WO2005035706A2

WO2005035706A2 - Increasing the water absorbency of textiles made of synthetic material

Info

Publication number: WO2005035706A2
Application number: PCT/EP2004/010706
Authority: WO
Inventors: Rolf Bayersdörfer; Doris HÜERLÄNDER; Martina Hutmacher; Birgit GLÜSEN
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2003-10-07
Filing date: 2004-09-24
Publication date: 2005-04-21
Also published as: WO2005035706A3; DE10347043A1

Abstract

The aim of the invention is to increase a water absorbency of synthetic textiles during washing by using specific polymers.

Description

"Increasing the water absorption capacity of textiles"

The present patent application relates to the use of certain polymers to increase the water absorption capacity of textiles made of synthetic material and detergents which contain such a polymer.

While textiles made of cotton or wool, for example, have a relatively high water absorption capacity and therefore easily reach a state of sufficient moisture, textiles made of synthetic material are usually only capable of extremely low water absorption and also quickly give off odors. For the consumer who attracts such textiles, the result is an uncomfortable feeling, which is essentially due to inadequate transport of moisture away from human skin. In order to improve the washing result even with textiles made from these materials, taking advantage of the above-mentioned effect, their water absorption capacity must consequently be increased.

On the part of the textile industry, especially in the case of sports functional clothing, there are so-called permanent equipment which are intended to remedy the disadvantages mentioned above. However, since these pieces of equipment are usually only of a temporary nature, the benefits usually wane after repeated washing.

Surprisingly, it has now been found that the water absorption capacity of textiles made of synthetic material increases when they are washed in the presence of certain polymers.

The invention therefore relates to the use of polymers selected from (A) the polyurethanes which are obtainable from polyisocyanates and polymeric polyols, (B) the vinyl acetate-polyalkylene glycol graft copolymers, (C) the cationically modified polyvinyl alcohols and (D) the in In the presence of polyvinyl alcohol available polymerization products of vinyl group-containing monomers, and mixtures of two or more of the polymers A, B, C and D, to increase the water absorption capacity of textiles made of synthetic material. The polyurethanes (polymer A) to be used according to the invention are preferably those which can be obtained by polymerizing polyisocyanates with polymeric polyols having an average molecular weight of more than 1000 D and a water solubility at 20 ° C. of more than 300 g of polymer per liter and Polyols with an average molar mass 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.

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 3 to 800, preferably 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 is a number from 1 to 4, - (CH2) _e -CH (CH ₂ -) - (CH ₂ ) e- with c = 3, where e is 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 an average molecular weight 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 (V)

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 stands for a number from 2 to 12, -CH ₂ - (CH-) _Γ CH ₂ - with i = I + 2, where I stands for a number from 1 to 4, - (CH ₂ ) I-CH (CH ₂ -) - (CH ₂ ) _Γ with c = 3, where I 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) ₀ -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 ) form _S , in which s is a number from 4 to 6 and R ⁵ and R ⁶ independently of one another are H or an alkyl group having 1 to 6 carbon atoms or a double bond, where R ⁵ and R ^{6 are} 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;

V [-OC (O) - (C (R ⁷ ) (R ⁸ )) _t - (CHOH) _u - (CH ₂ ) _w -H] _i (V)

in which R ⁷ and R ^{8 can} independently represent H or an alkyl group having 1 to 6 C atoms or a multiple bond to the adjacent C atom, where R ⁷ and R ⁸ can vary within one molecule, t and w independently of one another a Are from 0 to 20 and u is the number 0 or 1, where t, u and w can vary within one molecule,

V can stand for H- or CH ₃ - with i = 1, - (CH ₂ ) _k - with i = 2, where k stands for a number from 2 to 12, -CH ₂ - (CH-) _r CH ₂ - with i = I + 2, where I stands for a number from 1 to 4, HO-CH ₂ - (CH-) _Γ CH ₂ - with i = 1 + 1, where I stands for a number from 1 to 4, - (CH ₂ ) _Γ CH (CH ₂ -) - (CH ₂ ) _I - with c = 3, where l is a number from 1 to 4, or for any aliphatic, alicyclic or aromatic radical or a radical which contains both aliphatic and aromatic groups.

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 neo -pentylglycol. Particularly preferred polymeric polyols according to formula (III) are polypropylene oxide and polytetrahydrofuran with average degrees of polymerization in the 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 polyols according to formula (V) are castor oil, partially hydrogenated castor oil, partially hydrolyzed castor oil and their derivatives.

Preferred further polyols are 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 correspond to the general 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 compounds, 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 represents a number from 1 to 4, - (CH ₂ ) _e -CH (CH ₂ -) - (CH ₂ ) _e - With c = 3, where e is 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 an average molecular weight of 300 D to 1000 D.

In a further preferred embodiment of the invention, polymers are used which are obtainable by using mixtures of at least two polymeric diols of different degrees of polymerization (b in formula I), the degrees of polymerization of the two polymer diol variants according to formula (I) preferably being at least that Distinguish factor 10, for example when using a first polymeric diol with a degree of polymerization in the range from 8 to 15 and a second polymeric diol with a degree of polymerization in the range from 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, preferred are compounds 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 di- Tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, the isomers of tolylene diisocyanate (TDI), 1-methyl-2,4-di-isocyanato-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'-diisocyanatophenyl perfluoroethane, tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-di-isocyanate (HDI), dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene di- isocyanate, bis-isocyanatoethyl phthalate, furthermore diisocyanates with 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 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- or 1, 4- are particularly suitable Tetramethylxylene, isophorone, 4,4-dicyclohexylmethane and lysine ester diisocyanate. 4,4'-Diphenylmethane diisocyanate and / or tetramethyl xylene diisocyanate are very particularly preferred, in particular the m-TMXDI.

The molar ratio of polyol - that is the sum of polymeric polyols according to formula (I) and polyol according to formulas (II) to (V) - 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 of preferred polyurethanes is in the range from 150O to 2,000,000, in particular from 8,000 to 150,000.

In the production of polyurethanes which are known in principle and which are particularly preferred in accordance with the invention, the procedure is preferably such that firstly the polyisocyanate, preferably a diisocyanate, and polymeric polyol of the formula (I), which is preferably a diol (c = 2 ), prepares prepolymers with excess polyol, which are extended in a second stage by reaction with further polyisocyanate and a polyol according to formula (II), (III), (IV) or (V), which is preferably also a diol. It is possible to use a different diisocyanate in the second stage than in the first stage, for example to carry out the reaction of the first stage with MDI and the reaction of the second stage with TMXDI. If, as stated above, several polymeric polyols according to formula (I) with different degrees of polymerization are to be used, it is preferred to use the one with the lowest degree of polymerization in the first stage and the one or those with higher degree of polymerization in the second stage together with the polyol according to formula ( II), (III), (IV) or (V). In the latter variant, a polymeric diol of the formula (I) in which b is a number from 3 to 16 is preferably used in the first stage and a polymeric diol of the formula (I) in which b is in the second stage a number from 17 to 800 is used. Urethane-based polymers thus obtainable are preferably used in the context of the present invention. The use of the polyurethanes mentioned here as polymers capable of removing dirt in washing processes for cotton textiles is known from international patent application WO 03/035712 A1.

Graft copolymers of polyalkylene glycol and vinyl ester (polymer B) are known from the European patent EP 0 285 038 B1. The preferred polyalkylene glycol is polyethylene glycol, molecular weights in the range from 600 to 40,000, in particular 6,000 to 20,000, being particularly preferred. The ratio of polyalkylene glycol to vinyl ester is preferably in the range from 2: 1 to 1:30. Such polymers have a so-called comb structure, the polyalkylene glycol acting as the main chain and the vinyl ester having been grafted onto the alkylene glycol polymer. In particular, a vinyl ester which is derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic acid or methacrylic acid can be used as graft monomer.

The cationically modified polyvinyl alcohols (polymer C) are, in particular, the reaction products of polyvinyl alcohol with compounds which contain an epoxy group in addition to a quaternized nitrogen atom, such as, for example, glycidyltrimethylammonium chloride, epoxybutyl and / or epoxypentylammonium chloride.

It should be noted that such reaction products, in addition to the cationic modification of the alcohol function, may have other substituents on these alcohol functions due to the production process. In fact, polyvinyl alcohols are not accessible through direct polymerization processes, since the necessary basic monomer vinyl alcohol does not exist. Polyvinyl alcohols are therefore produced in polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (for example methanol) in solution. Polyvinyl alcohols which are preferably used as starting materials for polymers to be used according to the invention and which are generally commercially available as white-yellowish powders or granules have molar masses in the range from 3000 g / mol to 320 000 g / mol, in particular 8000 g / mol to 200000 g / mol (corresponding to degrees of polymerization in the range of approx. 75-8000, in particular approx. 200 to 5000). They preferably have degrees of hydrolysis from 20% by weight to 100% by weight, in particular from 30% by weight to 90% by weight. Different in terms of expression, these are wholly or partially saponified polyvinyl alcohol esters, in particular polyvinyl acetates, with a residual content of acyl groups, in particular acetyl groups, of up to about 80% by weight, in particular from 10% by weight to 70% by weight. The polyvinyl alcohols can be characterized in more detail by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity. The transition temperatures of the polyvinyl alcohols depend on the acetyl group content, the distribution of the acetyl groups along the chain and the tacticity of the polymers. Fully saponified polyvinyl alcohols have a glass transition temperature of 85 ° C, whereby the value for partially saponified (87-89%) products is significantly lower at approx. 58 ° C. Polyvinyl alcohols, which normally have a density of about 1.2-1.3 g / cm ³ , are normally soluble in water and highly polar organic solvents such as formamide, dimethylformamide and dimethyl sulfoxide, (chlorinated) hydrocarbons, esters, fats, depending on the degree of hydrolysis and oils are not attacked.

In the following formula, the reaction of glycidyltrimethylammonium chloride (= epoxypropyltrimethylammonium chloride) with partially saponified (30% acetate group fraction) polyvinyl acetate is exemplified to illustrate the reaction products:

- 70% - 30% I

Possible polymerization products of vinyl group-containing monomers (polymer D) in the presence of polyvinyl alcohol are, in particular, those of hydrophobic vinyl group-containing monomers, such as, for example, styrene, t-butyl methacrylate and / or vinyl acetate. The polymerization products made of polyvinyl alcohol and vinyl acetate are commercially available from Cordes. Polymerization products made of polyvinyl alcohol with styrene in a ratio of 1: 1, for. B. Erkol® V03 / 140 (from Acetex, formerly Wacker) and polymerization products made of polyvinyl alcohol with tert-butyl methacrylate, e.g. B. Mowiol® 3-83 (from Clariant).

The use according to the invention is preferably carried out in the course of a washing and / or post-treatment step in which a polymer defined above is used. Another object of the invention is therefore a method for increasing the water absorption capacity of textiles made of synthetic material by washing and / or post-treating the textile in the presence of such polymer.

As described above, the polymers used according to the invention can be produced in a simple manner and are ecologically and toxicologically harmless. They lead to a significantly higher water absorption capacity of textiles made of synthetic material when they are treated with them, which improves the wearing comfort of the textile treated in this way. The transport of water away from the body of the person wearing the textiles is accelerated and more efficient, a feeling of moisture does not arise at all or does decrease quickly.

It is preferred if the textiles to be treated according to the invention consist of or contain polyester, polyamide, polyacrylonitrile, elastane or mixtures thereof. The latter variant means, for example, so-called cotton blends which contain cotton and synthetic material in the blended fabric.

The use according to the invention can take place in the course of a washing process in such a way that the polymer is added to a detergent-containing liquor or, preferably, the polymer is introduced into the liquor as part of a detergent. Another object of the invention is therefore a detergent which contains an above-mentioned polymer.

The use according to the invention in the context of a laundry aftertreatment process Accordingly, the polymer can be added separately to the rinse liquor which is used after the wash cycle using a detergent, or as a component of the laundry aftertreatment agent, in particular a fabric softener. In this aspect of the invention, the said detergent used in the wash cycle can also contain a polymer to be used according to the invention, but it can also be free of this. The invention therefore furthermore relates to a laundry aftertreatment composition which contains an abovementioned polymer.

Agents which contain a polymer to be used according to the invention can contain all the usual other constituents of such agents which do not interact with the polymer in an undesirable manner. The polymer is preferably incorporated in amounts of from 0.01% by weight to 7% by weight, in particular 0.1% by weight to 5% by weight, into detergents or laundry aftertreatment agents.

Surprisingly, it was found that the polymer used according to the invention has a positive effect on the action of certain other detergent and cleaning agent ingredients and that, conversely, the action of the polymer used according to the invention is enhanced 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, in particular based on oxidized carbohydrates, in the case of peroxygen-based bleaching agents, in particular in the case of alkali percarbonate, in the case of synthetic anionic surfactants of the sulfate and sulfonate type and in Graying inhibitors, for example cellulose derivatives, in particular anionic cellulose ethers such as carboxymethyl cellulose, and laundry softening agents, in particular ester quats, which is why the use of at least one of the other ingredients mentioned together with the polymer 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, in particular in an amount in the range from 1% by weight to 20% by weight, preferably from 1% by weight to 20% by weight. 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 processes specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as they are in accordance with the processes of the US patents US 1 985424, US 2 016 962 and US 2703 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. Preferred monomer building block is because the good availability of glucose. 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. Agents which have an alkyl polyglycoside content in the range from 0.1 G% to 7 G% are particularly preferred.

Another embodiment of such agents comprises the presence of synthetic anionic surfactants of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfofatty acid esters and / or sulfofatty acid disalts, in particular in an amount in the range from 0.01% by weight to 15% by weight. %, preferably 0.01% to 5% by weight. The anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms.

Synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms, which carry an alkali metal, ammonium or alkyl or hydroxyalkyl substituted ammonium ion as countercation. The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the .alpha.-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 up to 6 carbon atoms, preferred example 1 to 4 carbon atoms, derivative sulfonation products, as well as the sulfofatty acids resulting from these by formal saponification.

Soaps can be considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.5% by weight to 7% by weight, but may also be absent entirely. However, in particular in liquid or gel-like compositions which contain a polymer used according to the invention, higher amounts of soap, as a rule, of up to 20% by weight can also be present.

If desired, the agents can also contain betaines and / or cationic surfactants which - if present - are preferably used in amounts of 0.5% by weight to 7% by weight. Among them, the ester quats discussed below are particularly preferred.

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

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 can also contain small amounts of polymerizable substances in copolymerized form 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 the 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 the third monomer 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 CC 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 is substituted in the 2-position with an alkyl radical, preferably with a CC alkyl radical, or with an aromatic radical which is preferably derived from benzene or benzene derivatives. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of 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 are. 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 used in the form of their water-soluble salts, in particular their alkali metal salts. An agent which contains a polymer to be used according to the invention preferably contains 0.1% by weight to 5% by weight of water-soluble organic builder.

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 agents 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. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na are used ₂ Si _x O _{2x + 1} ^■ yH ₂ O, in which x, known as the modulus, an integer of 1, 9 to 4 and y a number from 0 to Is 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x 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, whereby 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 produced 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 0 425 428 described, can be used in agents containing a cellulose derivative used according to the invention. In a further preferred embodiment of the compositions, 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 or cleaning agents containing a cellulose derivative used 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 aluminum silicate, in particular zeolite, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance , The weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

In addition to the builder substances mentioned, other water-soluble or water-insoluble inorganic substances can be used in the compositions which contain a cellulose derivative to be used according to the invention. Are suitable in this Relationship between the alkali carbonates, alkali hydrogen carbonates and alkali sulfates and their mixtures. Such additional inorganic material can be present in amounts up to 70% by weight.

In addition, the agents can contain other constituents customary in washing and cleaning agents. These optional ingredients include, in particular enzymes, enzyme stabilizers, bleaching agents, bleach activators, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic, polyphosphonic acids and / or aminopolyphosphonic acids, Farbfixierwirkstoffe, Farbübertragungsinhibito- reindeer, for example, polyvinyl pyrrolidone or polyvinyl pyridine-N-oxide, foam inhibitors, for example organopolysiloxanes or paraffins , Solvents, thickeners, and optical brighteners, for example stilbene disulfonic acid derivatives. Agents containing a combination used according to the invention preferably contain up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight 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, of graying inhibitors and up to 2% by weight, in particular 0.1% by weight contain up to 1% by weight of foam inhibitors, the proportions by weight referred to in each case based on the total average.

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

Enzymes which may be present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. Protease obtained from microorganisms such as bacteria or fungi is primarily suitable. It can be obtained in a known manner by means of fermentation processes from suitable microorganisms, which are described, for example, in German Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 21 01 803 and DE 21 21 397, US Pat. Nos. 3,623,957 and 4,264,738, European patent application EP 006 638 and international patent application WO 91/02792. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384 717 , from Pseudomonas species, such as in 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 described in European patent application EP 130 064, from Rhizopus species, such as described in European patent application EP 117 553, or from Aspergillus species, such as in European Patent application EP 167 309 described can be obtained. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5. Such cellulases are known, for example, from German published applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 and the international patent applications WO 95/02675 and WO 97/14804 known and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.

The usual enzyme stabilizers which are optionally present, in particular in liquid and gel form, include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, lower carboxylic acids, for example from European patent applications EP 376 705 and EP 378 261 known, boric acid or alkali borates, boric acid-carboxylic acid combinations, as known, for example, from European patent application EP 451 921, boric acid esters, such as from international patent application WO 93/11215 or the European European patent application EP 511 456, boronic acid derivatives, such as known from European patent application EP 583 536, calcium salts, for example the calcium formic acid combination known from European patent EP 28 865, magnesium salts, such as from European patent application EP 378 262, and / or sulfur-containing reducing agents, as known, for example, from European patent applications EP 080 748 or EP 080 223.

Suitable foam inhibitors include long-chain soaps, in particular behen soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate compositions, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150 386.

A further embodiment of such an agent, which contains a cellulose derivative to be used according to the invention, contains bleaching agents based on peroxygen, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts in the range of 2% by weight .-% to 10 wt .-%. These bleaching agents that can be considered are the per compounds generally used in detergents, such as hydrogen peroxide, perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts. Bleaching agents of this type are obtained in detergents which contain a cellulose derivative used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight on the entire medium, with percarbonate in particular being used. The optional component of the bleach activators comprises the N- or O-acyl compounds commonly used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopamide and sulfuryl amines Cyanurates, also carboxylic anhydrides, in particular phthalic anhydride, carbonic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile Salts. The bleach activators can be coated or granulated with coating substances in a known manner in order to avoid the interaction with the per-compounds during storage, with the aid of carboxymethyl cellulose granulated tetraacetyl ethylenediamine with average grain sizes of 0.01 mm to 0.8 mm, as described, for example, by can be prepared in the process described in European Patent EP 37 026, granulated 1,5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, as produced by the process described in German Patent DD 255 884 and / or according to the processes described in the international patent applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927, trialkylammonium acetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.

It is also possible to use a polymer mentioned together with a dirt-releasing polymer made from a dicarboxylic acid and an optionally polymeric diol.

The known dirt-releasing polymers, which are particularly active on polyester and can be used in addition to the polymer 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- (CHRn-) _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- (CHRn-) _a O- and polymer diol units - are located in the polyesters obtainable from these. (O- (CHR ¹¹ -) _a ) _b θ- 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. The degree of polymerization b in the polymer diol units is preferably in the range ranges 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 preferred selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among 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 group-capped, alkyl groups with 1 to 22 C atoms and esters of monocarboxylic acids being suitable as end groups. The end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 C atoms, in particular 5 to 18 C atoms. These include valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaic acid, petroselaic acid, petroselaic acid, oleroselaic acid, petroselaic acid , Linolaidic acid, linolenic acid, eläostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupa- nodonic acid, lignoceric acid, cerotinic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can in turn be connected to one another via their hydroxyl group and their carboxyl group and can therefore be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers made from ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units Have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used together with the combination essential to the invention.

The dirt-releasing polymers are preferably water-soluble, the term "water-soluble" being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8. Under these conditions, however, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter.

Preferred laundry aftertreatment compositions which contain a polymer to be used according to the invention have what is known as an ester quat, that is to say a quaternized ester of carboxylic acid and amino alcohol, as the softening active ingredient. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this context, reference is made to the international patent application WO 91/01295, according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. German patent DE 43 08794 also discloses a process for the preparation of solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Overviews on this topic have been published, for example, by R.Puchta et al. in Tens.Surf.Det, 30, 186 (1993), M.Brock in Tens.Surf.Det. 30, 394 (1993), R. Lagerman et al. in J.Am.Oil.Chem.Soc, 71. 97 (1994) and I.Shapiro in Cosm.Toil. 109, 77 (1994) appeared.

Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow the formula (VI)

R ⁴ [R ¹ CO- (OCH ₂ CH ₂ ) _m OCH ₂ CH ₂ -N ⁺ -CH ₂ CH ₂ O- (CH ₂ CH ₂ O) _n R ² ] X ^" (VI) CH ₂ CH ₂ O ( CH ₂ CH ₂ O) _p R ³

in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures , as they occur, for example, in the pressure splitting of natural fats and oils. Preferably Technical C _{12 18} cocofatty acids and, in particular partly hydrogenated _{C16 /} ι ₈ tallow or palm oil fatty acids, as well as elaidic acid-rich Ci employed _6/18 -fatty acid. For the preparation of the quaternized esters, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1. With regard to the application properties of the esterquats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/ ₈ -tallow or palm fatty acid (iodine number 0 to 40) from. Quaternized fatty acid triethanolamine ester salts of the formula (I) in which R ¹ CO for an acyl radical having 16 to 18 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m, n and p for 0 and X for Methyl sulfate is particularly advantageous. In addition to the quaternized carboxylic acid triethanolamine ester salts, quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (VII) are also suitable as esterquats.

R ⁴ [R ¹ CO- (OCH ₂ CH ₂ ) _m OCH ₂ CH ₂ -N ⁺ -CH ₂ CH ₂ O- (CH ₂ CH ₂ O) _n R ² ] X ^" (II)

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X stands for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

Finally, a further group of suitable ester quats are the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyl dialkylamines of the formula (VIII),

R ⁶ O- (CH ₂ CH ₂ O) _m OCR ¹ [R ⁴ -N ⁺ -CH ₂ CHCH ₂ O- (CH ₂ CH ₂ O) _Π R ² ] X- (III) k in the R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X stands for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the exemplary information given for (VI) also applies analogously to the esterquats of the formulas (VII) and (VIII). The esterquats are usually commercially available in the form of 50 to 90 percent by weight alcoholic solutions, which can also be diluted with water without problems, ethanol, propanol and isopropanol being the usual alcoholic solvents.

Ester quats are preferably used in amounts of 5% by weight to 25% by weight, in particular 8% by weight to 20% by weight, based in each case on the total laundry aftertreatment agent, used. If desired, the laundry aftertreatment agents used according to the invention can additionally contain detergent ingredients listed above, provided that they do not interact unreasonably with the esterquat. It is preferably a liquid, water-containing agent which is easily accessible by mixing the ingredients.

In a preferred embodiment, an agent into which a polymer to be used according to the invention is incorporated is liquid and contains 0.01% by weight to 10% by weight, in particular 0.1% by weight to 6% by weight, of synthetic material Anionic surfactant, which is preferably free of alkylbenzenesulfonates, 1% by weight to 25% by weight, in particular 2% by weight to 20% by weight of nonionic surfactant, 0.5% by weight to 7% by weight, in particular 1% by weight to 5% by weight of cationic and / or zwitterionic surfactant, in particular esterquat, and up to 90% by weight, in particular 50% by weight to 85% by weight of water and 0.01% by weight. -% to 8 wt .-%, in particular 0.1 wt .-% to 5 wt .-% non-aqueous solvent.

In a further preferred embodiment, a liquid agent into which a polymer to be used according to the invention is incorporated contains 1% by weight to 30% by weight, in particular 4% by weight to 25% by weight of nonionic surfactant, 0.5 % By weight to 7% by weight, in particular 1% by weight to 5% by weight of cationic and / or zwitterionic surfactant, in particular esterquat, and up to 95% by weight, in particular 50% by weight to 85 % By weight of water and 0.01% by weight to 8% by weight, in particular 0.1% by weight to 5% by weight of non-aqueous solvent.

A liquid composition according to the invention preferably has a pH (undiluted) in the range from 4.0 to 7, in particular 4.5 to 7. In a preferred embodiment, it contains enzyme, in particular cellulase.

In a further preferred embodiment, an agent into which a polymer to be used according to the invention is incorporated is gel-like and contains 1% by weight to 20% by weight, in particular 1.5% by weight to 15% by weight, of synthetic anionic surfactant , 1% by weight to 20% by weight, in particular 2% by weight to 20% by weight of nonionic surfactant, 0.5% by weight to 7% by weight, in particular 1% by weight to 5 % By weight of soap, 0.1% by weight to 7% by weight, in particular 1% by weight to 5% by weight of organic builder, in particular polycarboxylate such as citrate, 0.05% by weight to 4% by weight .-%, in particular 0.1 wt .-% to 2 wt .-% % Thickeners and up to 95% by weight, in particular 50% by weight to 85% by weight of water and 0.1% by weight to 10% by weight, in particular 1% by weight to 7% by weight % non-aqueous solvent. A gel-like agent according to the invention preferably has a pH (undiluted) in the range from 7.5 to 9. It preferably has a viscosity (at 20 ° C, Brookfield viscometer, 20 rpm) in the range from 500 mPa.s to 2500 mPa.s, in particular 800 mPa.s to 1800 mPa.s. In a preferred embodiment, it contains enzyme, in particular protease, amylase and / or cellulase.

Solid agents are preferably prepared in such a way that a particle which contains the polymer essential to the invention is mixed with further detergent ingredients in solid form. A spray drying step is preferably used to produce the particle containing the polymer. Alternatively, it is also possible to use a compacting compounding step to produce this particle and, if appropriate, also to produce the finished solid agent.

Examples

Example 1: Synthesis of a PEG-vinyl acetate graft copolymer (B1)

210 g of polyethylene glycol 6000 were introduced and heated to 90 ° C. 4.2 g of dibenzolyperoxide (50% in ethyl acetate) were added under nitrogen. The solution was then stirred for 4 hours to destroy any radical scavengers. The mixture was then allowed to cool to 80 ° C., 29.25 g of vinyl acetate were added and 0.42 g of t-butyl peroxybenzoate were added. After 10 minutes, 0.36 g of dibenzoyl peroxide (50% in ethyl acetate) in 2.1 g of ethyl acetate were added and 360.8 g of vinyl acetate were added dropwise over the course of about 3 hours. The mixture was then stirred at 80 ° C for 3 hours and another 0.36 g of dibenzoyl peroxide (50% in ethyl acetate) were added. After 30 minutes the solution was evacuated for about 45 minutes to remove the solvent. The ratio of PEG 6000 to vinyl acetate is 35:65.

Example 2: Synthesis of a polystyrene / polyvinyl alcohol dispersion (B2)

600 g of polyvinyl alcohol (Erkol®V03 / 140) were dissolved in 3 liters of water under nitrogen at approx. 80 ° C. Then 70 g of styrene were added, emulsified at 85 ° C. for 2 hours and then 12 g of potassium peroxodisulfate (starter) were added. 530 g of styrene were then added dropwise over a further 2 hours. The mixture was then left to stir for a further 1 hour and the solution was cooled.

Example 3: Synthesis of a poly-tert-butyl methacrylate / polyvinyl alcohol dispersion (B3)

The synthesis was carried out analogously to Example 2, but using tert-butyl methacrylate instead of styrene.

Example 4: Synthesis of a cationically modified polyvinyl alcohol (B4)

400 g of N-methylpyrrolidone were introduced, heated to 85 ° C and flushed with nitrogen. Approximately 116.7 g of polyvinyl alcohol (partially saponified polyvinyl acetate, 70% OH groups and 30% acetate groups) were added. After its solution, 22.33 g of glycidyltrimethylammonium chloride (approx. 0.67%) and boron trifluoride (3 drops, initiator) were added rapidly. After the reaction was completed, the product was precipitated in 7 liters of isopropanol. The solid was then filtered off and cleaned twice with 1.5 liters of isopropanol each time. On- the product was then dried in a vacuum in a heating cabinet and then chopped using a kitchen mixer.

Example 5: Application tests

In a gel-like agent V1, containing 5% by weight of synthetic anionic surfactant, 12% by weight of ethoxylated fatty alcohol, 1.5% by weight of alkyl polyglucoside, 4.5% by weight of soap, 1.5% by weight of sodium citrate, 0.2% by weight of thickener, the rest essentially water, were incorporated (with a corresponding reduction in the water content) in each case 3% by weight of the polymers B1, B2, B3 and B4 described in the preceding examples. The suction speed of fabrics made of polyester (Table 1) or polyester / cotton blended fabrics (45% / 55%; Table 2) was determined according to DIN 53924 (measuring length 100 mm) after 1, 3, 5 and 10 minutes. Tables 1 and 2 below show the percentage increase in suction speed of the fabric after 10 washes with the respective detergent compared to the unwashed fabric.

Table 1: Polyester

According to the TEGEWA drip test published in Melliand Textile Reports 1987, pp. 581-583, the sinking times (Table 3) and spreading diameter (Table 4) were also determined using the same textile materials and agents.

Table 3: Sink times in s

Textiles made of polyester or polyester / cotton blended fabrics washed with agents V1 + B1, V1 + B2, V1 + B3 or V1 + B4 were much more comfortable to wear than those that had been washed with agent V1.

Claims

claims

1. Use of polymers selected from (A) the polyurethanes which are obtainable from polyisocyanates and polymeric polyols, (B) the vinyl acetate-polyalkylene glycol graft copolymers, (C) the cationically modified polyvinyl alcohols and (D) those in the presence of Polyvinyl alcohol available polymerization products of vinyl group-containing monomers, and mixtures of two or more of the polymers A, B, C and D, to increase the water absorption capacity of textiles made of synthetic material.

2. Use according to claim 1, characterized in that the polymer is a polyurethane which is obtainable by polymerizing polyisocyanates with 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 and Polyols with an average molar mass 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.

3. Use according to claim 2, characterized in that the polymeric polyol with an average molecular weight of over 1000 D and a water solubility at 20 ° C of over 300 g of polymer per liter of a compound according to formula (I) W [(O- (CH ₂ -) _a ) _{b is} -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 is within one molecule can vary, 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 is a number from 1 to 4, - (CH2) _e -CH (CH ₂ -) - (CH ₂ ) e- with c = 3, where e is a number from 1 to 4 , or for any aliphatic, alicyclic or aromatic radical or a radical which contains both aliphatic and aromatic groups.

4. Use according to claim 2 or 3, characterized in that the polymeric polyol with an average molecular weight of over 1000 D and a water solubility at 20 ° C of over 300 g of polymer per liter of a polyethylene glycol, in particular with an average molecular weight between 3000 and 12000 D, is. Use according to one of claims 2 to 4, 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 (V),

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 \ f and h can vary within a molecule; V for H- with i = 1, - (CH ₂ ) _k - with i = 2, where k stands for a number from 2 to 12, -CH ₂ - (CH-) _r CH ₂ - with i = I + 2 , where I stands for a number from 1 to 4, - (CH ₂ ) ι-CH (CH ₂ -) - (CH ₂ ) r with c = 3, where I stands for a number from 1 to 4, or for one any aliphatic, alicyclic or aromatic radical or a radical which contains both aliphatic and aromatic groups,

in which Cy represents phenylene or cyclohexylidene, R ^{2 represents} hydrogen or an alkyl group with 1 to 6 C atoms, R ³ and R ⁴ independently of one another represent hydrogen or an alkyl group with 1 to 6 C atoms or together represent an aliphatic bridge (CR ⁵ R ⁶ ) form _S , in which s represents a number from 4 to 6 and R ⁵ and R ⁶ independently of one another are 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,

V [-OC (O) - (C (R ⁷ ) (R ⁸ )) _t - (CHOH) _u - (CH ₂ ) _w -H] i (V) in which R ⁷ and R ^{8 can} independently represent H or an alkyl group having 1 to 6 C atoms or a multiple bond to the adjacent C atom, where R ⁷ and R ⁸ can vary within one molecule, t and w independently of one another are a number from 0 to 20 and u is the number 0 or 1, where t, u and w can vary within one molecule, V is H- or CH ₃ - with i = 1, - (CH ₂ ) _k - with i = 2, where k is a number from 2 to 12, -CH ₂ - (CH-) _Γ CH ₂ - with i = I + 2, where I is a number from 1 to 4, HO-CH ₂ - (CH-) _r CH ₂ - with i = 1 + 1, where I represents a number from 1 to 4, - (CH ₂ ) ι-CH (CH ₂ -) - (CH ₂ ) ι- with c = 3 , where I represents a number from 1 to 4, or any aliphatic, alicyclic or aromatic radical or a radical which contains both aliphatic and aromatic groups.

6. Use according to claim 1, characterized in that the polymer is a graft copolymer of polyalkylene glycol and vinyl ester, in which polyalkylene glycol acts as the main chain and the vinyl ester has been grafted onto the alkylene glycol polymer.

7. Use according to claim 6, characterized in that the vinyl ester is derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or is a methyl or ethyl ester of acrylic acid.

8. Use according to claim 6 or 7, characterized in that the polyalkylene glycol is a polyethylene glycol, in particular with a molecular weight in the range from 600 to 40,000.

9. Use according to claim 1, characterized in that the polymer is a reaction product of polyvinyl alcohol with compounds which, in addition to a quaternized nitrogen atom, contain an epoxy group, in particular glycidyltrimethylammonium chloride, epoxybutyl and / or epoxypentylammonium chloride.

10. Use according to claim 1, characterized in that the polymer is a polymerization product which is obtainable in the presence of polyvinyl alcohol and contains hydrophobic vinyl group-containing monomers, in particular styrene, t-butyl methacrylate and / or vinyl acetate.

11. Use according to one of claims 1 to 10, characterized in that it takes place in the context of a washing and / or laundry post-treatment step.

12. Use according to claim 11, characterized in that the polymer is used as a constituent of a washing or laundry aftertreatment agent which, in addition to the polymer, contains at least one further ingredient selected from enzymatic active ingredients, in particular proteases and lipases, water-insoluble inorganic builders, water-soluble inorganic and organic builders, in particular based on oxidized carbohydrates, bleaching agents based on peroxygen, in particular alkali percarbonate, synthetic anionic surfactants of the sulfate and sulfonate type, graying inhibitors, in particular cellulose ethers, and laundry softening agents, in particular ester quats.

13. Use according to one of claims 1 to 12, characterized in that the textiles consist of or contain polyester, polyamide, polyacrylonitrile, elastane or mixtures thereof.

14. A method for increasing the water absorption capacity of textiles made of synthetic material by washing and / or aftertreatment of the textile in the presence of polymers, selected from (A) the polyurethanes which are obtainable from polyisocyanates and polymeric polyols, (B) the vinyl acetate-polyalkylene glycol Graft copolymers, (C) the cationically modified polyvinyl alcohols and (D) the polymerization products of styrene or t-butyl methacrylate obtainable in the presence of polyvinyl alcohol, and mixtures of two or more of the polymers A, B, C and D.

15. Detergent containing a polymer selected from (A) the polyurethanes which are obtainable from polyisocyanates and polymeric polyols, (B) the vinyl acetate-polyalkylene glycol graft copolymers, (C) the cationically modified polyvinyl alcohols and (D) the in In the presence of polyvinyl alcohol obtainable polymerization products of styrene or t-butyl methacrylate, and mixtures of two or more of the polymers A, B, C and D.

16. laundry aftertreatment agent containing a polymer selected from (A) the polyurethanes which are obtainable from polyisocyanates and polymeric polyols, (B) the Vinyl acetate-polyalkylene glycol graft copolymers, (C) the cationically modified polyvinyl alcohols and (D) the polymerization products of styrene or t-butyl methacrylate obtainable in the presence of polyvinyl alcohol, and mixtures of two or more of the polymers A, B, C and D.