HK1070376B

HK1070376B - Cotton active, dirt removing urethane-based polymers

Info

Publication number: HK1070376B
Application number: HK05103027.6A
Authority: HK
Inventors: 约瑟夫．彭宁格; 沃尔夫冈．德尼尔; 雷纳．舍恩菲尔德
Original assignee: 汉高两合股份公司
Priority date: 2001-10-22
Filing date: 2002-10-12
Publication date: 2010-10-29

Description

Cotton-active, soil release urethane-based polymers

The present invention relates to the use of certain soil release polymers to increase the soil release efficiency of detergents in the laundering of cotton or cotton-containing textiles and detergents containing such soil release polymers.

In addition to the substances which are essential in the washing process, such as surfactants and builders, detergents usually contain what are known as detergency builders, including substances of different active ingredients, such as foam regulators, antiresoiling agents, bleaches and transfer agents, and also substances which impart soil repellency to the fibres being washed, if present during the washing process, to the effect that the detergent components usually have detergency, the same meaning applies to detergents for cleaning hard surfaces. Such materials having the ability to remove soil are often referred to as "soil release" actives or as "soil release agents" because of their ability to remove soil from the surface being treated, such as fibers. Because of the chemical similarity of textiles constructed from such materials to polyester fibers, particularly effective soil release active materials are copolyesters containing dicarboxylic acid units, alkylene glycol and polyalkylene glycol units, which are known for a long time for use in chemical detergents.

A washing process with addition of polyethylene terephthalate-polyoxyethylene glycol-copolymers is described, for example, in German patent publication DT1617141, in which the washing agent referred to in German patent publication DT2200911 comprises a nonionic surfactant and a mixed polymer of polyoxyethylene glycol and polyethylene terephthalate, and the acidic textile finish proposed in German patent publication DT2253063 comprises a copolymer of a dicarboxylic acid and an alkylene-or cycloalkylene polyglycol and optionally an alkylene-or cycloalkylene glycol, the molar weight of polyethylene glycol units in the polymer of ethylene terephthalate and polyoxyethylene-terephthalate being from 750 to 5000 and the molar ratio of ethylene terephthalate to polyoxyethylene-terephthalate being from 50: 50 to 90: 10, the use of these additives in detergents is described in German patent specification DE 2857292. A polymer having a molar weight of 15000 to 50000 consisting of ethylene terephthalate and polyoxyethylene-terephthalate, wherein the molar weight of polyethylene glycol units is 1000 to 10000, ethylene terephthalate and polyoxyethylene-terephthalateThe formates can be added to the detergents in a molar ratio of from 2: 1 to 6: 1, according to German patent publication DE 3324258. European patent EP066944 relates to textile treatment agents containing copolyesters made from ethylene glycol, polyethylene glycol, an aromatic dicarboxylic acid and a sulfonated aromatic dicarboxylic acid in a molar ratio. From european patent EP185427, methyl-or ethyl-terminated polyesters containing ethylene terephthalate and/or propylene glycol terephthalate units and detergents containing such soil release polymers are known. European patent EP241984 relates to a polyester containing, in addition to oxyethylene and terephthalic acid units, substituted ethylene units and glycerol units. Polyesters known from EP241985 contain, in addition to oxyethylene and terephthalic acid units, 1, 2-propanediyl, 1, 2-butanediyl and/or 3-methoxy-1, 2-propanediyl units and glycerol units and are composed of C₁To C₄And (4) alkyl end capping. European patent EP253567 relates to soil release polymers having a molar mass of ethylene terephthalate and polyoxyethylene terephthalate of 900 to 9000, wherein the molar weight of the polyethylene glycol units is 300 to 3000 and the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate is 0.6 to 0.95. It is known from European patent EP272033 that polyesters containing polytrimethylene terephthalate and polyoxyethylene terephthalate units are at least partially made by C_1-4Alkyl or acyl terminated. European patent EP274907 describes sulfonated ethyl-terminated terephthalate-containing soil release-polyesters. In European patent application EP357280, compounds containing terephthalate, alkylene glycol and poly-C are prepared by sulfonation of unsaturated end groups_2-4-a glycol-unit soil release polyester. German patent application DE2655551 describes the reaction of such polyesters with polymers containing isocyanate groups and the polymers prepared in such a way that they are used for preventing the reabsorption of soiling when washing synthetic fibres. It is known from German patent specification DE2846984 that detergents contain, as soil release polymers, products obtained by reacting a polyester with an isocyanate-terminated prepolymer prepared from a diisocyanate and a hydrophilic, nonionic macrodiol.

The polymers known according to the state of the art in the wide range mentioned above have the disadvantage that they have no effect or little effect on textiles which are not composed of polyester or at least not predominantly composed of polyester. Currently, a significant proportion of textiles are constructed from cotton or cotton-polyester blended fabrics, and thus, more effective soil removal is required for the greasy soil of such textiles.

It has surprisingly been found that this task is solved by using certain polyurethane-based polymers.

The object of the invention is to increase the soil release efficiency of detergents in the washing of cotton or cotton-containing fabrics, using polymers having soil release properties which are obtained by polymerizing polyisocyanates with polymeric polyols having a water solubility of more than 1000D at 20 ℃ of more than 300g polymer per liter and an average molar mass of 12000D and at 20 ℃ of less than 100g polyol per liter and, if present, further polyols and mixtures thereof.

The polymers used according to the invention increase the cleaning efficiency of the soil removal even more markedly in the case of multiple use, i.e. in particular when the corresponding fabrics have been washed with the polymers before the occurrence of soil.

Preferred polymeric polyols having an average molar mass of over 1000D and a water solubility at 20 ℃ of more than 300g polymer per liter can be described by the general formula I,

W[(O-(CH₂-)_a)_b-OH]_c (I)

wherein a is a number from 1 to 3, b is a number from 3 to 800, preferably from 17 to 800, and c is a number from 1 to 6, wherein b varies in any molecule,

here, the

W is H-, when c is 1;

is- (CH)₂)_d-, where d is a number from 2 to 12, when c is 2;

is-CH₂-(CH-)_e-CH₂-, where e is a number from 1 to 4, when c ═ e + 2;

is- (CH)₂)_e-CH(CH₂-)-(CH₂)_e-, where e is a number from 1 to 4, when c is 3; or

Is any aliphatic, cycloaliphatic, or aromatic radical or a radical containing both aliphatic and aromatic groups.

Particularly preferred high water solubility polymeric polyols are polyethylene glycols, with particularly preferred polyethylene glycols having an average molar mass of between 3000 and 12000D.

Preferred average molar masses are less than 12000D, polyols having a water solubility at 20 ℃ of less than 100g per liter can be described by the general formulae (II) to (V),

HO-X-CHY-OH (II)

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

V[(O-((CH₂-)_fCHR¹-)_g)_hOH]_i (III)

in the formula R¹Is hydrogen or alkyl 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 is¹F and h may vary in either molecule,

here, the

V is H, when i is 1;

is- (CH)₂)_k-, where k is a number from 2 to 12, when i is 2;

is-CH₂-(CH)_I-CH₂-, in which I isNumbers 1 to 4, when I ═ I + 2;

is- (CH)₂)_I-CH(CH₂)-(CH₂)_I-, where I is a number from 1 to 4, in which case I is 3, or

Is any aliphatic, cycloaliphatic, or aromatic radical or a radical containing both aliphatic and aromatic radicals,

HO((-CHR²(-CH₂)_m)_n-O)_o-Cy-C(R³)(R⁴)-Cy-(O-((CH₂-)_pCHR²-)_q)_rOH

(IV)

wherein Cy is phenylene or cyclohexylene, R²Is hydrogen or an alkyl radical containing 1 to 6C atoms, R³And R⁴Independently of one another, hydrogen or an alkyl radical containing 1 to 6C atoms or together form an aliphatic bridge (CR)⁵R⁶)_sWherein S is a number from 4 to 6 and R⁵And R⁶Independently of one another, is H or an alkyl radical having 1 to 6C atoms or is a double bond, where R⁵And R⁶Can vary in the bridge chain, m and p are numbers 0 to 3, n and q are numbers 1 to 4, and O and R are numbers 0 to 20, where R is independent of one another²M and p may vary in either molecule,

V[-O-C(O)-(C(R⁷)(R⁸))_t-(CHOH)_u-(CH₂)_w-H]_i (V)

in the formula R⁷And R⁸Independently of one another, H or alkyl having 1 to 6C atoms or may form multiple bonds with adjacent C atoms⁷And R⁸And can vary in any molecule, t and w are numbers 0 to 20, independently of one another, and u is a number 0 to 1, where t, u and w can vary in any molecule,

here, the

V is H or CH₃-, when i is 1;

is- (CH)₂)_k-, where k is a number from 2 to 12, when i is 2;

is-CH₂-(CH)_I-CH₂-, where I is a number from 1 to 4, when I ═ I + 2;

is- (CH)₂)_I-CH(CH₂-)-(CH₂)_I-, where I is a number from 1 to 4, in which case I is 3, or

The polymeric polyols according to formula (III) are preferably derived from 1, 2-propanediol, 1, 2-butanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and/or neopentanediol, particularly preferred polymeric polyols according to formula (III) being polypropylene oxides and polytetrahydrofurans having an average degree of polymerization in the range from 3 to 70.

The polymeric diols according to formula (IV) are preferably derived from bisphenol A or bisphenol F, particularly preferred diols according to formula (IV) being propoxylated and ethoxylated bisphenol A.

Preferred polyols according to formula (V) are castor oil, partially hydrogenated castor oil, partially hydrolyzed castor oil and derivatives thereof.

Preferred further polyols are dimethylolpropionic acid and its salts, N-alkyldiethanolammines and their salts and water-soluble polymeric polyols having an average molar mass of less than 1000D at 20 ℃ of more than 500g per liter of water, corresponding to the 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 varies in any molecule, and

w is H-, when c is 1;

is- (CH)₂)_d-, where d is a number from 2 to 12, when c is 2;

is-CH₂-(CH-)_e-CH₂-, where e is a number from 1 to 4, when c ═ e + 2;

Polyethylene glycols having an average molar mass of from 300D to 1000D are particularly preferred polyols.

In another embodiment of the invention, polymers are used which have different degrees of polymerization (b in formula 1) by adding a mixture of at least two polymeric diols, wherein the degree of polymerization of the two diol variants according to formula (I) is preferably at least 10-fold different, for example with a first polymeric diol having a degree of polymerization in the range from 8 to 15 and a second polymeric diol having a degree of polymerization in the range from 100 to 150.

Polyisocyanate means a compound of the general structure (O-C-N-)_tZ, wherein t is the number 2 or 3, Z is an aliphatic or aromatic radical or a radical containing both aliphatic and aromatic radicals, preference being given to compounds in which the isocyanate groups are linked to the aryl radicals via alkylene groups or compounds in which the isocyanate groups are bound to directly interconnected aryl radicals or to aryl radicals which are interconnected via alkylene groups, the polyisocyanate being in a preferred embodiment of the invention a diisocyanate.

Examples of suitable diisocyanates include 1, 5-naphthylene diisocyanate, 4, 4' -diphenylmethane diisocyanate (MDI), hydrogenated MDI (H)₁₂MDI), Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4, 4 '-diphenyldimethylmethane diisocyanate, di-and tetraalkyldiphenylmethane diisocyanates, 4, 4' -dibenzyl diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, the isomeric Tolylene Diisocyanates (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, tetramethylolbutane-1, 4-diisocyanate, butane-1, 4-diisocyanate, hexane-1, 6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, cyclohexane-1, 4-diisocyanate, ethylene diisocyanates, bis-isocyanatoethyl phosphophthalate, diisocyanates which additionally bear reactive halogen atoms, such as 1-chloromethylphenyl-2, 4-diisocyanate, 1-bromomethylphenyl-2, 6-diisocyanate, 3, 3-bis-chloromethylether-4, 4-diphenyl-diisocyanate, sulfur-containing polyisocyanates being obtainable by reacting 2 mol of hexamethylene-diisocyanate with 1 mol of thiodiethylene glycol or dihydroxydihexyl sulfide, other important diisocyanates being trimethylhexamethylene diisocyanate, 1, 4-diisocyanatobutane, 1, 12-diisocyanatododecane and dimeric fatty acid-diisocyanates, particularly suitably tetramethylene diisocyanate, hexamethylene-, undecane-, dodecamethylene-, 2, 2, 4-trimethylhexane-, 1, 3-cyclohexane-, 1, 4-cyclohexane-, 1, 3-or 1, 4-tetramethylxylene-, isophorone-, 4, 4-dicyclohexylmethane-and lysine ester-monoisocyanate. Particularly preferred are 4, 4-diphenylmethane diisocyanate and/or tetramethylxylene diisocyanate, in particular m-TMXDT.

The molar ratio of polyol, which means the sum of the polymeric polyol according to formula (I) and the polyols according to formulae (II) to (V), to isocyanate is preferably from 1: 1 to 1.5: 1, in particular from 1.05: 1 to 1.3: 1. Preferred soil release polyurethanes have a molecular weight or average molecular weight or molecular weight distribution, respectively, of from 1500 to 2000,000. Especially between 8000 and 150000.

Polyurethanes which are particularly preferably usable according to the invention are known in principle and are preferably prepared by first preparing a prepolymer from a polyisocyanate, preferably a diisocyanate and a polymeric polyol of the formula (I), preferably a diol (C.sub.2), using an excess of polyol in a first step and then reacting this with further polyisocyanate and a polyol of the formula (II), (III), (IV) or (V), preferably also a diol, to lengthen its (molecular) length in a second step, it being possible in the second step to use further diisocyanates different from the first step, for example MDI in the first step and TMXDI in the second step, if several polymeric polyols of the formula (I) having different degrees of polymerization are added in the above-described manner, preferably in the first step a low-degree of polymerization is added and in the second step the low-degree and high-degree of polymerization are added according to the formula (II), (III), (IV) or (V) are added together, b in the polymeric diol according to formula (I) added in the first step, among the variables mentioned above, preferably being a number from 3 to 16; in the second step, the polymeric diols according to formula (I) in which b is a number from 17 to 800 are added, so that the urethane-based polymers obtained can be used preferably within the scope of the present invention.

The polyurethanes used according to the invention are simple to prepare as described above. Without being concerned about ecological and toxicity, it is satisfactory for the removal of greasy and cosmetic soils from cotton or cotton-containing fabrics, better than the compounds known hitherto for this purpose. In addition, considerable amounts of surfactant can be saved while maintaining the same degreasing capacity.

Another object of the invention is the use of such a cotton-reactive material. A detergent composition of a urethane-based polymer and a polyester-active, detergent-releasing polymer made from a dibasic acid and a polymeric glycol to improve the detergency of the detergent in the laundering of textile articles.

Polymers known to be active on polyesters and having soil-release properties which can additionally be used in the context of the present invention, based on essentially urethanes, are prepared from dicarboxylic acids, such as adipic acid, phosphophthalic acid or terephthalic acid, dibasicCopolymers of alcohols such as ethylene glycol, diols and polyglycols such as polyethylene glycol or polypropylene glycol, preferably the added soil release polyester is provided by esterification of two monomer components in the form of a compound in which the first monomer is a diacid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR')_aOH, which can also be used as a polymeric diol H- (O- (CHR)₁₁)_a-)_bOH, where Ph is-O-, m-or p-phenylene which may bear 1 to 4 alkyl substituents selected from 1 to 22C-atoms and may also bear sulfonic acid groups, carboxyl groups and mixtures thereof, R' is hydrogen, alkyl groups containing 1 to 22C-atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300, preferably the polyester thus obtained is either as the monomeric diol unit-O- (CHR)₁₁)_athe-O-may also be a polymeric diol unit- (O- (CHR)¹¹-)_a)_bThe molar ratio of monomeric diol units to polymeric diol units, in the O-form, is preferably from 100: 1 to 1: 100, in particular from 10: 1 to 1: 10, the degree of polymerization b in the polymeric diol units is preferably in the range from 4 to 200, in particular from 12 to 140, and the molecular weight or average molecular weight or molecular weight distribution of the soil release polyester is preferably in the range from 250 to 100000, in particular from 500 to 50000, at its maximum. The parent acids corresponding to the Ph group are preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, sulfonated phthalic acid isomers, sulfonated isophthalic acid and sulfonated terephthalic acid and mixtures thereof, preferably in the form of salts, in particular alkali metal or ammonium salts, particularly preferably sodium and potassium salts, if their acid groups in the polymer are not part of the ester bonds. It is sometimes desirable for a small proportion (in the sense of Ph, not more than 10 mol%) of the monomers HOOC-Ph-COOH in the soil-release polyester to be replaced by other acids having at least two carboxyl groups, such as alkylene-and alkenylene dicarboxylic acids, e.g.malonic acid, succinic acid, quaternary acids, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, preferably diolsHO-(CHR¹¹)_a-OH is selected from those R¹¹Is hydrogen and a is a number from 2 to 6, and those in which a is 2, R¹¹Diols which are hydrogen and alkyl having 1 to 10, in particular 1 to 3C atoms, the last-mentioned HO-CH being particularly preferred₂-CHR¹¹A diol of the formula-OH, wherein R¹¹Have the above-mentioned meanings. Examples of diols are ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol, particularly preferred polymeric diols are polyethylene glycols having an average molar mass in the range from 1000 to 6000.

It is sometimes desirable for the combination polyesters listed above to be capable of being capped, it being possible here for the end groups to be esters of alkyl and monocarboxylic acids having 1 to 22C atoms, the end groups which are connected by ester bonds being based on alkyl-, alkenyl-and aryl monocarboxylic acids having 5 to 32C atoms, in particular 5 to 18C atoms, to be mentioned as such, valeric, caproic, enanthic, caprylic, pelargonic, capric, undecylic, undecylenic, lauric, tridecylic, tetradecanoic, tetradecenoic, pentadecylic, palmitic, stearic, petroselinic, oleic, linoleic, elaidic, linolenic, eleostearic, eicosanoic, eicosenoic, arachidonic, docosanoic acids, Erucic acid, brassidic acid, docosahexen-5-oic acid, ditetradecanoic acid, hexacosanoic acid, triacontanoic acid, benzoic acids which have 1 to 5 substituents and which can carry up to 25C atoms in total, in particular 1 to 12C atoms, such as tert-butylbenzoic acid, terminal groups which can also be hydroxymonocarboxylic acids having 5 to 22C atoms, such as hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, hydrogenation products thereof, hydroxystearic acid and o-, m-and p-hydroxybenzoic acids belonging to this class of acids, the hydroxymonocarboxylic acids can be bonded to one another via hydroxyl and carboxyl groups between them and thus constitute a terminal group, preferably the number of hydroxymonocarboxylic acids per terminal group, i.e.the degree of oligomerization of which is in the range from 1 to 50, in particular from 1 to 10. In a preferred design of the invention, a polymer of ethylene terephthalate and polyoxyethylene-terephthalate in which the molar weight of polyethylene glycol units is from 750 to 1500 and the molar ratio of ethylene terephthalate to polyoxyethylene-terephthalate is from 50: 50 to 90: 10 is used in combination with a nitrogen-containing soil release polymer.

The soil release polymers used according to the invention are preferably water-soluble, the term "water-soluble" here being understood to mean that at a pH of 8 and room temperature at least 0.01g, preferably at least 0.1g, of polymer are dissolved per liter of water, more preferably at least 1g per liter, in particular at least 10g per liter, of added polymer being soluble under these conditions.

The use according to the invention can be carried out in a washing process in which the urethane-based polymer is added to the washing liquor containing the detergent alone or as a component of the detergent, so that another subject of the invention is a detergent containing the above-mentioned urethane-based polymer.

Detergents containing a urethane-based polymer used according to the invention may contain all other customary constituents of corresponding lotions which do not interact adversely with the soil-release polymers according to the invention, it being preferred to add the polymer to the detergent in an amount of from 0.1 to 5% by weight, in particular from 0.5 to 2.5% by weight.

It has surprisingly been found that such polymers having the above-mentioned properties have a positive effect on certain other materials consisting of detergents and cleansers. Conversely, certain other detergent compositions may enhance the action of soil release polymers active on cotton, particularly in the presence of enzyme activities, especially proteases and lipases, in non-water soluble inorganic builders. In the presence of water-soluble inorganic and organic builders, in particular substances based on oxygenated carbohydrates, in the presence of peroxides, in particular alkali metal percarbonates. Bleaching agents and anionic surfactants of the synthetic sulphate and sulphonate type are present, so that the above-mentioned components are advantageously added together with the polymers used according to the invention.

In a preferred embodiment, the detergent contains a nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and/or propoxylates, ethoxylation and/or propoxylation products of fatty alkyl polyhydroxyamides and/or fatty alkylamines, and vicinal diols. Fatty acid alkyl esters and/or fatty acid amides and mixtures thereof, in particular in amounts ranging from 2% to 25% by weight.

In a further embodiment of this type of lotion, synthetic sulfate and/or sulfonate anionic surfactants are included, in particular fatty alkyl sulfates, fatty alkyl ether sulfates, sulfonated fatty acid esters and/or sulfonated fatty acid disalts, in particular in a content of between 2% and 25% by weight, preferably from sulfuric acid-alkyl or alkenyl esters and/or sulfuric acid alkyl ether esters or alkenyl ether esters, in which the alkyl or alkenyl groups are from 8 to 22, in particular from 12 to 18C atoms.

Nonionic surfactants which may be used are, in particular, saturated or straight-chain or branched, unsaturated or branched, containing from 10 to 22C atoms. Preferably 12 to 18C-atom alcohols, where the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10, which can be prepared by known methods, by reacting the corresponding alcohols with the appropriate alkylene oxides, the usable alkoxylates being prepared from derivatives of fatty alcohols, although it is also possible to use branched isomeric, in particular carbonyl, alcohols. Alkoxylates which can be used in this way are, in particular, linear primary alcohols, in particular ethoxylates of dodecyl, tetradecyl, hexadecyl or octadecyl and also their mixed alcohols. Furthermore, the corresponding alkoxylates of alkylamines, vicinal diols and carboxylic acid amides, the alkyl moieties of which correspond to the alcohols mentioned above, are also employable. Furthermore, it is also possible to use ethylene oxide and/or propylene oxide insertion products of fatty acid alkyl esters,such as those proposed in International patent application WO90/13533, and fatty acid polyhydroxyamides, according to the methods of U.S. Pat. Nos. WS1985424, US2016962 and US2703798 and International patent application WO 92/06984. Suitable for addition to the lotion of the present invention are those known as alkyl polyglycosides of the general formula (G)_n-OR¹²A compound of (1), wherein R¹²Being an alkyl or alkenyl radical containing 8 to 22C-atoms, G being a glucose unit and n being a number between 1 and 10, and processes for their preparation, for example as described in European patent application 92355, EP301298, EP357969 and EP362671 or in U.S. Pat. No. 3,3547828, the glycoside component (G)_nIt is intended to mean oligomers or polymers of naturally occurring aldose-or ketose monomers, of the class of which glucose, mannose, fructose, galactose, too-ose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose are monomers which are bonded by this glycosidic process, and the oligomers formed from the monomers which are bonded by this glycosidic process can be characterized, in addition to their identity by the type of sugar contained therein, by the number of them (sugars), i.e. the degree of oligomerization, n, which is a value calculated analytically and is generally a fraction which lies between 1 and 10, preferably the glycoside used has a value of less than 1.5, in particular between 1.2 and 1.4. As preferred base monomers, the alkyl or alkenyl moiety R of the glycoside due to the convenient source of glucose¹²Preference is likewise given to readily available starting materials from renewable sources, such as fatty alcohols, although branched isomers thereof, in particular the carbonyl alcohols, may also be used for preparing glycosides, suitable for this purpose in particular containing straight-chain primary octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-or octadecyl-alcohols and mixtures thereof, particularly preferred alkyl glycosides comprising a cocoalkyl radical, i.e. predominantly R¹²Dodecyl and R¹²Mixtures of tetradecyl groups.

The nonionic surfactants in the detergents containing the detersive active used in the present invention are preferably used in an amount of from 1% to 30% by weight, where the surfactant is preferably added to the liquid detergent first in the upper part of the dosage range, while the granular detergent preferably contains a minor portion up to 5% by weight first.

Instead of the above-mentioned lotions, it is possible to contain or supplement other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, for example alkylbenzenesulfonates, preferably in amounts of more than 20% by weight, in particular from 0.1% by weight to 18% by weight, based on the total lotion, with particularly suitable synthetic anionic surfactants added to the lotion being alkyl and/or alkenyl sulfates having from 8 to 22C atoms, which carry an alkali metal-ammonium-or alkyl-or hydroxyalkyl-substituted ammonium ion as the corresponding anion, preferably fatty alcohols having from 12 to 18C atoms and branched homologues thereof, so-called derivatives of carbonyl alcohols. Alkyl-and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol components with conventional sulfating agents, in particular sulfur trioxide or chlorosulfonic acid, and subsequently neutralizing with alkali metal-, ammonium-or alkyl-or hydroxyalkyl-substituted ammonium bases. The content of such alkyl-and/or alkenyl sulfates in lotions containing a urethane-based polymer according to the invention is from 0.1 to 15% by weight, in particular from 0.5 to 10% by weight.

Surfactants belonging to this type of addible sulfates and also the sulfated alkoxylation products of the above-mentioned alcohols, known as ether sulfates, preferably such ether sulfates contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule; suitable anionic surfactants which are of the sulfonate type are 2-sulfonates which are prepared by reaction of a fatty acid ester with sulfur trioxide and subsequent neutralization, in particular fatty acids having from 8 to 22C atoms, preferably from 12 to 18C atoms, and from 1 to 6C atoms. Preferably 1 to 4C-atoms, and sulfonated fatty acids resulting from the saponification of formal.

As further alternative substances with a surfactant action are soaps, where soaps of saturated fatty acids, such as lauric, myristic, palmitic or stearic acid, and of natural fatty acid mixtures, e.g. coconut, palm or tallow fatty acid, are suitableFor this purpose, particular preference is given to from 50 to 100% by weight of saturated C₁₂-C₁₈Soap mixtures of fatty soaps and up to 50% by weight of oleic soaps, the soap content preferably being from 0.1% to 5% by weight, and in particular in liquid lotions containing the polymers used according to the invention the soap content can generally be increased to up to 20% by weight.

In another embodiment, a lotion containing the polymer used according to the invention comprises water-soluble and/or water-insoluble builders, in particular selected from the group consisting of alkali metal aluminosilicates, crystalline alkali metal silicates having a modulus greater than 1, monomeric polycarboxylates, polymeric polycarboxylates and mixtures thereof, in particular in an amount ranging from 2.5% to 60% by weight.

A lotion containing the polymer used according to the invention, preferably containing 20% to 55% by weight of water-soluble and/or water-insoluble organic and/or inorganic builders, those substances which belong to the group of water-soluble organic builders and which are in particular polycarboxylic acids, especially citric acid and saccharic acid and also polycarboxylic acids, in particular polycarboxylic compounds which are formed by oxidation of polysaccharides, see International patent application WO93/16110, polymerized acrylic acid, methacrylic acid, maleic acid and mixed polymers thereof, it being possible for small amounts of polymerizable substances without carboxylic acid functions to be present in the polymerization, the relative molecular mass of the homopolymers of unsaturated carboxylic acids then being between 5000 and 200000 and the relative molecular mass of the copolymers being between 2000 and 200000, preferably between 50000 and 120000, in relation to the free acids. A particularly preferred acrylic-maleic acid copolymer has a relative molecular mass of 50000 to 10000, and suitable, although not most preferred, compounds of this class are copolymers of acrylic or methacrylic acid and vinyl ethers, such as vinyl methyl ether, vinyl esters, copolymers of ethylene, propylene and styrene, in which the acid component is at least 50% by weight. As water-soluble organic builder substances, terpolymers can be used, as monomers two carboxylic acids and/or salts thereof and as third monomer vinyl alcohol and/or vinyl alcohol derivatives or a carbohydrate. The first acidic monomer or salt thereof being derived from a monomerUnsaturated C of vinyl group₃-C₈-carboxylic acid and preferably derived from one C₃-C₄-a polycarboxylic acid, in particular methacrylic acid; the second acidic monomer or salt thereof may be C₄-C₈Derivatives of dicarboxylic acids, maleic acid being particularly preferred here; the third monomer unit in this case is derived from vinyl alcohol and/or preferably an esterified vinyl alcohol, particularly preferably a vinyl alcohol derivative, which is derived from a short-chain carboxylic acid, for example C₁-C₄An ester of a carboxylic acid with a vinyl alcohol, the preferred terpolymers here containing 60% to 95% by weight, in particular 70% to 90% by weight, of methacrylic acid or methacrylate, particularly preferably acrylic acid or acrylate and maleic acid or maleate and 5% to 40% by weight, preferably 10% to 30% by weight, of vinyl alcohol and/or vinyl acetate, the particularly preferred terpolymers here having a weight ratio of methacrylic acid or methacrylate to maleic acid or maleate of between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1. In particular between 2: 1 and 2.5. The amounts and weight ratios are for the esters. The second ester monomer is a salt thereof. It may also be an allylsulfonic acid which is substituted in the second position with an alkyl group, preferably C₁-C₄Alkyl or aryl, preferably derived from benzene or a benzene derivative, is substituted. Preferred terpolymers contain, in this case, from 40% to 100% by weight, in particular from 45 to 55% by weight, of methacrylic acid or a salt of methacrylic acid, particularly preferably acrylic acid or a salt of acrylic acid, from 10% to 30% by weight, preferably from 15% to 25% by weight, of methallylsulfonic acid or a salt of methallylsulfonic acid, and, as third monomer, from 15% to 40% by weight, preferably from 20% to 40% by weight, of a carbohydrate which may be, for example, a monosaccharide, disaccharide, oligosaccharide or polysaccharide, preferably a monosaccharide, disaccharide, or oligosaccharide, particularly preferably sucrose, it being possible by addition of the third monomer to envisage the formation of cleavable sites in the polymer, which is of importance for the biodegradation of the polymer, the terpolymers being able, in particular, according to German patent specification DE4221381 and German patent application DE4221381The process described in application DE4300772, which is generally prepared with a relative molecular mass of between 1000 and 200000, preferably between 200 and 50000 and in particular between 3000 and 10000, can be formulated as liquid lotions, formed as aqueous solutions, in particular in the form of 30 to 50% by weight aqueous solutions, all the mentioned polycarboxylic acids generally being used in the form of water-soluble salts, in particular alkali metal salts.

These organic builders 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, preferably in amounts close to the upper limit, are used in pasty or liquid, in particular aqueous, lotions, which contain the polymers according to the invention.

As water-insoluble, water-dispersible inorganic builder material, in particular alkali metal aluminosilicates in crystalline or amorphous form, up to a content of 50% by weight, preferably not more than 40% by weight, and 1 to 5% by weight being used in liquid lotions, where crystalline aluminosilicates contribute to the quality of the detergent, in particular zeolite NaA and sometimes NaX, preferably in amounts such as the abovementioned upper limits, preferably in solid, granular lotions, suitable aluminosilicates are in particular free of particles having a particle size of more than 30mm, preferably at least 80% by weight, consisting of particles of less than 10mm, the binding capacity to calcium being determined as given in German patent specification DE2412837, in the range from 100 to 200mg CaO per g, suitable substitutes or partial substitutes for the abovementioned aluminosilicates being crystalline alkali metal silicates, which may be present alone or in admixture with amorphous silicates, alkali metal silicates suitable as building agents in lotions are preferably alkali metal oxides and SiO₂Should be less than 0.95, in particular from 1: 1.1 to 1: 1.2, and may be present in amorphous or crystalline form, the preferred alkali metal silicate being sodium silicate, in particular amorphous sodium silicate, Na₂O∶SiO₂In a molar ratio of from 1: 2 to 1: 2.8, amorphous alkali metal silicates of this type being commercially available, for exampleCan be obtained under the trade name of (A), and can be made into Na by the method of European patent application EP0425427₂O∶SiO₂The materials are preferably used in the production as solids rather than in the form of solutions in a molar ratio of 1: 1.9 to 1: 2.8, as crystalline silicates which may be present alone or in admixture with amorphous silicate Hao, preferably in the form of Na₂Si_xO_2x+1YH₂Crystalline layered silicates of O, in which X has the so-called modulus of 1.9 to 4 and Y has the number 0 to 20, X having the preferred value 2, 3 or 4, crystalline layered silicates having the scope of this formula being described, for example, in European patent application EP0164514, preferred crystalline layered silicates being those of the type in which X has the general value 2 or 3, not only beta-but delta-sodium disilicates (Na)₂Si₂O₅·YH₂O) is also preferred, beta-sodium disilicate being obtainable, for example, according to the method described in International patent application No 91/08171; sodium- δ -silicates with moduli between 1.9 and 3, 2 can be obtained according to Japanese patent application JP04/238809 or JP 04/260610; the amorphous alkali metal silicates used are virtually anhydrous crystalline alkali metal silicates of the above formula in which X is from 1.9 to 2.1, and their preparation is described in European patent applications EP0548599, EP0502325 and EP 0452428. In a further preferred embodiment of the lotion according to the invention, crystalline layered sodium silicates having a modulus of 2 to 3, obtainable from sand and soda according to the process of European patent application EP0436935, such as those having a modulus of 1.9 to 3.5, obtainable according to the process of European patent application EP0164553 and/or European patent application EP0294753, can be used in a further preferred embodiment of a washing or cleaning agent containing the polymer according to the invention, the alkali metal sodium silicates being present in an amount of 1 to 250% by weight, in particular 5 to 35% by weight, with respect to the anhydrous active substance, such as, as additional builders and aluminosilicates, in particular zeolites, preferably in an amount of 1 to 15% by weight, in particular 2 to 8% by weight, with respect to the anhydrous active substance, the alkali metal silicates being present with respect to the anhydrous active substance, the aluminosilicate and the silicate being present in combination with the anhydrous active substanceA weight ratio of from 4: 1 to 10: 1 for anhydrous active substances, a lotion containing both amorphous and crystalline alkali metal silicate, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate preferably being from 1: 2 to 2: 1, in particular from 1: 1 to 2: 1.

Other water-soluble or water-insoluble inorganic materials may also be added to the inorganic builders described above in the lotions containing the soil-releasing polymers used according to the invention, suitable for use in connection therewith being alkali metal carbonates, alkali metal argon carbonates and alkali metal sulfates and mixtures thereof, the additional inorganic materials being present in amounts of up to 70% by weight.

In addition, other components customary in detergents and cleaning agents can be included in the lotion, and such alternative components include, in particular, enzymes, enzyme inhibitors, bleaching agents, bleach activators, heavy metal complex ligands, for example aminopolycarboxylic acids, polyphosphoric acids and/or aminopolyphosphoric acids; anti-redeposition agents such as cellulose ethers, anti-dye transfer agents, for example polyvinylpyrrolidone or polyvinylpyridine-N-oxide, antifoams, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives, preferably the optical brighteners in lotions containing the polymers according to the invention can be added to 1% by weight, in particular 0.01% by weight0.5% by weight, in particular substituted 4.4-bis- (2, 4-6-triamino-s-triazinyl) -stilbene-22-Sulfonic acid compounds; a heavy metal complex ligand content of 3 to 5% by weight, in particular 0.1% to 2% by weight, especially aminoalkylenephosphoric acid and salts thereof; the anti-redeposition agent content can be up to 3 wt.%, in particular 0.5 wt.% to 2 wt.%; the antifoam content can be up to 2% by weight, in particular from 0.1% by weight to 1% by weight, all of these weight proportions being relative to the respective total lotion.

The solvents used in the liquid lotions containing the polymers according to the invention are, in addition to water, preferably those which are miscible with water, and belong to the class of low molecular alcohols, such as ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, low molecular glycols, such as ethylene glycol, propylene glycol, and ethers derived from the above classes of compounds, in which the polyesters according to the invention are generally dissolved or in suspension.

Among the enzymes commonly used, those selected from the group consisting of proteases, amylases, lipases, cellulases, hemicellulases, oxidases, peroxidases and mixtures thereof are preferred. Proteases which are obtained from microorganisms such as bacteria or molds are considered, for example, and are described in German patent specifications DE1940488, DE2044161, DE2201803 and DE2121397, U.S. Pat. Nos. 3632957 and US4264738, European patent application EP006638 and International patent application WO91/02792, for example, commercially available proteasesOrThe product of the name; lipases which can be used are described, for example, in European patent applications EP258068, EP305216 and EP341947, which can be obtained from Humicola lanuginosa, for example in International patent application WO91/16422 or European patent application EP384717, from the genus Bacillus, for example in European patent applications EP468102, EP385401, EP375102, EP334462, EP331376, EP330641, EP214761, EP218272 or EP204284 or International patent WO90/10695, from the genus Pseudomonas, for example in European patent application EP130064, from Fusarium, for example in European patent application EP117553, from the genus Rhizopus or in European patent application EP167309, suitable lipases being commercially available, for example-Lipase，Toyo--Lipase，Lipase and-products under the name Lipase; suitable amylases are, for example, commercially available asAndproduct of the name OXAM; cellulases which can be used are enzymes obtainable from bacteria or moulds which exhibit a pH-optimum in the weak to weak alkaline range of preferably from 6 to 9.5, which cellulases are known, for example, from German patent laid-open Specifications DE3117250, DE3207825, DE3207847, DE3322950 or European patent applications EP265832, DE269977, EP270974, EP273125 and EP339550 and international patent applications WO95/02675 and WO97/14804 and are commercially availableAndthe name of (1) appears.

In particular in liquid lotions, the usual enzyme stabilizers are frequently present, the known aminoalcohols such as mono-, di-, triethanolamine and propanolamine and mixtures thereof, low carboxylic acids, as are known for example from european patent applications EP376705 and EP 378261; boric acid or alkali metal borates, boric acid-carboxylic acid compositions, such as boric acid esters known from european patent application EP451921, such as boric acid derivatives known from international patent application WO93/11215 or european patent application EP511456, such as european patent application EP 583536; calcium salts, such as the Ca-formic acid compositions known from european patent specification EP 28865; magnesium salts, for example, are known from european patent application EP378262, and/or sulfur-containing reducing agents, for example, from european patent application EP080748 or EP 080223.

Long-chain soaps belong to the class of suitable antifoams, in particular behenic soap, fatty amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain finely divided, sometimes silane-or otherwise treated hydrophobic silicic acids, the antifoams used in granular lotions preferably being incorporated on granular water-soluble carriers, as described, for example, in German laid-open patent specification DE3436194, European patent applications EP262588, EP301414, EP309931 or EP 150386.

In addition, in lotions containing one of the polymers used according to the invention, which contain anti-redeposition agents, the function of which is to keep the soil dissolved from the fibres suspended in the solution and thus to prevent them from being redeposited, colloids which are mostly organic, such as water-soluble polymeric carboxylates, glue compounds, gelatin, ether carboxylic acids or ether sulfonates of starch or cellulose, or salts of acid sulfates of cellulose or starch, water-soluble polyamides containing acid groups, are also suitable for this purpose; in addition, soluble starch preparations and other starch products other than those described above are also useful, for example partially hydrolyzed starch, sodium hydroxymethylcellulose, methylcellulose, hydroxymethylethylcellulose and mixtures thereof may preferably be employed.

In a further embodiment of the lotions containing the soil release polymers used according to the invention, which comprise peroxide-based bleaching agents, in particular in amounts of between 5% and 70% by weight, and optionally bleach activators, in particular in amounts of between 2% and 10% by weight, per-compounds customary in detergents, such as hydrogen peroxide, as tetrahydrated or monohydrated perborates, percarbonates, perpyrophosphates and persilicates, generally present as alkali metal salts, in particular as sodium salts, such bleaching agents being preferably used in detergents containing the polymers used according to the invention in amounts of up to 25% by weight, in particular up to 15% by weight, and particularly preferably in amounts of from 5% to 15% by weight, based on the total lotion, with percarbonate being particularly suitable, it being possible to select existing bleach activator components including the N-or O-acyl compounds customary for use, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacylglycoluril, N-acetylated hydantoin, hydrazide, triazole, urazole, diketopiperazine, sulphamides and cyanurates, and also carboxylic anhydrides, in particular phthalic anhydride, carboxylic esters, in particular sodium isononanoylphenol sulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, bleach activators which prevent interaction with per-compounds on storage, are coated or granulated in the usual way with a coating material, in which case tetraacetylethylenediamine granulated with the aid of carboxymethylcellulose has an average particle diameter of from 0.01mm to 0.8mm, for example as can be prepared according to the method described in European patent specification EP37026, and/or granulated 1, 5-diacetyl-2, 4-dicarbonylhexahydro 1, 3, 5-triazines, for example, prepared by the process described in German patent specification DE255884, are particularly preferred, such bleach activators being present in the detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based on the total amount of the corresponding lotion.

In a preferred embodiment, a lotion formulation incorporating the soil release polymer used in the present invention is in particulate form and comprises from 2% to 55% by weight of an inorganic builder, from 10% to 10% by weight, especially from 2% to 8% by weight of a water soluble organic builder, from 10% to 25% by weight of a synthetic anionic surfactant, from 1% to 5% by weight of a nonionic surfactant, from 25% to 25% by weight, especially from 5% to 20% by weight of a bleach, especially an alkali metal percarbonate, from 15% to 10% by weight of a bleach activator, and from 25% by weight, especially from 0.1% to 25% by weight of an inorganic salt, especially an alkali metal carbonate and/or bicarbonate.

Examples of the invention

Example 1: preparation of polyurethanes

492.4g or 1208.5g of polyethylene glycol 600 (degree of polymerization given as 13) were prepared and dewatered at 80 ℃ for about 2 hours at 1mbar, and 187.7g or 375.4g of 4, 4' -diphenylmethane diisocyanate were added in portions over a period of about 90 minutes at 80 ℃ under nitrogen protection, and then stirred at 80 ℃ under nitrogen protection until complete consumption of the isocyanate (about 2 hours), whereupon prepolymer P1 (to an average molar weight of about 6600) or P2 (to an average molar weight of about 2700) was obtained.

465g of 465g P1 were dehydrated with 468g of polyethylene glycol 6000 (degree of polymerization: 137) and 23g of 12-hydroxy-octadecan-1-ol at 100 ℃ and 2mbar with stirring for about 2 hours, and then reacted with 44g of tetramethylxylylene diisocyanate at 150 ℃ and 160 ℃ until a constant melt viscosity was reached, giving SRP1 polymer (OH: NCO ratio: 1.21).

575g P2 was stirred with 318g of polyethylene glycol 6000 (degree of polymerization: 137) and 30g of 12-hydroxy-octadecan-1-ol at 100 ℃ and 2mbar for about 2 hours and then reacted with 77g of tetramethylxylylene diisocyanate at 150 ℃ and 160 ℃ until a constant melt viscosity was reached, giving SRP2 polymer (OH: NCO ratio: 1.14).

267g P2 was dehydrated with 118g of polyethylene glycol 6000 (degree of polymerization: 137) and 14g of 12-hydroxy-octadecan-1-ol and 23g of dimethylolpropionic acid under stirring at 90 ℃ and 1ml ar for about 1 hour, and then reacted with 78g of tetramethylxylylene diisocyanate at 140 ℃ and 150 ℃ until a constant melt viscosity was reached, giving SRP3 polymer (OH: NCO ratio: 1.06).

Example 2:

a detergent (V1) contains

12 parts by weight of ABS

FAS 5 parts by weight

C12/147 EO 3 parts by weight

TAED 7 parts by weight

Percarbonate 17 parts by weight

13 parts of soda

28 parts by weight of zeolite

Sokalan CP 55 weight parts

Tinopal DMS-X0.2 part by weight

Blended with 2 parts by weight of SRP1(W1) or with 2 parts by weight of SRP2(W2), a blend fabric of pure cotton, finished cotton and polyester/cotton 50/50 was treated as follows:

washing equipment: miele W918 Novotronic

Original washing efficiency: normal operation procedure in inflow mode

Washing temperature: 40 deg.C

And (3) determination: 3 times of

Volume of the bath lotion: 181

Water hardness: 16 DEG dH

The added amount of the washings: 3.5kg of clean laundry

The fabrics were washed three times with the corresponding detergent to be tested under the conditions given above, dried after each wash, and after three pre-washes the fabrics were stained with the following standard contaminants:

0.15g rouge

0.10g lipstick

0.10g of black shoe polish

0.10g dirt/sebum

The stained fabric was tested with a mimolla CR200 and thereafter aged at room temperature for 7 days, after which the stained fabric was treated on a towel with an aufgetackert and washed according to the conditions given above.

The fabrics were dried and tested again with a Mimolta CR200 test, at which time the following wash results (dde-value) were obtained.

TABLE 2

	Lipstick	Black silicone oil	Rouge cream	Dirt/sebum
	Lipstick	Black silicone oil	Rouge cream	Dirt/sebum	V1	68.2	41.8	42.1	54.4
W1	72.5	40.1	45.1	58.1	V1	68.2	41.8	42.1	54.4
W1	72.5	40.1	45.1	58.1	W2	76.9	47.7	44.8	59.6

TABLE 3

	Lipstick	Black silicone oil	Rouge cream	Dirt/sebum
	Lipstick	Black silicone oil	Rouge cream	Dirt/sebum	V1	67.5	41.3	26.4	43.3
W1	74.6	42.9	29.7	46.5	V1	67.5	41.3	26.4	43.3
W1	74.6	42.9	29.7	46.5	W2	75.1	42.9	31.0	46.7

TABLE 4

	Lipstick	Rouge cream	Dirt/sebum
	Lipstick	Rouge cream	Dirt/sebum	V1	65.8	41.4	47.1
W1	73.9	41.6	55.9	V1	65.8	41.4	47.1
W1	73.9	41.6	55.9	W2	77.7	43.0	60.9

It can be seen that the detergent containing the polymers used in the present invention (WT and W2) has a much improved cleaning effect over the detergent without the polymer.

Claims

1. Use of a soil release polymer obtained by the polymerisation of a polyisocyanate with a polymeric polyol having an average molar mass of more than 1000D and a water solubility at 20 ℃ of more than 300g of polymer per litre and a polyol having an average molar mass of less than 12000D and a water solubility at 20 ℃ of less than 100g per litre and optionally other polyols and mixtures thereof to increase the soil release efficiency of a detergent when washing cotton or cotton-containing fabrics,

wherein

The polymeric polyol having an average molar mass of more than 1000D and a water solubility of more than 300g of polymer per liter at 20 ℃ is a compound of formula (I)

W[(O-(CH₂-)_a)_b-OH]_c (I)

Wherein 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 in any molecule,

w is H-, when c is 1;

is- (CH)₂)_d-, where d is a number from 2 to 12, when c is 2;

is-CH₂-(CH-)_e-CH₂-, where e is a number from 1 to 4, when c ═ e + 2;

is- (CH)₂)_e-CH(CH₂-)-(CH₂)_e-, where e is a number from 1 to 4, when c is 3;

and wherein

Polyols having an average molar mass of less than 12000D and a water solubility at 20 ℃ of less than 100g per liter have the following formulae (II) to (V),

HO-X-CHY-OH (II)

wherein X is a straight or branched alkyl group containing 1 to 48 carbon atoms and Y is hydrogen or an alkyl group containing 1 to 24 carbon atoms,

V[(O-((CH₂-)_fCHR¹-)_g)_hOH]_i (III)

in the formula R¹Is hydrogen or alkyl having 1 to 6C 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 is¹F and h may vary in either molecule,

v is H, when i is 1;

is- (CH)₂)_k-, where k is a number from 2 to 12, when i is 2;

is-CH₂-(CH)_I-CH₂-, where I is a number from 1 to 4, when I ═ I + 2;

is- (CH)₂)_I-CH(CH₂)-(CH₂)_IWhere I is a number from 1 to 4, in which case I is 3,

HO((-CHR²(-CH₂)_m)_n-O)_o-Cy-C(R³)(R⁴)-Cy-(O-((CH₂-)_pCHR²-)_q)_rOH

(IV)

wherein Cy is phenylene or cyclohexylene, R²Is hydrogen or an alkyl radical containing 1 to 6C atoms, R³And R⁴Independently of one another, hydrogen or alkyl groups containing 1 to 6C atoms or bridges which together form an aliphatic radical (CR)⁵R⁶)_sWherein S is a number from 4 to 6 and R⁵And R⁶Independently of one another, hydrogen or alkyl having 1 to 6C atoms or a double bond, where R⁵And R⁶Variable in any bridge, m and p are numbers 0 to 3, n and q are numbers 1 to 4, and O and R are numbers 0 to 20, independently of one another, where R is²M and p may vary in either molecule,

V[-O-C(O)-(C(R⁷)(R⁸))_t-(CHOH)_u-(CH₂)_w-H]_i (V)

in the formula R⁷And R⁸Independently of one another, hydrogen or alkyl having 1 to 6C atoms or a multiple bond to an adjacent C atom, where R⁷And R⁸And can vary in any molecule, t and w are numbers 0 to 20, independently of one another, and u is a number 0 to 1, where t, u and w can vary in any molecule,

v is H or CH₃-, when i is 1;

is- (CH)₂)_k-, where k is a number from 2 to 12, when i is 2;

is-CH₂-(CH)_I-CH₂-, where I is a number from 1 to 4, when I ═ I + 2;

is- (CH)₂)_I-CH(CH₂-)-(CH₂)_IWhere I is a number from 1 to 4, in which case I is 3.

2. Use of a soil release polymer obtained by the polymerisation of a polyisocyanate with a polymeric polyol having an average molar mass of more than 1000D and a water solubility at 20 ℃ of more than 300g per litre of polymer and a polyol having an average molar mass of less than 12000D and a water solubility at 20 ℃ of less than 100g per litre of polyol and optionally other polyols and mixtures thereof to increase the soil release efficiency of a detergent for washing cotton or cotton-containing fabrics which have been washed in the presence of the polymer before the fabrics are stained,

wherein

W[(O-(CH₂-)_a)_b-OH]_c (I)

w is H-, when c is 1;

is- (CH)₂)_d-, where d is a number from 2 to 12, when c is 2;

is-CH₂-(CH-)_e-CH₂-, where e is a number from 1 to 4, when c ═ e + 2;

is- (CH)₂)_e-CH(CH₂-)-(CH₂)_e-, where e is a number from 1 to 4, in which case c is 3

And wherein

HO-X-CHY-OH (II)

V[(O-((CH₂-)_fCHR¹-)_g)_hOH]_i (III)

v is H, when i is 1;

is- (CH)₂)_k-, where k isNumbers 2 to 12, when i ═ 2;

is-CH₂-(CH)_I-CH₂-, where I is a number from 1 to 4, when I ═ I + 2;

HO((-CHR²(-CH₂)_m)_n-O)_o-Cy-C(R³)(R⁴)-Cy-(O-((CH₂-)_pCHR²-)_q)_rOH

(IV)

V[-O-C(O)-(C(R⁷)(R⁸))_t-(CHOH)_u-(CH₂)_w-H]_i (V)

v is H or CH₃-, when i is 1;

is- (CH)₂)_k-, where k is a number from 2 to 12, when i is 2;

is-CH₂-(CH)_I-CH₂-, where I is a number from 1 to 4, when I ═ I + 2;

3. Use of a composition consisting of a polymer having soil release properties obtainable by polymerising a polyisocyanate with a polymeric polyol having an average molar mass of more than 1000D and a water solubility of more than 300g per litre of polymer at 20 ℃ and a polyol having an average molar mass of less than 12000D and a water solubility of less than 100g per litre of polymer at 20 ℃ and optionally other polyols and mixtures thereof, and a polymer active on polyesters having soil release properties obtainable by a dicarboxylic acid and an optionally polymeric diol to improve the soil release efficiency of a detergent when laundering textiles,

wherein

W[(O-(CH₂-)_a)_b-OH]_c (I)

w is H-, when c is 1;

is- (CH)₂)_d-, where d is a number from 2 to 12, when c is 2;

is-CH₂-(CH-)_e-CH₂-, where e is a number from 1 to 4, when c ═ e + 2;

And wherein

HO-X-CHY-OH (II)

V[(O-((CH₂-)_fCHR¹-)_g)_hOH]_i (III)

v is H, when i is 1;

is- (CH)₂)_k-, where k is a number from 2 to 12, when i is 2;

is-CH₂-(CH)_I-CH₂-, where I is a number from 1 to 4, when I ═ I + 2;

HO((-CHR²(-CH₂)_m)_n-O)_o-Cy-C(R³)(R⁴)-Cy-(O-((CH₂-)_pCHR²-)_q)_rOH

(IV)

V[-O-C(O)-(C(R⁷)(R⁸))_t-(CHOH)_u-(CH₂)_w-H]_i (V)

v is H or CH₃-, when i is 1;

is- (CH)₂)_k-, where k is a number from 2 to 12, when i is 2;

is-CH₂-(CH)_I-CH₂-, where I is a number from 1 to 4, when I ═ I + 2;

4. Use according to one of claims 1 to 3, characterized in that the polymeric polyol having an average molar mass of more than 1000D and a water solubility of more than 300g of polymer per liter at 20 ℃ is a polyethylene glycol.

5. Use according to claim 4, characterized in that the polyethylene glycol has an average molar mass of between 3000 and 12000D.

6. Use according to one of claims 1 to 3, characterized in that the compound of the general formula (O ═ C ═ N-)_tZ, where t is the number 2 or 3, and Z is an aliphatic or aromatic group, or a group that is both aliphatic and aromatic.

7. Use according to claim 6, characterized in that the polyisocyanate is a diisocyanate.

8. Use according to claim 7, characterized in that the diisocyanate is diphenylmethane diisocyanate and/or tetramethylxylylene diisocyanate.

9. Use according to one of claims 1 to 3, characterized in that the molar ratio of polyol to polyisocyanate is from 1: 1 to 1.5: 1.

10. Use according to claim 9, characterized in that the molar ratio of polyol to polyisocyanate is from 1.05: 1 to 1.3: 1.

11. Use according to one of claims 1 to 3, characterized in that, to obtain the polymer, a mixture of diisocyanate and a polymeric diol of the formula (I),

W[(O-(CH₂-)_a)_b-OH]_c (I)

wherein a is a number from 1 to 3, b is a number from 3 to 800 and c is a number from 1 to 6, wherein b varies in any molecule,

w is H-, when c is 1;

is- (CH)₂)_d-, where d is a number from 2 to 12, when c is 2;

is-CH₂-(CH-)_e-CH₂-, where e is a number from 1 to 4, when c ═ e + 2;

the compounds of formula (I) are preferably polymeric polyols having an average molar mass of more than 1000D and a water solubility at 20 ℃ of more than 300g polymer per litre,

in the presence of an excess of diol, a prepolymer is produced which is lengthened in a second step by reaction with further diisocyanates and a diol of the formula (II), (III), (IV) or (V).

12. Use according to claim 11, wherein in the second step a further diisocyanate is added which is different from the first step to obtain the polymer.

13. Use according to claim 11, characterized in that a plurality of polymeric diols having different degrees of polymerization according to formula (I) are used in the first step with the diol having the lowest degree of polymerization, and in the second step the diol or diols having a higher degree of polymerization are added together with those diols according to formula (II), (III), (IV) or (V) to obtain the polymer.

14. Use according to claim 13, characterized in that in the first step a polymeric diol according to formula (I) is used, wherein b is a number from 3 to 16, and in the second step a polymeric diol according to (I) is added, wherein b is a number from 17 to 800.

15. Detergent comprising a polymer with detergency obtained by polymerising a polyisocyanate with a polymeric polyol having an average molar mass of more than 1000D and a water solubility of more than 300g polymer per litre at 20 ℃ and a polyol having an average molar mass of less than 12000D and a water solubility of less than 100g polyol per litre at 20 ℃ and optionally other polyols and mixtures thereof,

wherein

W[(O-(CH₂-)_a)_b-OH]_c (I)

w is H-, when c is 1;

is- (CH)₂)_d-, where d is a number from 2 to 12, when c is 2;

is-CH₂-(CH-)_e-CH₂-, where e is a number from 1 to 4, when c ═ e + 2;

And wherein

HO-X-CHY-OH (II)

V[(O-((CH₂-)_fCHR¹-)_g)_hOH]_i (III)

v is H, when i is 1;

is- (CH)₂)_k-, where k is a number from 2 to 12, when i is 2;

is-CH₂-(CH)_I-CH₂-, where I is a number from 1 to 4, when I ═ I + 2;

HO((-CHR²(-CH₂)_m)_n-O)_o-Cy-C(R³)(R⁴)-Cy-(O-((CH₂-)_pCHR²-)_q)_rOH

(IV)

wherein Cy is phenylene or cyclohexylene, R²Is hydrogen or an alkyl radical containing 1 to 6C atoms, R³And R⁴Independently of one another, hydrogen or alkyl groups containing 1 to 6C atoms or bridges which together form an aliphatic radical (CR)⁵R⁶)_sWherein S is a number from 4 to 6 and R⁵And R⁶Independently of one another, hydrogen or alkyl having 1 to 6C atoms or a double bond, where R⁵And R⁶Variable in any bridge, m and p are numbers 0 to 3, n and q are numbers 1 to 4 and O and r are numbers 0 to 20,where R is²M and p may vary in either molecule,

V[-O-C(O)-(C(R⁷)(R⁸))_t-(CHOH)_u-(CH₂)_w-H]_i (V)

v is H or CH₃-, when i is 1;

is- (CH)₂)_k-, where k is a number from 2 to 12, when i is 2;

is-CH₂-(CH)_I-CH₂-, where I is a number from 1 to 4, when I ═ I + 2;

16. The lotion according to claim 15, characterized in that the polymer content is 0.1 to 5% by weight.

17. The lotion according to claim 16, wherein the polymer is present in an amount of 0.5 to 2.5% by weight.