in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size of more than 30 mm and preferably consist of at least 80% by weight of particles with a size of less than 10 mm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is in the range from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the alumosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the compositions 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, especially the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar Na ₂ O: SiO ₂ ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. They are preferably added as a solid and not in the form of a solution during production. Crystalline sheet silicates of the general formula Na ₂ Si _x O _{2x + 1} .yH ₂ O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Crystalline layered silicates which come 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 in the general formula mentioned assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. δ- sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 described, can be used in agents containing a polymer 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 0 436 835. 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 EP 0 164 552 and / or European patent application EP 0 294 753, are used in a further preferred embodiment of washing machines. or cleaning agents which contain a polymer according to the invention. Their alkali silicate content 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 aluminosilicate, 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 especially 1: 1 to 2: 1.

In addition to the inorganic builder mentioned, other water-soluble or water-insoluble inorganic substances in the agents, which according to the invention containing soil-release polymer used. Are suitable in this Relationship between the alkali carbonates, alkali hydrogen carbonates and alkali sulfates as well their mixtures. Such additional inorganic material can be used in amounts of up to 70% by weight. to be available.

In addition, the agents can be further customary in detergents and cleaning agents Components included. These optional components include in particular Enzymes, enzyme stabilizers, bleaches, 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 inhibitors, for example Polyvinylpyrrolidone or polyvinylpyrdine-N-oxide, foam inhibitors, for example Organopolysiloxanes or paraffins, solvents and optical brighteners, for example Stilbene disulfonic acid derivatives. Preferably, agents that are an inventive Polymer contain up to 1 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-% 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 up to 2% by weight complexing agent 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 Graying inhibitors and up to 2% by weight, in particular 0.1% by weight to 1% by weight Contain foam inhibitors, the weight percentages being based on draw all funds.

Solvents, in particular in the case of liquid agents which have an inventive In addition to water, polymer used are preferably those which are miscible with water. These include the lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerin, lower glycols, for example Ethylene and propylene glycol, and those derived from the classes of compounds mentioned Ether. The polyesters according to the invention are generally in such liquid compositions dissolved or in suspended form.

Any enzymes present are preferably included in the group Protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or Mixtures selected from these. Primarily comes from microorganisms such as Bacteria or fungi, protease obtained in question. You can by in a known manner Fermentation processes can be obtained from suitable microorganisms, for example in the German patent applications DE 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and 4,264,738, the European patent application EP 006 638 and the international patent application WO 91/02792 are described. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem® available. The usable lipase can be from Humicola lanuginosa, such as for example in European patent applications EP 258 068, EP 305 216 and EP 341 947 described, from Bacillus species, such as in the international Patent application WO 91/16422 or European patent application EP 384 717 described, from Pseudomonas species, such as in the European Patent applications EP 468 102, EP 385 401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international patent application WO 90/10695 described, from Fusarium species, such as in the European Patent application EP 130 064 described, from Rhizopus species, such as in the European patent application EP 117 553 described, or from Aspergillus species, such as described, for example, in European patent application EP 167 309 become. Suitable lipases are, for example, under the names Lipolase®, Lipozym®, Lipomax®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase available in the stores. Suitable amylases are, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm commercially available. The usable Cellulase can be an enzyme that can be obtained from bacteria or fungi, which has a pH Optimal preferably in the weakly acidic to weakly alkaline range from 6 to 9.5. Such cellulases are, for example, from the German Publications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or the European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 and international patent applications WO 95/02675 and WO 97/14804 known and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.

Regarding the usual ones, especially those present in liquid funds Enzyme stabilizers include amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, such as from the European patent applications EP 376 705 and EP 378 261 known boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from the European patent application EP 451 921 known boric acid esters, such as from international patent application WO 93/11215 or European Patent application EP 511 456 known, boronic acid derivatives, such as from the European Patent application EP 583 536 known calcium salts, for example those from the European patent EP 28 865 known Ca-formic acid combination, Magnesium salts, such as from European patent application EP 378 262 known, and / or sulfur-containing reducing agents, such as from the European patent applications EP 080 748 or EP 080 223 known.

Suitable foam inhibitors include long chain soaps, in particular Beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and their mixtures, the moreover microfine, optionally silanized or otherwise May contain hydrophobized silica. For use in particulate media such foam inhibitors are preferably granular, water-soluble Carrier substances bound, as for example in German Offenlegungsschrift DE 34 36 194, the European patent applications EP 262 588, EP 301 414, EP 309 931 or the European patent EP 150 386 described.

Furthermore, an agent which contains a polymer used according to the invention can Graying inhibitors included. Graying inhibitors have the task of being controlled by the Fiber detached dirt to keep suspended in the fleet and so the graying of the To prevent fibers. Water-soluble colloids of mostly organic nature are suitable for this, 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. Also water-soluble, acidic Group-containing polyamides are suitable for this purpose. Furthermore, use soluble starch preparations and other starch products than the above to Example of partially hydrolyzed starch. Na carboxymethyl cellulose, methyl cellulose, Methylhydroxyethyl cellulose and mixtures thereof are preferably used.

Another embodiment of such an agent, which according to the invention Soil-release polymer used, contains peroxygen-based bleach, in particular in amounts in the range from 5% by weight to 70% by weight, and if appropriate Bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight. This Possible bleaches are those that are usually used in detergents Per compounds such as hydrogen peroxide, perborate, which as a tetra or monohydrate Percarbonate, perpyrophosphate and persilicate, which are usually available as Alkali salts, in particular as sodium salts, are present. Such bleaches are in Detergents which contain a polymer used according to the invention, preferably in amounts up to 25% by weight, in particular up to 15% by weight and particularly preferred from 5% by weight to 15% by weight, based in each case on the total average, where Percarbonate in particular is used. The optional component of the Bleach activators includes the commonly used N- or O-acyl compounds, for example multiple acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, Hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, also Carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, in particular Sodium isononanoyl phenol sulfonate, and acylated sugar derivatives, in particular Pentaacetylglucose. The bleach activators can be used to avoid interaction with the Per compounds in storage in a known manner coated with coating substances or have been granulated, with the help of carboxymethyl cellulose granulated tetraacetylethylenediamine with average grain sizes from 0.01 mm to 0.8 mm, such as that described in European Patent EP 37 026 Process can be prepared and / or granulated 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine, as described in the German patent DD 255 884 described method can be prepared, is particularly preferred. In Such bleach activators are preferably 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 average.

In a preferred embodiment, an agent in which is according to the invention Soil-release polymer is incorporated, particulate and contains 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular 2% by weight to 8% by weight of water-soluble organic builder, 10% by weight to 25% by weight synthetic anionic surfactant, 1% by weight to 5% by weight nonionic surfactant, up to 25% by weight, in particular 5% by weight to 20% by weight of bleaching agent, in particular alkali percarbonate, up to 15% by weight, in particular 1% by weight to 10% by weight, of bleach activator and up to 25% by weight, in particular 0.1% by weight to 25% by weight, of inorganic salts, in particular Alkali carbonate and / or bicarbonate.

Examples example 1 Manufacture of polyurethanes

492.4 g and 1208.5 g of polyethylene glycol 600 (degree of polymerization approx. 13) were submitted and dewatered at 80 ° C and 1 mbar for about 2 h. Then was under Nitrogen at 80 ° C in portions of 187.7 g or 375.4 g of 4,4'-diphenylmethane diisocyanate of 40-50 g added over about 90 min and then at 80 ° C under nitrogen stirred until the isocyanate was completely consumed (about 2 h). Here, the Prepolymers P1 (average molecular weight approx. 6600) or P2 (average Molecular weight approx. 2700).

465 g P1 were mixed with 468 g polyethylene glycol 6000 (degree of polymerization approx. 137) and 23 g 12-Hydroxy-octadecan-1-ol dewatered for about 2 h at 100 ° C. and 2 mbar with stirring and then with 44 g of tetramethylxylylene diisocyanate at 150-160 ° C to constant melt viscosity to the polymer SRP1 (ratio OH: NCO 1.21) implemented.

575 g of P2 were mixed with 318 g of polyethylene glycol 6000 (degree of polymerization approx. 137) and 30 g 12-Hydroxy-octadecan-1-ol dewatered for about 2 h at 100 ° C. and 2 mbar with stirring and then with 77 g of tetramethylxylylene diisocyanate at 150-160 ° C to constant melt viscosity to the polymer SRP2 (ratio OH: NCO 1.14) implemented.

267 g of P2 were mixed with 118 g of polyethylene glycol 6000 (degree of polymerization approx. 137), 14 g 12-hydroxy-octadecan-1-ol and 23 g dimethylolpropionic acid for approx. 1 h at 90 ° C and 1 mbar dehydrated with stirring and then with 78 g of tetramethylxylylene diisocyanate at 140-150 ° C to constant melt viscosity to the polymer SRP3 (OH: NCO ratio 1.06) implemented.

Example 2

Containing a detergent (V1) SECTION 12 parts by weight FAS 5 parts by weight C12 / 14 7 EO 3 parts by weight TAED 7 parts by weight percarbonate 17 parts by weight soda 13 parts by weight zeolite 28 parts by weight Sokalan CP 5 5 parts by weight Tinopal DMS-X 0.2 parts by weight

2 parts by weight of SRP1 (W1) or 2 parts by weight of SRP2 (W2) were added. Fabrics made from pure cotton, refined cotton and polyester / cotton blended fabrics 50/50 were treated as follows:
Washing machine: Miele W 918 Novotronic
Primary washing performance: normal program single-washing process
Washing temperature: 40 ° C
Determination: 3 times
Fleet volume: 18 l
Water hardness: 16 ° dH
Filling laundry: 3.5 kg clean laundry

The fabrics were washed uncontaminated three times with the detergent to be tested under the conditions specified above and dried after each wash. After prewashing three times, the fabrics were soiled with the following standardized soiling by hand:
0.15 g cream rouge
0.10 g lipstick
0.10 g black shoe polish
0.10 g dust / skin fat

The soiled tissues were measured with a Minolta CR 200 and then aged for 7 days at RT. After that, the soiled tissues were opened Towels stapled and washed under the conditions specified above.

The tissues were dried and measured again with a Minolta CR 200. The following washing results (dde values) resulted: Table 2 pure cotton

Table 3 cotton refined

Table 4 Cotton / polyester

It can be seen that the detergents with the polymers to be used according to the invention (W1 and W2) show a significantly better washing performance than the agent to which the polymer is missing.

Claims (15)

1. Use of soil release polymers which are obtainable by Polymerization of polyisocyanates with polymeric polyols with an average molecular weight of over 1000 D and a water solubility at 20 ° C of over 300 g polymer per Liters and polyols with an average molecular weight of less than 12000 D and one Water solubility at 20 ° C of less than 100 g per liter and other, if necessary Polyols and their mixtures, to enhance the cleaning performance of Detergents when washing textiles made of cotton or Cotton included. 2. Use of dirt-releasing polymers which are obtainable by Polymerization of polyisocyanates with polymeric polyols with an average molecular weight of over 1000 D and a water solubility at 20 ° C of over 300 g polymer per Liters and polyols with an average molecular weight of less than 12000 D and one Water solubility at 20 ° C of less than 100 g per liter and other, if necessary Polyols and their mixtures, to enhance the cleaning performance of Detergents when washing textiles made of cotton or Contain cotton and have already been washed in the presence of the polymer were before they were soiled. 3. Use of a combination of soil release polymer is obtainable by polymerizing polyisocyanates with polymeric polyols an average molecular weight of over 1000 D and a water solubility at 20 ° C of over 300 g polymer per liter and polyols with an average molecular weight of less than 12000 D and a water solubility at 20 ° C of less than 100 g per liter as well optionally further polyols and their mixtures, and a polyester-active soil release polymer from a dicarboxylic acid and a optionally polymeric diol to enhance the cleaning performance of Detergents when washing textiles. 4. Use according to one of claims 1 to 3, characterized in that the polymeric polyol with a mean molecular weight of over 1000 D and a water solubility at 20 ° C of over 300 g of polymer per liter of a compound of formula (I)

W [(O- (CH ₂ -) _a ) _b -OH] _c (I)

in which a is a number from 1 to 3, b is a number from 17 to 800 and c is a number from 1 to 6, where b can vary within one molecule,
W for H- with c = 1,
- (CH ₂ ) _d - with c = 2, where d stands for a number from 2 to 12,
-CH ₂ - (CH-) _e -CH ₂ - with c = e + 2, where e stands for a number from 1 to 4,
- (CH ₂ ) _e -CH (CH ₂ -) - (CH ₂ ) _e - with c = 3, where e represents a number from 1 to 4,
or represents any aliphatic, alicyclic or aromatic radical or a radical which contains both aliphatic and aromatic groups. 5. Use according to one of claims 1 to 3, characterized in that the polymeric polyol with an average molecular weight of over 1000 D and one Water solubility at 20 ° C of over 300 g polymer per liter a polyethylene glycol, in particular with an average molecular weight between 3000 and 12000 D. 6. Use according to one of claims 1 to 5, characterized in that the polyol with an average molecular weight of less than 12000 D and a water solubility at 20 ° C of less than 100 g per liter corresponds to one of the general formulas II to IV,

HO-X-CHY-OH (II),

in which X represents a linear or branched alkylene group having 1 to 48 carbon atoms and Y represents hydrogen or an alkyl group having 1 to 24 carbon atoms,
V [(O - ((CH ₂ -) _f CHR ¹ -) _g ) _h OH] _i (III)

in which R ^{1 is} hydrogen or an alkyl group having 1 to 6 carbon atoms, f is a number from 0 to 3, g is a number from 1 to 4 and h is a number from 5 to 300, where R ¹ , f and h can vary within a molecule;
V for H- with i = 1,
- (CH ₂ ) _k - with i = 2, where k is a number from 2 to 12,
-CH ₂ - (CH-) ₁ -CH ₂ - with i = 1 + 2, where 1 stands for a number from 1 to 4,
- (CH ₂ ) ₁ -CH (CH ₂ ) - (CH ₂ ) ₁ - with c = 3, where 1 stands for a number from 1 to 4,
or represents any aliphatic, alicyclic or aromatic radical or a radical which contains both aliphatic and aromatic groups,

HO ((- CHR ² (-CH ₂ ) _m ) _n -O) _o -Cy-C (R ³ ) (R ⁴ ) -Cy- (O - ((CH ₂ -) _p CHR ² -) _q ) _r OH (IV)

in which Cy represents phenylene or cyclohexylidene, R ^{2 represents} hydrogen or an alkyl group having 1 to 6 C atoms, R ³ and R ⁴ independently of one another represent hydrogen or an alkyl group having 1 to 6 C atoms or together represent an aliphatic bridge (CR ⁵ R ⁶ ) _s form in which s can represent a number from 4 to 6 and R ⁵ and R ⁶ independently of one another H or an alkyl group having 1 to 6 C atoms or a double bond, R ⁵ and R ^{6 being} within a bridge can vary, m and p independently of one another represent a number from 0 to 3, n and q independently of one another represent a number from 1 to 4 and o and r independently of one another represent a number from 0 to 20, where R ² , m and p can vary within a molecule. 7. Use according to one of claims 1 to 6, characterized in that the polymers are obtainable by using polyisocyanates of the general structure (O = C = N-) _t Z, where t represents the number 2 or 3, Z is an aliphatic or is an aromatic radical or a radical which contains both aliphatic and aromatic groups. 8. Use according to claim 7, characterized in that the polyisocyanate Is diisocyanate. 9. Use according to claim 8, characterized in that the diisocyanate Diphenylmethane diisocyanate and / or tetramethylxylene diisocyanate. 10. Use according to one of claims 1 to 9, characterized in that the Molar ratio of polyol to polyisocyanate 1: 1 to 1.5: 1, in particular 1.05: 1 to 1.3: 1. 11. Use according to one of claims 1 to 10, characterized in that the Polymer is obtainable by a diisocyanate and a polymeric diol according to formula (I) prepolymers with excess diol produces in a second stage by reaction with further diisocyanate and a diol according to formula (II), (III) or (IV) can be extended. 12. Use according to claim 11, characterized in that the polymer thereby is available that a different diisocyanate is used in the second stage than in the first stage. 13. Use according to claim 11 or 12, characterized in that the polymer is obtainable in that several polymeric diols according to formula (I) with different degrees of polymerization are used and the one with the lowest degree of polymerization in the first stage and that or those with higher degree of polymerization in the second stage together with the diol Formula (II), (III) or (IV) can be used. 14. Detergent containing a soil release polymer which is available by polymerizing polyisocyanates with polymeric polyols with a medium Molar mass of over 1000 D and a water solubility at 20 ° C of over 300 g Polymer per liter as well as polyols with an average molecular weight of less than 12000 D. and a water solubility at 20 ° C of less than 100 g per liter and optionally other polyols and their mixtures. 15. Composition according to claim 14, characterized in that it contains the polymer in amounts of Contains 0.1% by weight to 5% by weight, in particular 0.5% by weight to 2.5% by weight.