AU2014336402B2 - Stabilisation of enzymes in aqueous systems containing surfactants - Google Patents

Abstract

The invention relates to the strengthening of the performance of enzymes in detergents or cleaning agents which contain water and surfactants, or at least to the conservation of same after storage. This is substantially achieved with the use of polymers that can be obtained by polymerising N-vinyl pyrrolidone with a co-monomer selected from the group comprising: N-vinyl caprolactam, N-vinyl piperidone, N-vinyl succinimide, N-vinyl glutarimide, N-vinylacetamide, N-alkyl-N-vinylacetamide, N-vinylformamide, N-alkyl-N-vinylformamide, dialkyl acrylamide, and mixtures of at least two of these.

Description

PT031885 PCT

Stabilization of enzymes in aqueous systems containing surfactants [0002] The present invention relates to the use of specific polymers to intensify or after storage at least to retain the performance of enzymes in water- and surfactant-containing detergents or cleaning agents, which are used in the washing of textiles or the cleaning of hard surfaces.

[0003] In order to increase their washing or cleaning performance, detergents or cleaning agents frequently contain at least one enzyme, often a plurality of enzymes. Frequently employed enzymes in this case are proteases, lipases, amylases, cellulases, and mannanases.

[0004] In particular in liquid detergent and cleaning agents in which the enzymatic active substances are present in dissolved or suspended form, undesirable interactions, which negatively affect the storage stability of the enzymes in the liquid formulation, can result from the direct contact of the enzymes with the other ingredients and/or with one another. Thus, it is known, for example, that proteolytic enzymes break down other enzymes present in a liquid detergent or cleaning agent, such as amylases, lipases, or cellulases, but themselves as well in particularly unfavorable cases. Even if the enzymes are not destroyed by the breakdown of their primary structure, changes in the folding of the tertiary structure of enzymes can occur due to the effects of other detergent and cleaning agent ingredients. As a result, with increasing storage time, a loss, increasing over time, in the cleaning performance of the agent in regard to enzyme-specific stains is observed. The detergent and cleaning agent ingredients that can lead to enzyme inactivation in aqueous systems include synthetic anionic surfactants, particularly those of the alkylbenzene sulfonate type.

[0005] The use of poly(N-vinylpyrrolidone) in detergents is known. Thus, for example, the international patent application WO 2011/001173 A1 describes liquid detergents, which contain 0.01 to 5% by weight of cellulase and 0.01 to 5% by weight of poly(N-vinylpyrrolidone) and/or the salt thereof with an average molecular weight of 20,000 g/mol to 60,000 g/mol. Crosslinked polymers comprising 10 to 50% by weight of N-vinylcaprolactam and 50 to 90% by weight of N-vinylpyrrolidone, which may be prepared in the presence of 0.5 to 7% by weight of a crosslinker, which can also be 1-vinyl-3(E)-ethylidene pyrrolidone produced in situ, are known from the international patent application WO 97/29139 A1. Such crosslinked polymers are suitable for filtering polyphenols from beer. The soil release effect of N-vinylcaprolactam homopolymers and copolymers with small amounts of other monomers such as, for example, N-vinylpyrrolidone is known from European patent application EP 0 181 204 A2. It is known from European patent application EP 0 181 205 A2 that such polymers may also be applied as coating materials to fibers, particularly made of polyester, to achieve the soil release effect. Detergents, containing an effective soil-releasing and fabric-softening amount of N-vinylcaprolactam homopolymer having a K value of at least 40, are known from US patent application US 2002/0177542. International Patent 1 2 2014336402 16 Aug 2017 application WO 2004/014326 A1 describes anionic surfactant-containing shampoos which contain silicone derivatives, having amino and hydroxy groups, and water-soluble cationic polymers having an average molecular weight of 100,000 g/mol to 2,000,000 g/mol and charge densities of 0.6 to 4 mEq/g, whereby N-vinylpyrrolidone/alkylaminoacrylate/N-vinylcaprolactam copolymers, among others, are named, and these are used therein due to their conditioning effect. It is known from international patent application WO 2013/034438 A1 that polymers, obtainable by polymerization of N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylsuccinimide, N-vinylglutarimide, N-vinylacetamide, N-alkyl-N-vinylacetamide, N-vinylformamide, N-alkyl-N-vinylformamide, or mixtures of at least two of said comonomers, intensify the primary washing power of detergents or cleaning agents in the washing of textiles or in the cleaning of hard surfaces particularly with respect to bleach- or enzyme-sensitive stains.

[0006] It has been found surprisingly that certain N-vinylpyrrolidone-containing polymers contribute to achieving the aforementioned object of improving enzyme stability-10007] The subject matter of the invention is the use of polymers obtainable by polymerizing N-vinylpyrrolidone with a comonomer selected from the group comprising N-vinylcaprolactam, N-vinylpiperidone, N-vinylsuccinimide, N-vinylglutarimide, N-vinylacetamide, N-alky!-N-vinylacetamide, N-vinylformamide, N-alkyl-N-vinylformamide, dialkyl acrylamide, and mixtures of at least two of said compounds - to improve the performance of enzymes and/or - to stabilize enzymes and/or - to slow enzyme degradation and/or - to prevent enzyme degradation in liquid water- and surfactant-containing detergents or cleaning agents.

In one aspect there is provided use of polymers obtained by polymerizing N-vinylpyrrolidone with a comonomer, selected from the group comprising N-vinylcaprolactam, N-vinylpiperidone, N-vinylsuccinimide, N-vinylglutarimide, N-vinylacetamide, N-alkyl-N-vinylacetamide, N-vinylformamide, N-alkyl-N-vinylformamide, dialkyl acrylamide, and mixtures of at least two of said compounds - to stabilize enzymes and/or - to slow enzyme degradation and/or - to prevent enzyme degradation in liquid water- and surfactant-containing detergents or cleaning agents.

(13481528_1):RTK 2a 2014336402 16 Aug 2017 [0008] An alkyl group in the named monomers preferably has 1 to 10 C atoms, particularly 1 to 3 C atoms, and can be linear or singly or optionally multiply branched; the methyl group is particularly preferred. The polymers used according to the invention are preferably not crosslinked. The polymer preferably is made up, apart from units originated from the monomer N-vinylpyrrolidone, of units originating from one other monomer, and has the two mentioned units in the weight ratio of 99:1 to 1:99, particularly of 97:3 to 70:30.

[0009] The polymeric active substance preferably has an average molecular weight in the range of 1000 g/mol to 500,000 g/mol, particularly of 1100 g/mol to 150,000 g/mol (here and below, the average molecular weights refer to number averages).

(134S1528_ ] ):RTK

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[0010] An enzyme-, surfactant-, and water-containing liquid detergent or cleaning agent, which lastingly has an improved washing or cleaning performance, particularly in the case of longer storage, is successfully provided by the invention.

[0011] Preferably, the polymer exhibits interactions with anionic surfactants such as linear alkylbenzene sulfonate in particular; these may be attributed to the formation of a surfactant-polymer aggregate. The effect can be substantiated by measuring the surface tension or interfacial tension, whereby the surface tension or interfacial tension is increased by the presence of the polymer. This increase may be due to the fact that an aggregate having cleaning activity forms in the solution, and therefore less surfactant is present at the interface. To determine the aggregation parameter Xag, the surface tension γ of an aqueous solution of 0.12 g/L of linear C10.i3 alkylbenzene sulfonate, as available under the trade names Disponil® LDBS 55 or Marlon® A360, for example, is measured in the absence and presence of 0.2 g/L of the polymer, and the value in the absence of the polymer is subtracted from the value in the presence of the polymer:

Xag = Yi (surfactant + polymer) - y2 (surfactant) [0012] The surface tension may be measured by means of the Du-Notiy ring method, for example, using a TE3 ring/plate tensiometer from the company Lauda (Lauda-Konigshofen). For this purpose, a ring made of metal, for example, which is attached to a torsion dynamometer, is immersed in the surfactant-polymer solution such that the ring is situated beneath the surface of the solution. The ring is then slowly pulled out of the solution, and the force exerted on the measuring ring just before the liquid film tears is measured with the torsion dynamometer. The surface tension can be calculated from the known diameter of the ring and the breakaway force.

[0013] Alternatively, the aggregation parameter Xag can be determined by measuring the dynamic interfacial tension, for example, by drop volume tensiometry, which can be carried out, for example, using a TVT2 drop volume tensiometer from the company Lauda (Lauda-Konigshofen). For this purpose, isopropyl myristate is forced out of a hollow needle into the aqueous solution of 0.12 g/L of the aforementioned linear C10-13 alkylbenzene sulfonate in the absence and presence of 0.2 g/L of the polymer. Measuring the drop volume permits the calculation of the dynamic surface tension, the drop volume being measured after 1 minute. The value in the absence of the polymer is subtracted from the value in the presence of the polymer and the result is multiplied by a normalization factor of 3:

Xag = 3 X [y 1 interface (surfactant + polymer) - Yzmterface (surfactant)] 3

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[0014] The measurements are performed in each case at 25°C with the measurement solutions being adjusted to pH 8.5. Polymers in which aggregation parameters Xag > 1 mN/m, preferably Xag > 4 mN/m, and particularly in the range of 5 mN/m to 8 mN/m occur, are particularly preferred.

[0015] The active substances used according to the invention can be prepared in a simple way by free-radical polymerization of the ethylenically unsaturated at least two monomers, whereby this is carried out preferably as a random copolymerization. If desired, however, blocks of vinylpyrrolidone units and units of a comonomer and optionally other blocks of other comonomers can also be present in the polymers.

[0016] The enzyme-stabilizing effect achieved according to the invention can become noticeable within the scope of a washing or cleaning process, if the polymeric active substance is introduced into the liquor as a component of a detergent or cleaning agent, whereby the concentration of the polymeric active substance in the liquor is preferably in the range of 0.01 g/L to 0.5 g/L, particularly of 0.02 g/L to 0.2 g/L.

[0017] The enzyme-stabilizing effect achieved according to the invention occurs with the use of one enzyme but also a plurality of enzymes. In principle, all enzymes established in the prior art can be used in this regard. Preferably, these are one or more enzymes that can display catalytic activity in a detergent or cleaning agent, particularly a protease, amylase, lipase, cellulase, hemicellulase, mannanase, a pectin-cleaving enzyme, a tannase, xylanase, xanthanase, β-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreductase, and mixtures thereof. Preferred hydrolytic enzymes comprise in particular proteases, amylases, especially a-amylases, cellulases, lipases, hemicellulases, especially pectinases, mannanases, β-glucanases, and mixtures thereof. Proteases, amylases, and/or lipases, and mixtures thereof are particularly preferred and lipases are very particularly preferred. These enzymes are of natural origin in principle; improved variants based on natural molecules are available for use in detergents and cleaning agents and are accordingly preferred for use.

[0018] Examples of the different enzyme classes that can be used within the scope of the present invention are described below: [0019] Examples of usable lipases (triacylglycerol acylhydrolases, EC 3.1.1.3) or cutinases, which are present particularly because of their triglyceride-cleaving activities, but also to produce peracids in situ from suitable precursors, are the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or the correspondingly further developed lipases, particularly those with the amino acid substitution D96L. They are marketed, for example, by the company Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme®, and Lipex®. Furthermore, for example, cutinases originally isolated from Fusarium solani pisi and Humicola 4

PT031885 PCT insolens can be used. Similarly usable lipases can be obtained from the company Amano under the names Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP®, and Lipase AML®. For example, the lipases or cutinases, whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii, from the company Genencor can be used. Other important commercial products that may be mentioned are the preparations M1 Lipase® and Lipomax®, originally marketed by the company Gist-Brocades, and the enzymes marketed by the company Meito Sangyo KK, Japan, under the names Lipase MY-30®, Lipase OF®, and Lipase PL®, and further the product Lumafast® from the company Genencor. Lipases from the family 1.1 or 1.2 of lipases (according to Apigny & Jaeger, Biochem. J. (1999) 343, 177-183), particularly a lipase from a bacterium from the genus Burkholderia or Pseudomonas are used in different preferred embodiments. A special example of a suitable lipase is the lipase lipA from Burkholderia cepacia.

[0020] Of the proteases, the subtilisin-type proteases are preferred. Examples of these are the subtilisins BPN' and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and the proteases TW3 and TW7, to be classified as subtilases and no longer as subtilisins in the strict sense. Subtilisin Carlsberg is obtainable in a further developed form under the trade name Alcalase® from the company Novozymes A/S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are marketed under the trade names Esperase® or Savinase® by the company Novozymes. The protease variants sold under the name BLAP® are derived from the protease from Bacillus lentus DSM 5483. Other usable proteases are, for example, the enzymes obtainable under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase®, and Ovozyme® from the company Novozymes, under the trade names Purafect®, Purafect® OxP, Purafect® Prime, Excellase®, and Properase® from the company Genencor, under the trade name Protosol® from the company Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® from the company Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P® from the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and under the designation Proteinase K-16 from the company Kao Corp., Tokyo, Japan. The proteases from Bacillus gibsonii and Bacillus pumilus are also used with particular preference.

[0021] Examples of usable amylases are the α-amylases from Bacillus licheniformis, Bacillus amyloliquefaciens, or Bacillus stearothermophilus, as well as the further developments thereof improved for use in washing or cleaning agents. The enzyme from B. licheniformis is obtainable from the company Novozymes under the name Termamyl® and from the company Genencor under the name Purastar® ST. Further development products of this α-amylase are obtainable from the company Novozymes under the trade names Duramyl® and Termamyl® Ultra, from the company Genencor under the name Purastar® OxAm, and from the company Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The α-amylase from B. amyloliquefaciens is marketed by the company 5

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Novozymes under the name BAN®, and derived variants of the α-amylase from B. stearothermophilus under the names BSG® and Novamyl® again by the company Novozymes. To be emphasized, furthermore, for this purpose are the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948). Fusion products of all the cited molecules can also be employed. Moreover, further developments of the α-amylase from Aspergillus niger and A. oryzae available from the company Novozymes under the trade names Fungamyl® are suitable. Additional commercial products that can be used advantageously are, for example, Amylase-LT® and Stainzyme® or Stainzyme Ultra® or Stainzyme Plus®, the last also from the company Novozymes. Variants of these enzymes obtained by point mutations can also be employed according to the invention. Amylases producible according to the invention are further preferably a-amylases.

[0022] Depending on the purpose, cellulases can be present as pure enzymes, as enzyme preparations, or in the form of mixtures, in which the individual components advantageously complement each other with respect to their different performance aspects. These performance aspects include in particular the contributions of the cellulase to the primary washing performance of the agent (cleaning performance), to the secondary washing performance of the agent (antiredeposition effect or graying inhibition), to softening (effect on fabric), or to exerting a "stone washed" effect. A usable fungal cellulase preparation rich in endoglucanase (EG), or the further developments thereof are offered by the company Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, likewise obtainable from the company Novozymes, are based on the 50 kD EG and 43 kD EG, respectively, from H. insolens DSM 1800. Other usable commercial products from this company are Cellusoft®, Renozyme®, and Celluclean®. For example, the 20 kD EG from Melanocarpus, which can be obtained from the company AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, can also be used. Other commercial products from the company AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are those from Bacillus sp. CBS 670.93 and CBS 669.93, whereby the cellulase from Bacillus sp. CBS 670.93 can be obtained from the company Genencor under the trade name Puradax®. Other commercial products from the company Genencor are "Genencor detergent cellulase L" and lndiAge®Neutra. Variants of these enzymes obtained by point mutations can also be employed according to the invention.

[0023] Further, other enzymes that are grouped under the term hemicellulases can be used particularly for removing certain problem strains. These include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-cleaving enzymes, and β-glucanases. The β-glucanase obtained from Bacillus subtilis can be obtained under the name Cereflo® from the company Novozymes. Hemicellulases particularly preferable according to the invention are mannanases, which are marketed, for example, under the trade names Mannaway® by the company Novozymes or Purabrite® by the company Genencor. In the context of 6

PT031885 PCT the present invention, the pectin-cleaving enzymes likewise include enzymes with the names pectinase, pectate lyase, pectinesterase, pectin demethoxylase, pectin methoxylase, pectin methylesterase, pectase, pectin methylesterase, pectinoesterase, pectin pectylhydrolase, pectin depolymerase, endopolygalacturonase, pectolase, pectinhydrolase, pectin polygalacturonase, endopolygalacturonase, poly-a-1,4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1,4-a-galacturonidase, exopolygalacturonase, poly(galacturonate) hydrolase, exo-D-galacturonase, exo-D-galacturonanase, exopoly-D-galacturonase, exo-poly-a-galacturonosidase, exopolygalacturonosidase, or exopolygalacturanosidase. Examples of enzymes suitable for this purpose are obtainable, for example, under the names Gamanase®, Pektinex AR®, X-Pect®, or Pectaway® from the company Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1L® from the company AB Enzymes, and under the name Pyrolase® from the company Diversa Corp., San Diego, CA, USA.

[0024] Particularly preferred of all these enzymes are those that are relatively stable per se to oxidation or have been stabilized, for example, by point mutagenesis.

[0025] To increase the bleaching effect, oxidoreductases, for example, oxidases, oxygenases, catalases (which react as peroxidases at low H202 concentrations), peroxidases such as halo-, chloro-, or bromoperoxidases or lignin, glucose, or manganese peroxidases, dioxygenases, or laccases (phenol oxidases, polyphenol oxidases) can also be present in the detergents and cleaning agents. Denilite® 1 and 2 from the company Novozymes or Gluzyme® mono BG from the company Novozymes can be cited as suitable commercial products.

[0026] The agents contain the enzyme preferably in an amount of 1 x 10'8% by weight to 5% by weight of active protein, particularly of 0.001% by weight to 3% by weight, preferably of 0.01% by weight to 1.5% by weight, particularly preferably of 0.05 to 1.25% by weight, based in each case on the total weight of the detergent or cleaning agent, whereby each contained enzyme taken separately can be present in the indicated amounts, if the agent contains more than one enzyme.

[0027] Enzyme-containing detergents or cleaning agents, containing a polymeric active substance to be used according to the invention, have surfactant and water and may contain all other typical components for such agents, which do not interact in an undesirable manner with the active substance essential to the invention. A polymeric active substance defined above is preferably incorporated into detergents or cleaning agents in amounts of 0.1% by weight to 10% by weight, particularly of 0.5% by weight to 2% by weight. 7

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[0028] In a preferred embodiment, an agent employed within the scope of the use of the invention contains a synthetic anionic surfactant, particularly alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, alkyl and/or dialkyl sulfosuccinate, sulfofatty acid esters, and/or sulfofatty acid disalts, particularly in an amount in the range of 0.1% by weight to 20% by weight and particularly preferably of 2% by weight to 15% by weight, whereby the alkyl group in them preferably has 8 to 22, particularly 12 to 18 C atoms. Preferred are the derivatives of the fatty alcohols having particularly 12 to 18 C atoms and the branched-chain analogs thereof, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a typical sulfating reagent, particularly sulfur trioxide or chlorosulfonic acid, and subsequent neutralization 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 aforementioned alcohols, the 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 α-sulfo esters which are obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular the sulfonation products derived from fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 C atoms, preferably 1 to 4 C atoms, and the sulfofatty acids which result from these by formal saponification. Preferred anionic surfactants are also the salts of sulfosuccinic acid esters, which are also called alkyl sulfosuccinates or dialkyl sulfosuccinates and represent the monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and particularly ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8 to C18 fatty alcohol groups or mixtures thereof. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol group, which in itself represents a nonionic surfactant. In this case, sulfosuccinates whose fatty alcohol groups derive from ethoxylated fatty alcohols with a narrow homologue distribution are again particularly preferred. To be considered as countercations for the synthetic anionic surfactants are in particular ions of alkali metal salts such as lithium, sodium, and potassium, but also ammonium ions, whereby the N atom in the ammonium ions can also bear in sum 1 to 4 0,.4 alkyl and/or C2.4 hydroxyalkyl groups. Preferably, the synthetic anionic surfactant is selected from alkylbenzene sulfonates in which the alkyl group has 8 to 22, particularly 10 to 18 C atoms. These are typically not individual substances but cuts or mixtures. Alkali C10-13 alkylbenzene sulfonate, particularly one in which the alkyl groups are linear, is preferably employed as the sole synthetic anionic surfactant or as part of the total amount of synthetic anionic surfactant.

[0029] A further embodiment of such agents comprises the presence of a nonionic surfactant, selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular fatty alkyl 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 of 2% by weight to 25% by weight. 8

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[0030] Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and/or propoxylates, of saturated or singly to multiply unsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The average degree of alkoxylation of the alcohols in this case is usually between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the appropriate alkylene oxides. The derivatives of the fatty alcohols in particular are suitable, although their branched-chain isomers, in particular so-called oxo alcohols, may be used for preparing usable alkoxylates. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols having linear, in particular dodecyl, tetradecyl, hexadecyl, or octadecyl groups and mixtures thereof are usable. In addition, appropriate alkoxylation products of alkylamines, vicinal diols, and carboxylic acid amides which correspond to the named alcohols with regard to the alkyl portion are also usable. Moreover, the ethylene oxide and/or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides are suitable. So-called alkyl polyglycosides which are suitable for incorporation into the agents are compounds of the general formula (G)n-OR12, in which R12 denotes an alkyl or alkenyl group having 8 to 22 C atoms, G a glycose unit, and n a number between 1 and 10. The glycoside component (G)n refers to oligomers or polymers of naturally occurring aldose or ketose monomers, which include in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose, and lyxose. The oligomers made up of such glycosidically linked monomers are characterized not only by the type but also by the number of sugars they contain, the so-called degree of oligomerization. The degree of oligomerization n generally assumes fractional numbers as values to be analytically determined; it has values between 1 and 10, and for the preferably used glycosides, a value less than 1.5, in particular between 1.2 and 1.4. Glucose is a preferred monomer structural unit because it is readily available. The alkyl or alkenyl portion R12 of the glycosides preferably likewise comes from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although the branched-chain isomers thereof, in particular so-called oxo alcohols, may also be used for preparing usable glycosides. In particular the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl, or octadecyl groups and mixtures thereof are therefore usable. Particularly preferred alkyl glycosides contain a coconut fatty alkyl group, i.e., mixtures with substantially R12 = dodecyl and R12 = tetradecyl.

[0031] Agents, containing an active substance used according to the invention, preferably contain the nonionic surfactant in amounts of 1% by weight to 30% by weight, particularly of 1% by weight to 25% by weight.

[0032] Soaps are appropriate as further optional surfactant-type ingredients, whereby saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, or stearic acid, and soaps derived from natural fatty acid mixtures, for example, coconut, palm kernel, or tallow fatty 9

PT031885 PCT acids are suitable. Preferred in particular are soap mixtures that are made up of 50% by weight to 100% by weight of saturated C12-C18 fatty acid soaps and 50% by weight of oleic acid soap. Soap is contained preferably in amounts of 0.1% by weight to 10% by weight.

[0033] If desired, the agents can also contain betaines and/or cationic surfactants, which, if present, are used preferably in amounts of 0.5% by weight to 7% by weight.

[0034] In a further embodiment, the agent contains water-soluble and/or optionally water-insoluble builders as well, selected in particular from alkali aluminosilicate, crystalline alkali silicate having a modulus greater than 1, monomeric polycarboxylate, polymeric polycarboxylate, and mixtures thereof, particularly in amounts of 0.5% by weight to 10% by weight.

[0035] The agent preferably contains 1% by weight to 10% by weight of a water-soluble organic builder. Water-soluble organic builder substances include in particular those from the class of polycarboxylic acids, in particular citric acid and sugar acids, as well as polymeric carboxylic acids and polycarboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids, and mixed polymers thereof, which can also contain, polymerized into them, small proportions of polymerizable substances having no carboxylic acid functionality. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is in general between 5000 g/mol and 200,000 g/mol; that of the copolymers is between 2000 g/mol and 200,000 g/mol, preferably 50,000 g/mol to 120,000 g/mol, based on free acid. An especially preferred acrylic acid/maleic acid copolymer has a relative molecular mass of 50,000 g/mol to 100,000 g/mol. 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, the acid fraction of which amounts to at least 50% by weight. Terpolymers containing as monomers two carboxylic acids and/or the salts thereof and, as a third monomer, vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate may also be used as water-soluble organic builder substances. The first acidic monomer or the salt thereof is derived from a monoethylenically unsaturated C3-C8 carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or the salt thereof may be a derivative of a C4-C8 dicarboxylic acid, maleic acid being particularly preferred. The third monomer unit in this case is formed by vinyl alcohol and/or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example, of CrC4 carboxylic acids, with vinyl alcohol, are especially preferred. Preferred terpolymers in this case contain 60% by weight to 95% by weight, particularly 70% by weight to 90% by weight of (meth)acrylic acid and/or (meth)acrylate, especially preferably acrylic acid and/or acrylate, and maleic acid and/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. Very especially preferred in this case are terpolymers in which the weight ratio of (meth)acrylic acid and/or (meth)acrylate to maleic acid 10

PT031885 PCT and/or maleate is between 1:1 and 4:1, preferably between 2:1 and 3:1, and particularly 2:1 and 2.5:1. In this case, both the amounts and the weight ratios are based on the acids. The second acidic monomer or salt thereof can also be a derivative of an allyl sulfonic acid, which is substituted in the 2-position with an alkyl group, preferably with a CrC4 alkyl group, or an aromatic group, derived preferably from benzene or benzene derivatives. Preferred terpolymers in this case contain 40% by weight to 60% by weight, particularly 45 to 55% by weight of (meth)acrylic acid and/or (meth)acrylate, especially preferably acrylic acid and/or acrylate, 10% by weight to 30% by weight, preferably 15% by weight to 25% by weight of methallyl sulfonic acid and/or methallyl sulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate. Said carbohydrate in this case can be, for example, a mono-, di-, oligo-, or polysaccharide, mono-, di-, or oligosaccharides being preferred and sucrose being particularly preferred. Predetermined breaking points, which are responsible for the good biodegradability of the polymer, are presumably incorporated into the polymer by the use of the third monomer. These terpolymers generally have a relative molecular mass between 1000 g/mol and 200,000 g/mol, preferably between 2000 g/mol and 50,000 g/mol, and particularly between 3000 g/mol and 10,000 g/mol. They can be used in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions, particularly for the production of liquid agents. All cited polycarboxylic acids are generally used in the form of their water-soluble salts, in particular their alkali salts.

[0036] Crystalline or amorphous alkali aluminosilicates in particular in amounts of preferably not greater than 6% by weight, particularly of 0.5% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. Among these, the crystalline aluminosilicates in detergent quality, particularly zeolite NaA and optionally NaX, are preferred. Amounts close to the cited upper limit are preferably used in solid, particulate agents. Suitable aluminosilicates have in particular no particles with a particle size greater than 30 pm and preferably consist of at least 80% by weight of particles with a size of less than 10 pm. The calcium binding capacity thereof, which may be determined according to the information in German patent document DE 24 12 837, is in the range of 100 to 200 mg of CaO per gram. Suitable substitutes or partial substitutes for the named aluminosilicate are crystalline alkali silicates, which may be present alone or in a mixture with amorphous silicates. Alkali silicates that can be used as builders in the agents preferably have a molar ratio of alkali oxide to Si02 of less than 0.95, particularly from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are sodium silicates, particularly amorphous sodium silicates, with a molar ratio of Na20:Si02 of 1:2 to 1:2.8. Such amorphous alkali silicates are commercially available under the name Portil®, for example. Within the scope of production, those having an Na20:Si02 molar ratio of 1:1.9 to 1:2.8 are preferably added as a solid and not in the form of a solution. Crystalline phyllosilicates of the general formula Na2Six02x+1 yH20, in which the so-called modulus x is a number from 1.9 to 4 and y is a number from 0 to 20, with preferred values for x being 2, 3, or 4, are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates. Crystalline phyllosilicates, 11

PT031885 PCT which are included in this general formula, are described, for example, in the European patent application EP 0 164 514. Preferred crystalline phyllosilicates are those in which x assumes the values 2 or 3 in the cited general formula. In particular both β- and δ-sodium disilicates (Na2Si205 yH20) are preferred. Practically anhydrous crystalline alkali silicates of the aforementioned general formula, in which x denotes a number from 1.9 to 2.1, which silicates are prepared from amorphous alkali silicates, can also be used in agents containing an active substance to be used according to the invention. In another preferred embodiment of the agents, a crystalline sodium phyllosilicate with a modulus of 2 to 3 is used, such as can be prepared from sand and soda. Crystalline sodium silicates having a modulus in the range of 1.9 to 3.5 are used in another preferred embodiment of detergents, containing an active substance used according to the invention.

[0037] In addition, the agents may contain other components customary in detergent or cleaning agents. These optional components include in particular other enzyme stabilizers, complexing agents for heavy metals, for example, aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids, and/or aminopolyphosphonic acids, foam inhibitors, for example, organopolysiloxanes or paraffins, nonqueous solvents, and optical brighteners, for example, stilbene disulfonic acid derivatives. Agents which contain an active substance used according to the invention preferably contain up to 1% by weight, particularly 0.01% by weight to 0.5% by weight of optical brighteners, in particular compounds from the class of substituted 4,4'-bis(2,4,6-triamino-s-triazinyl)stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylene phosphonic acids and salts thereof, and up to 2% by weight, in particular 0.1% by weight to 1% by weight of foam inhibitors, whereby the weight proportions given here and elsewhere in the description in each case refer to the entire agent.

[0038] Solvents, which may be used in addition to water, are preferably those that are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, for example, ethylene glycol and propylene glycol, and the ethers derivable from the named compound classes. Agents with the polymeric active substance used according to the invention preferably contain 10% by weight to 90% by weight, particularly 60% by weight to 80% by weight of water.

[0039] Customary enzyme stabilizers, optionally present in addition, include amino alcohols, for example, mono-, di-, and triethanolamine and propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali borates, boric acid/carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example, a Ca/formic acid combination, magnesium salts, and/or sulfur-containing reducing agents. 12

PT031885 PCT

[0040] Suitable foam inhibitors include long-chain soaps, in particular behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes, and mixtures thereof, which may contain moreover microfine, optionally silanized or otherwise hydrophobized silicic acid.

[0041] The known polyester-active soil-release polymers that may be used in addition to the active substances essential to the invention include copolyesters of dicarboxylic acids, for example, adipic acid, phthalic acid, or terephthalic acid, and diols, for example, ethylene glycol or propylene glycol, and polydiols, for example, polyethylene glycol or polypropylene glycol. The preferably used soil-release polyesters include compounds that are obtainable formally by esterification of two monomer portions, whereby the first monomer is a dicarboxylic acid HOOC-Ph-COOH, and the second monomer a diol HO-(CHR11-)nOH, which may also be present as a polymeric diol H-(0-CHR11-)a)b0H. Ph therein denotes an 0-, m-, or p-phenylene group which may bear 1 to 4 substituents selected from alkyl groups having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups, and mixtures thereof, R11 denotes hydrogen, an alkyl group having 1 to 22 C atoms, and mixtures thereof, a denotes a number from 2 to 6, and b a number from 1 to 300. The polyesters obtainable therefrom preferably contain both monomer diol units -0-(CHR11-)a0- and polymer diol units -0-(CHR11-)a)b0-. The molar ratio of monomer diol units to polymer diol units is preferably 100:1 to 1:100, particularly 10:1 to 1:10. The degree of polymerization b in the polymer diol units is preferably in the range of 4 to 200, in particular 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil-release polyesters is in the range of 250 to 100,000, in particular 500 to 50,000. The acid forming the basis for the Ph group is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid, and sulfoterephthalic acid, and mixtures thereof. Provided the acid groups thereof are not part of the ester bonds in the polymer, they are preferably present in the form of a salt, particularly an alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small quantities, in particular no more than 10 mol %, based on the content of Ph having the meaning stated above, of other acids which have at least two carboxyl groups may be contained in the soil-release 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-(CHR11-)aOH include those in which R11 is hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R11 is selected from among hydrogen and alkyl groups having 1 to 10, in particular 1 to 3 C atoms. Of the last-mentioned diols, those of formula HO-CH2-CHR11-OH, in which R11 has the aforementioned 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. Among the polymeric diols, polyethylene glycol having an average molar 13

PT031885 PCT mass in the range of 1000 g/mol to 6000 g/mol is particularly preferred. If desired, these polyesters may also be closed by end groups, whereby alkyl groups having 1 to 22 C atoms and esters of monocarboxylic acids are suitable end groups.

[0042] Liquid agents are generally prepared by simple mixing of the ingredients, which can be added to the substance or as a solution in an automatic mixer.

Examples

Example 1: Determination of the aggregation parameter Xag via static surface tension [0043] The surface tension y of an aqueous solution, adjusted to pH 8.5, of 0.2 g/L of linear alkylbenzene sulfonate (LAS; Disponil® LDBS 55) was measured at 25°C using a TE3 ring/plate tensiometer from Lauda. The measurement was repeated with solutions which were otherwise identical but contained in addition 0.2 g/L of the polymer to be tested in each case. The aggregation parameter Xag was determined by subtracting the measured value for the system without polymer from that for the system with polymer.

Xag = Yi (surfactant + polymer) - y2 (surfactant) [0044] Tested were an N-vinylpyrrolidone homopolymer (PVP), an N-vinylcaprolactam homopolymer (PVCap), a copolymer of these two monomers (P(VP-co-VCap)) (average molecular weight in each case 10,000 g/mol), and a vinylpyrrolidone/vinylsuccinimide copolymer (P(VP-co-VSuc); average molecular weight 31,000 g/mol), and a vinylpyrrolidone/vinylpiperidone copolymer (P(VP-co-VPip); average molecular weight 18,000 g/mol). The aggregation parameters given in the following Table 1 were determined:

Table 1: Aggregation parameters of the surfactant/polymer systems

System Xag LAS + PVP 4.7 LAS + PVCap 6.6 LAS + P(VP-co-VCap) 6.4 P(VP-co-VSuc) 5.0 P(VP-co-VPip) 5.5 [0045] The surface tension in the presence and absence of polymer was also measured in a detergent frame formulation containing alkylbenzene sulfonate. Here as well, the interaction of the polymer was clearly discernible. This demonstrates that the formation of the aggregate with 14

PT031885 PCT cleaning activity is not a phenomenon limited to the isolated surfactant-polymer system. Rather, it is an application-relevant effect which brings about an improved performance in the cleaning application.

Example 2: Determination of the aggregation parameter Xag via dynamic interfacial tension [0046] The dynamic interfacial tension γ of an aqueous solution, adjusted to pH 8.5, of 0.2 g/L of linear alkylbenzene sulfonate (LAS; Disponil® LDBS 55) was measured with respect to isopropyl myristate at 25°C using a TVT2 drop volume tensiometer from Lauda. The measurement was repeated with solutions which were otherwise identical but contained in addition 0.2 g/L of the polymer to be tested in each case. The measurements were each made after 1 minute.

[0047] Tested were an N-vinylpyrrolidone homopolymer (PVP), an N-vinylcaprolactam homopolymer (PVCap), and a copolymer of these two monomers (P(VP-co-VCap) (average molecular weight in each case 30,000 g/mol). Because the interfacial tension generally has appreciably lower values than the surface tension, a normalization factor of 3 was used so that the values of the aggregation parameter determined from the surface tension measurements could be compared with the values determined from the interfacial tension measurements:

Xag = 3 [Ylinterface (Surfactant + polymer) - Y2,nterface (Surfactant)] [0048] The aggregation parameters given in the following Table 2 were determined:

Table 2: Aggregation parameters of the surfactant/polymer systems

System Xag LAS + PVP 4.5 LAS + PVCap 6.0 LAS + P(VP-co-VCap) 6.0

Example 3 [0049] The following substances were tested for their stabilizing effect: an N-vinylpyrrolidone/N,N-dimethylacrylamide copolymer (P(VP-co-DMA), average molecular weight 15,000 g/mol); a vinylpyrrolidone/vinylpiperidone copolymer (P(VP-co-VPip), average molecular weight 18,000 g/mol); an N-vinylpyrrolidone/vinylsuccinimide copolymer (P(VP-co-VSuc), average molecular weight 31,000 g/mol); an N-vinylpyrrolidone/N-vinylcaprolactam copolymer (P(VP-co-VCap), average molecular weight 30,000 g/mol); and for comparison, a sodium 15 PT031885 PCT polystyrene sulfonate (PSS) and the sodium salt of a sulfonate-terminated acrylic acid polymer (Acusol® 445N).

[0050] To this end, a protease, comprising an amino acid sequence according to SEQ ID NO:2 of the international patent application WO 2012/080201 A2 (Glu at position 99 (99E)) in a concentration of 0.04 mg/ml_ (based on the active enzyme) was incubated in a solution of 1% of the corresponding polymer and 1% of the linear C10-13 alkylbenzene sulfonate Na salt in 0.1 M Tris-buffer with pH 8.0 at 50°C, and the activity was checked at regular intervals by measurement in the AAPF test for protease activity. The activities declining over time were used by taking the logarithm and assuming pseudo-1st-order degradation kinetics to determine the protease half-lives. These were then related to the half-life standardized as 1 in a solution with an otherwise identical composition but without polymer.

[0051] The following results were achieved:

Table 3: Half-lives with use of polymer

Polymer Half-life P(VP-co-DMA) 2.3 P(VP-co-VPip) 3.0 P(VP-co-VSuc) 3.8 P(VP-co-VCap) 4.4 PSS 1.1 Acusol® 445N 0.7 [0052] The results show that the polymers used according to the invention produce an increase in the stability to 2.3 to 4.4-fold half-life, whereas no stabilization can be achieved with other polymers.

Example 4: Washing tests

Table 4: Detergent compositions (quantities given in % by weight) A B C D E F G H C9_13 alkylbenzene sulfonate, Na salt 9 10 6 7 5 15 15 9 C12-18 alcohol with 7 EO 8 9 6 7 5 6 11 10 C12-14 fatty alcohol sulfate with 2 EO - - 8 7 10 2 2 5 C12_18 fatty acid, Na salt 4 3 3 3 4 2 4 7 Citric acid 2 3 3 2 2 2 2 3 Sodium hydroxide, 50% 3 3 2 3 3 3 3 4 16

PT031885 PCT

Boric acid 1 1 1 1 1 1 1 1 Purafect Prime® 4000 L 2 4 0.7 0.2 0.7 1.2 2.2 3 Stainzyme® 12.0 L 1 0.5 0.25 0.125 1 0.5 0.5 0.5 Biotouch® NCD 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Perfume 1 0.5 0.5 1 1 1 1 1 Propanediol - - - - - 5 5 - Ethanol 1.5 1.5 1.5 1.5 1.5 1.5 1.5 5 PVA/Maleic acid copolymer 0.1 - 0.1 - - - - - Optical brightener - 0.1 - 0.1 0.2 0.2 0.2 0.2 Opacifier 0.2 - - - - - - - Phosphonic acid, Na salt 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Polymer essential to the invention 2 2 2 2 2 2 2 2 Water To 100 [0053] Domestic washing machines (Miele W 1514) were loaded with 3.5 kg of clean accompanying laundry and the test textiles, made of cotton and soil ballast and provided with standardized stains given in Table 5. 75 ml_ of the listed detergent C with P(VP-co-VCap) with an average molecular weight of 30,000 g/mol was dosed in and washing was carried out at 40°C. After drying by hanging and pressing of the test textiles, the whiteness thereof was determined by spectrophotometry (Minolta CR200-1). The differences in the reflectance values (Rd) from a detergent with an otherwise identical composition but without the polymer essential to the invention are given in the following Table 5 as averages of 5 determinations, as well as the errors for the 5-fold determination (LSD).

Table 5: Washing results, differences in reflectance values in %

Rd LSD Blueberry juice 2.6 1.7 Red wine-1 1.8 1.3 Salad dressing/natural black 2.2 1.5 Tea-1 2.4 1.1 Tea-2 1.2 0.7 Tea-3 1.3 0.8 Coffee 1.2 0.7 Black currant juice 3.1 2.3 Blackberry juice-1 4.9 1.3 Blackberry juice -2 4.5 1.8 Red wine-2 2.9 1.1 Curry 1.3 0.4 17

PT031885 PCT

Blood 3.4 2.8 Chocolate milk/rust 6.9 4 Cocoa 3.1 2.4 Chocolate pudding 2.7 1.4 Chocolate cream 3.6 2.3 Porridge 2.5 1.9 Bilberry juice 6.3 2.4 Chocolate mousse 5.1 3.7 Cherry juice 2.8 0.7 Assam-Ceylon tea 2.1 0.8 [0054] The detergent with an active substance to be used according to the invention exhibited a considerably better washing performance than the agent with the otherwise-identical composition but without the said substance. 18

Claims (19)

1. Use of polymers obtained by polymerizing N-vinylpyrrolidone with a comonomer, selected from the group comprising N-vinylcaprolactam, N-vinylpiperidone, N-vinylsuccinimide, N-vinylglutarimide, N-vinylacetamide, N-alkyl-N-vinylacetamide, N-vinylformamide, N-alkyl-N-vinylformamide, dialkyl acrylamide, and mixtures of at least two of said compounds - to stabilize enzymes and/or - to slow enzyme degradation and/or - to prevent enzyme degradation in liquid water- and surfactant-containing detergents or cleaning agents.

2. The use according to claim 1, characterized in that the polymer has an aggregation parameter Xag with Xag > 4 mN/m.

3. The use according to claim 2 wherein Xag is in the range of 5 mN/m to 8 mN/m.

4. The use according to any one of claims 1 to 3, characterized in that the polymer has an average molecular weight in the range of 1000 g/mol to 500,000 g/mol.

5. The use according to claim 4 wherein the average molecular weight is in the range of 1100 g/mol to 150,000 g/mol.

6. The use according to one of claims 1 to 5, characterized in that the polymer is made up, apart from units originating from the monomer N-vinylpyrrolidone, of units originating from one other monomer, and has the two mentioned units in the weight ratio of 99:1 to 1:99.

7. The use according to claim 6 wherein the two mentioned units are in the weight ratio of 97:3 to 70:30.

8. The use according to one of claims 1 to 7, characterized in that the agent contains 0.1% by weight to 10% by weight of the polymer.

9. The use according to claim 8 wherein the agent contains 0.5% by weight to 2% by weight of the polymer.

10. The use according to one of claims 1 to 9, characterized in that the enzyme is selected from protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-cleaving enzyme, tannase, xylanase, xanthanase, β-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreductase, and mixtures thereof.

11. The use according to claim 10 wherein the enzyme is selected from protease, amylase, and lipase and mixtures thereof.

12. The use according to one of claims 1 to 11, characterized in that the agent contains the Q enzyme in an amount of 1 x 10' % by weight to 5% by weight of active protein, whereby each contained enzyme taken separately can be present in the indicated amounts, if the agent contains more than one enzyme.

13. The use according to claim 12 wherein the agent contains the enzyme in an amount of 0.001% by weight to 3% by weight of active protein, whereby each contained enzyme taken separately can be present in the indicated amounts, if the agent contains more than one enzyme.

14. The use according to one of claims 1 to 13, characterized in that the agent contains 0.1% by weight to 20% by weight of synthetic anionic surfactant.

15. The use according to claim 14 wherein the agent contains 2% by weight to 15% by weight of synthetic anionic surfactant.

16. The use according to claim 14 or claim 15, characterized in that alkali C10-13 alkylbenzene sulfonate is employed as the sole synthetic anionic surfactant or as part of the total amount of synthetic anionic surfactant.

17. The use according to claim 16 wherein the alkali C10-13 alkylbenzene sulfonate, is one in which the alkyl groups are linear,

18. The use according to one of claims 1 to 17, characterized in that the agent contains 10% by weight to 90% by weight of water.

19. The use according to claim 18, characterized in that the agent contains 60% by weight to 80% by weight of water. Henkel AG and Co. KGaA Fraunhofer Gesellschaft zur Forderung der angewandten Forschung e.V. Patent Attorneys for the Applicant/Nominated Person SPRUSON & FERGUSON