EP2918664A2 - Washing or cleaning agent comprising hydrolytically active enzyme and steroid acids - Google Patents

Abstract

Detergents and cleaners containing at least one hydrolytic enzyme and - At least one steroid acid of the formula (I) or its salt wherein R 1, R 2 and R 3 independently represent a hydrogen atom or a hydroxyl group, R 4 is a hydroxyl group, a group * -NH-CH 2 -COOH or a group * -NH-CH 2 -CH 2 -SO 3 H, have an increased cleaning performance, especially at temperatures between 10 ° C and 50 ° C on.

Description

The present invention relates to the field of cleaning surfaces, in particular textiles. Specifically, the invention is directed to the removal of enzyme-sensitive soils.

The use of enzymes in detergents and cleaners is well established in the art. They serve to extend the range of services of the funds concerned according to their specific activities. These include in particular enzymes such as proteases, amylases, lipases and cellulases. The first three hydrolyze proteins, starches and fats and thus contribute directly to soil removal. Hydrolytic enzymes according to the invention are enzymes which catalyze the hydrolytic bond cleavage of the enzyme substrate.

The enzymes that have long been established and are contained in virtually all modern, high-performance detergents and cleaners are proteases, and in particular serine proteases, which include the subtilases. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are attributed to the serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases, that is, they hydrolyze any acid amide linkages that are internal to peptides or proteins.

A disadvantage of these enzymes used in detergents and cleaning agents, in particular proteases, from the prior art is that they are especially at low temperatures, for example between 10 ° C and 40 ° C, in particular between 10 ° C and 30 ° C or even between 10 ° C and 25 ° C, an improvement in hydrolytic activity, in particular proteolytic activity, and therefore in particular in detergents and dishwashing detergents in this temperature range show no optimal cleaning performance.

It has surprisingly been found that the addition of certain steroid acids considerably improves the cleaning performance of detergents and cleaners which contain hydrolytic enzymes, in particular proteases and / or amylases, in particular at comparatively low temperatures, in particular between 10 ° C. and 50 ° C. 10 ° C and 40 ° C and preferably between 10 ° C and 30 ° C and 10 ° C and 25 ° C.

The present invention is therefore based on the object to improve the cleaning performance (washing power) of detergents or cleaning agents, in particular with regard to soiling, which are sensitive to degradation by hydrolytic enzymes, in particular by proteases. Another object of the invention is to improve the cleaning performance of hydrolytic enzymes, in particular proteases, in detergents or cleaners or the wash liquor formed by the washing or cleaning agents, in particular with regard to soiling, which are sensitive to degradation by hydrolytic enzymes, in particular by proteases and / or amylases, and in particular in a temperature range between 10 ° C and 50 ° C, between 10 ° C and 40 ° C and preferably between 10 ° C and 30 ° C and 10 ° C and 25 ° C.

The object has been achieved by the use of at least one hydrolytic enzyme in combination with at least one special steroid acid.

• mindestens ein hydrolytisches Enzym und
• mindestens eine Steroidsäure der Formel (I) oder deren Salz
  
  worin
  R¹, R² und R³ unabhängig voneinander für ein Wasserstoffatom oder eine Hydroxylgruppe stehen,
  R⁴ für eine Hydroxylgruppe, eine Gruppe *-NH-CH₂-COOH oder eine Gruppe *-NH-CH₂-CH₂-SO₃H steht.

A first subject of the invention is a washing and cleaning agent containing

• at least one hydrolytic enzyme and
• at least one steroid acid of the formula (I) or its salt
  
  wherein
  R ¹ , R ² and R ³ independently represent a hydrogen atom or a hydroxyl group,
  R ^{4 is} a hydroxyl group, a group * -NH-CH ₂ -COOH or a group * -NH-CH ₂ -CH ₂ -SO ₃ H.

An * next to a bond of a chemical group means that it is a free valence that binds, for example, to the main body of the corresponding formula.

The washing and cleaning agent according to the invention is preferably suitable for textiles.

Preferred hydrolytic enzymes include in particular proteases, amylases, (in particular α-amylases), cellulases, lipases, hemicellulases (in particular pectinases, mannanases, β-glucanases), and mixtures thereof. The hydrolytic enzyme is particularly preferably selected from at least one protease, amylase or lipase and also mixtures thereof and very particularly preferably from at least one protease and / or at least one amylase. Most preferably, the agent of the invention contains as hydrolytic enzyme at least one protease and at least one amylase. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.

A protease is an enzyme that cleaves peptide bonds by hydrolysis. Each of the enzymes from class EC 3.4 is included according to the invention (comprising each of the thirteen subclasses below). The EC number corresponds to the Enzyme Nomenclature 1992, NC-IUBMB, Academic Press, San Diego, California, included supplements 1 through 5 , published in Eur. J. Biochem. 1994, 223, 1-5 ; Eur. J. Biochem. 1995, 232, 1-6 ; Eur. J. Biochem. 1996, 237, 1-5 ; Eur. J. Biochem. 1997, 250, 1-6 ; and Eur. J. Biochem. 1999, 264, 610-650 ,

Subtilase names a subgroup of serine proteases. The serine proteases or serine peptidases are a subset of the proteases that have serine in the active site of the enzyme that forms a covalent adduct with the substrate. Furthermore, the subtilases (and serine proteases) are characterized by having two more amino acid residues in the active site besides said serine with histidine and aspartame. The subtilases can be divided into 6 subclasses, namely the subtilisin family, the thermitase family, the proteinase K family, the family of lantibiotic peptidases, the kexin family, and the pyrolysin family. The proteases preferably contained as part of the compositions according to the invention are endopeptidases (EC 3.4.21).

"Protease activity" is present according to the invention if the enzyme has proteolytic activity (EC 3.4). Various types of protease activity are known: the three main types are: trypsin-like, with cleavage of the amide substrate following the amino acids Arg or Lys at P1; Chymotrypsin-like, with cleavage after one of the hydrophobic amino acids at P1; and elastase-like, wherein cleavage of the amide substrate after Ala occurs at P1.

The protease activity can after the in Surfactants, Vol. 7 (1970), pp. 125-132 method described. It is accordingly stated in PE (protease units). The protease activity of an enzyme can be determined according to customary standard methods, in particular using BSA as substrate (bovine albumin) and / or with the AAPF method.

Among the proteases, those of the subtilisin type are preferable. Examples thereof 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 subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsværd, Denmark. The subtilisins 147 and 309 are sold under the trade name Esperase®, or Savinase® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP® protease variants derived. Further useful proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, sold under the trade name Protosol® by Advanced Biochemicals Ltd., Thane, India sold under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P® by Amano Pharmaceuticals Ltd., Nagoya, Japan, and the product called Proteinase K-16 of enzymes available from Kao Corp., Tokyo, Japan. Particular preference is also given to using the proteases from Bacillus gibsonii and Bacillus pumilus, which are disclosed in the international patent applications WO2008 / 086916 and WO2007 / 131656 ,

The agents according to the invention preferably contain at least one α-amylase as the hydrolytic enzyme. α-Amylases (EC 3.2.1.1) hydrolyze internal α-1,4-glycosidic bonds of starch and starch-like polymers as an enzyme. This α-amylase activity, for example, the applications WO 97/03160 A1 and GB 1296839 measured in KNU (Kilo Novo Units). Here, 1 KNU stands for the amount of enzyme which hydrolyses 5.25 g of starch (available from Merck, Darmstadt, Germany) per hour at 37 ° C., pH 5.6 and in the presence of 0.0043 M calcium ions. An alternative activity determination method is the so-called DNS method, which is described, for example, in the application WO 02/10356 A2 is described. Thereafter, the oligosaccharides, disaccharides and glucose units released by the enzyme in the hydrolysis of starch are detected by oxidation of the reducing ends with dinitrosalic acid (DNS). The activity is obtained in μmol reducing sugars (in terms of maltose) per min and ml; This results in activity values in TAU. The same enzyme can be determined by various methods, whereby the respective conversion factors can vary depending on the enzyme and must therefore be determined by means of a standard. As an approximation one can calculate that 1 KNU corresponds to approx. 50 TAU. Another activity determination method is the measurement using the Quick-Start ^® test kit from Abbott, Abott Park, Illinois, USA.

The preferred use according to the invention of the agents according to the invention is the cleaning of textiles. Because detergents and cleaners for textiles predominantly have alkaline pH values, in particular α-amylases which are active in the alkaline medium are used for this purpose. Such are produced and secreted by microorganisms, ie fungi or bacteria, especially those of the genera Aspergillus and Bacillus. Based on these natural enzymes, there remains an almost unmanageable wealth of variants that have been derived by mutagenesis and have specific advantages depending on the field of application.

Examples of amylases which can be used according to the invention are the .alpha.-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and their derivatives Use in detergents or cleaning agents improved developments. The B. licheniformis enzyme is available from Novozymes under the name Termamyl® and from Genencor under the name Purastar®ST. Further development products of this α-amylase are available from Novozymes under the trade names Duramyl® and Termamyl®ultra, from Genencor under the name Purastar®OxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. B. amyloliquefaciens α-amylase is sold by Novozymes under the name BAN®, and variants derived from the B. stearothermophilus α-amylase under the names BSG® and Novamyl®, also from Novozymes. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). In addition, the amylolytic enzymes belonging to the sequence space of α-amylases which can be used in the international patent application WO 03/002711 A2 is defined, and the ones in the application WO 03/054177 A2 to be discribed. Likewise, fusion products of said molecules can be used. In addition, the further developments of the α-amylase from Aspergillus niger and A. oryzae available under the trade names Fungamyl® from Novozymes are suitable.

Further preferably usable commercial products are selected from Amylase-LT®, Stainzyme®, Stainzyme ultra®, Stainzyme plus® (the latter also from Novozymes) or mixtures thereof. Also variants of these enzymes obtainable by point mutations can be used according to the invention.

Very particular preference is given to an agent according to the invention which contains as hydrolytic enzyme at least one serine protease as protease and at least one α-amylase as amylase.

The compositions of the invention may contain as hydrolytic enzyme preferably at least one lipase. A lipase contained in the washing and cleaning agents according to the invention has a lipolytic activity, that is, it is capable of hydrolysis (lipolysis) of lipids such as glycerides or cholesterol esters. This lipase activity is determined in the usual way, preferably as described in US Pat Bruno Stellmach, "Methods of Determination Enzymes for Pharmacy, Food Chemistry, Engineering, Biochemistry, Biology, Medicine" (Steinkopff Verlag Darmstadt, 1988, p. 172 et seq ). In this case, lipase-containing samples are added to an olive oil emulsion in emulsifier-containing water and incubated at 30 ° C and pH 9.0. This fatty acids are released. These are done with an autotitrator over 20 min. titrated continuously with 0.01 N sodium hydroxide solution so that the pH remains constant ("pH-stat titration"). Based on the sodium hydroxide consumption, the determination of the lipase activity takes place by reference to a reference lipase sample. Another suitable method for measuring lipase activity is the release of a dye from a suitable pNP-labeled substrate. Lipase enzymes preferred according to the invention are selected from at least one enzyme of the group which is formed from triacylglycerol lipase (EC 3.1.1.3) and lipoprotein lipase (EC 3.1.1.34) and monoglyceride lipase (EC 3.1.1.23).

Examples of lipases or cutinases which can be used according to the invention, which are contained in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors, are the lipases which are originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold for example by the company Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases which are likewise useful are sold by Amano under the names Lipase CE®, Lipase P®, Lipase B® or Lipase CES®, Lipase AKG®, Bacillis sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML®. By Genencor, for example, the lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Further important commercial products are the preparations M1 Lipase.RTM. And Lipomax.RTM., Which were originally sold by Gist-Brocades, and the enzymes marketed by Meito Sangyo KK, Japan, under the name Lipase MY-30®, Lipase OF® and Lipase PL® to mention also the product Lumafast® from the company Genencor.

A most preferred lipase is commercially available under the trade name Lipex® from the company Novozymes (Denmark) and can advantageously be used in the cleaning compositions according to the invention. Particularly preferred here is the lipase Lipex® 100 L (ex Novozymes A / S, Denmark).

Further, as the hydrolytic enzyme may be used those which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable enzymes for this purpose are, for example, available under the names Gamanase® and Pektinex AR® from Novozymes, under the name Rohapec® B1L from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA , The β-glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes. Hemicellulases which are particularly preferred according to the invention are mannanases which are sold, for example, under the trade names Mannaway® by the company Novozymes or Purabrite® by the company Genencor.

Furthermore, within the scope of the invention, the enzymes may be formulated together with accompanying substances, for example from the fermentation or with stabilizers.

The agent according to the invention preferably contains hydrolytic enzymes, based on the weight of the agent, in a total amount of 1 × 10 ^-8 to 5 percent by weight, based on active protein. Preferred are, based on the weight of the agent, the enzymes in a total amount of 0.001 to 5 wt .-%, more preferably from 0.01 to 5 wt .-%, even more preferably from 0.05 to 4 wt .-% and especially preferably from 0.075 to 3.5 wt .-% in these agents.

The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ).

In addition to at least one hydrolytic enzyme, the agent according to the invention additionally necessarily contains at least one steroid acid of the above formula (I).

Advantageously, the agent according to the invention preferably contains said steroid acid or its salt in a total amount of from 0.1 to 5.0% by weight, particularly preferably from 1.0 to 3.0% by weight, in each case based on the weight of the composition.

It has been found to be particularly suitable according to the invention if the steroid acid according to formula (I) is selected from one or more compounds according to formula (I) which, as a possible combination of R ¹ , R ² and R ^{3, has} one of the following combinations: R ¹ R ² R ³ OH H OH OH H H H H OH H H H H OH OH H OH H

Furthermore, compounds of the formula (I) are particularly preferred in which the radical R ^{4 is} a group * -NH-CH ₂ -CH ₂ -SO ₃ H.

It is preferred according to the invention if said steroidal acids are contained in salt form in the agent according to the invention. The said steroid acid is - as is customary - deprotonated by neutralization of the carboxyl group or the sulfonic acid group of the structural unit * -C (= O) -R ^{4 of} the formula (I) with an alkalizing agent and converted into the salt form. When According to the invention, preferred alkalizing agents are the substances mentioned below as preferred alkalizing agents according to the invention ( vide infra ). In the salt form the radicals R ⁴ are of formula (I) * -O ^-, a group * -NH-CH ₂ -COO or a group * -NH-CH ₂ -CH ₂ -SO ₃ ^-, where in each case a 1 / n equivalent of a counterion M ^{n +} with n = number of charges compensating the negative charge. Corresponding to the alkalizing agent sodium, potassium, magnesium or alkanolammonium are particularly preferred as counterions.

worin
R¹, R² und R³ unabhängig voneinander für ein Wasserstoffatom oder eine Hydroxylgruppe stehen,
R⁴ für eine Hydroxylgruppe, eine Gruppe *-NH-CH₂-COOH oder eine Gruppe *-NH-CH₂-CH₂-SO₃H steht.The compounds of the formula (I) can be present in all stereoisomeric forms, in particular in all enantiomeric forms. However, the steroid acids used in the agents according to the invention are preferably based on the base body of the 5β-cholan. With regard to stereocenters, therefore, the steroid acid according to formula (I) is preferably selected from at least one compound of the formula (Ia) or its salt,

wherein
R ¹ , R ² and R ³ independently represent a hydrogen atom or a hydroxyl group,
R ^{4 is} a hydroxyl group, a group * -NH-CH ₂ -COOH or a group * -NH-CH ₂ -CH ₂ -SO ₃ H.

For the preferred representatives of the formula (Ia), the same preferred embodiments as previously defined for the formula (I) apply ( vide supra ).

It is particularly preferred if the agent according to the invention as steroid acid at least taurocholic acid (in formulas (I) or (Ia): R ¹ = OH, R ² = H, R ³ = OH, R ⁴ = * -NH-CH ₂ -CH ₂ -SO ₃ H) or their salt.

Preferred agents are liquid and preferably contain water as the main solvent. It is preferred that the agent contains more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of agent, water. Particularly preferred liquid agents contain - based on their weight - 5 to 90 wt .-%, preferably 10 to 85 wt .-%, particularly preferably 25 to 75 wt .-% and in particular 35 to 65 wt .-% water. Alternatively, the agents may be low to anhydrous, with the level of water in a preferred embodiment less than 10 wt .-%, and more preferably less than 8 wt .-%, each based on the total liquid agent.

In addition, non-aqueous solvents may be added to the composition. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range. Preferably, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof Solvent. However, it is preferred that the agent contains an alcohol, in particular ethanol and / or glycerol, in amounts of between 0.5 and 5 wt .-%, based on the total agent.

The herein described (especially liquid) agents, particularly the described low to zero water resources, can be filled into a water-soluble wrapper and thus be part of a water-soluble wrapper. When the liquid agent is packaged in a water-soluble casing, it is preferred that the content of water is less than 10% by weight based on the total liquid agent and that anionic surfactants, if present, are in the form of their ammonium salts.

The neutralization with amines, unlike bases such as NaOH or KOH, does not lead to the formation of water. Thus, low-water liquid detergents can be prepared which are directly suitable for use in water-soluble coatings.

A water-soluble packaging contains, in addition to the (liquid) detergent, a water-soluble coating. The water-soluble coating is preferably formed by a water-soluble film material.

Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.

The thermoforming process generally includes forming a first layer of water-soluble film material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the surface bulges filled with the composition having a second layer of a water-soluble film material and sealing the first and second layers together at least around the bulges.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.

The water-soluble package comprising a (liquid) composition according to the invention and the water-soluble envelope may have one or more chambers. The (liquid) agent may be contained in one or more chambers, if any, of the water soluble envelope. The amount of (liquid) detergent preferably corresponds to the full or half dose needed for a wash.

It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol-1, preferably 20,000 to 500,000 gmol-1, more preferably 30,000 to 100,000 gmol-1 and especially from 40,000 to 80,000 gmol-1.

A suitable for preparing the water-soluble coating sheet material may additionally polymers, selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

Suitable water-soluble films for use in the enclosures of the water-soluble packaging according to this embodiment of the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The water-soluble packages may have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.

The water soluble package may include one or more chambers for storing one or more agents. If the water-soluble packaging has two or more chambers, at least one chamber contains a liquid agent according to the invention. The further chambers may each contain a further solid or another liquid agent.

The agent according to the invention preferably contains at least one alkalizing agent in addition to hydrolytic enzyme and said steroid acid. Preferred alkalizing agents are selected from alkali metal hydroxides (for example, sodium hydroxide or potassium hydroxide), alkanolamines (such as 2-aminoethanol, diethanolamine, triethanolamine, or a mixture thereof, with monoethanolamine being preferred.

Particularly preferred agents according to the invention contain, in addition to the abovementioned compulsorily contained ingredients, at least one surfactant. The described compositions according to the invention may in particular advantageously additionally contain at least one anionic and / or at least one nonionic surfactant.

Suitable additional anionic surfactants are different from the compounds of formula (I) ( vide supra ) and include, but are not limited to, alkylbenzene sulfonates, olefin sulfonates, alkane sulfonates, fatty alcohol sulfates, fatty alcohol ether sulfates or a mixture of two or more of these anionic surfactants. Of these anionic surfactants, alkylbenzenesulfonates, fatty alcohol ether sulfates and mixtures thereof are particularly preferred. Other suitable anionic surfactants are soaps, ie salts of fatty acids, especially the Na or K salts of C _12-18 fatty acids.

Preferred surfactants of the sulfonate type are alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis the sulfonation obtained. Also suitable are C _12-18 alkanesulfonates and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

in der R' und R" unabhängig H oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 C-Atome enthalten. Ein ganz besonders bevorzugter Vertreter ist Natriumdodecylbenzylsulfonat.Alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula

in which R 'and R "are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms A particularly preferred representative is sodium dodecylbenzylsulfonate.

As alk (en) ylsulfate are the salts of sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ -oxo alcohols and those half esters secondary alcohols of these chain lengths are preferred. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also alkyl ether sulfates having the formula

R ^{1 is} -O- (AO) _n -SO ₃ ^- X ⁺

are suitable. In this formula, R ^{1 is} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na ⁺ or K ⁺ including Na, with Na ^{+ being} extremely preferred is. Other cations X + may be selected from NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel A-1). Der angegebenen Ethoxylierungsgrad stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann. Die angegebenen Alkoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoxylate/Ethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE).Particularly preferred detergents contain an alkyl ether sulfate selected from fatty alcohol ether sulfates of the formula

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-C _12-14 fatty alcohol _ether sulfates with 2 EO (k = 11-13, n = 2 in formula A-1). The stated degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product. The indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

Soaps according to the invention are the water-soluble sodium or potassium salts of saturated and unsaturated fatty acids having 10 to 20 carbon atoms, rosin acids (yellow resin soaps) and naphthenic acids which are used as solid or semi-solid mixtures mainly for washing and cleaning purposes. Sodium or potassium salts of the saturated and unsaturated fatty acids having 10 to 20 carbon atoms, in particular having 12 to 18 carbon atoms, are preferred soaps according to the invention. Particularly preferred agents according to the invention are characterized in that they contain, based on their weight, from 0.1 to 15.0% by weight, particularly preferably from 1.0 to 10.0% by weight, very particularly preferably from 3.0 to 8.0 wt .-% soap (s) included.

The anionic surfactants including the soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts and / or ammonium salts. Amines which can be used for the neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being preferred.

In various embodiments, the agent according to the invention contains as additional surfactant at least one nonionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl (poly) glucosides, and mixtures thereof.

R²

für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest,

AO

für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

m

für ganze Zahlen von 1 bis 50 stehen.

Preferred agents according to the invention additionally contain at least one fatty alcohol alkoxylate of the formula

R ^{2 is} -O- (AO) _m -H,

in the

R ²

a linear or branched, substituted or unsubstituted alkyl radical,

AO

for an ethylene oxide (EO) or propylene oxide (PO) grouping,

m

stand for integers from 1 to 50.

In the abovementioned formula, R ^{2 is} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, Eicosylresten and mixtures thereof, wherein the agent with an even number of C Atoms are preferred. Particularly preferred radicals R ² are derived from C ₁₂ -C ₁₈ -fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ -oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The subscript m is an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, m is the numbers 2, 3, 4, 5, 6, 7 or 8.

mit k = 11 bis 19, m = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind C_12-18 Fettalkohole mit 7 EO (k = 11-17, m = 7 in Formel C-1).In summary, particularly preferred fatty alcohol alkoxylates are those of the formula

with k = 11 to 19, m = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are C _12-18 fatty alcohols with 7 EO (k = 11-17, m = 7 in formula C- 1).

As amine oxide, in principle all amine oxides established for this purpose in the prior art are compounds which have the formula R ¹ R ² R ³ NO, where each of R ¹ , R ² and R ^{3 is} independently of the others an optionally substituted C ₁ -C ₃₀ hydrocarbon chain is used. Particularly preferably used amine oxides are those in which R ^{1 is} C ₁₂ -C ₁₈ alkyl and R ² and R ^{3 are} each independently C ₁ -C ₄ alkyl, in particular C ₁₂ -C ₁₈ alkyl dimethyl amine oxides. Exemplary representatives of suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-dihydroxyethylamine oxide, myristyl / cetyldimethylamine oxide or lauryldimethylamine oxide.

In various embodiments of the invention, the agent according to the invention additionally contains at least one anionic surfactant, in particular an alkylbenzenesulfonate and / or a Alkyl ether sulfate, and at least one other nonionic surfactant, in particular a fatty alcohol ethoxylate.

Preferred detergents based on the total amount of the detergent 2 to 25 wt .-%, preferably 2.5 to 20 wt .-%, more preferably 3 to 17.5 wt .-% and in particular 5 to 12.5 wt .-% Alkyl ether sulfate (s), especially fatty alcohol ether sulfate (s).

Further preferred detergents based on the total amount of the detergent 2.5 to 20 wt .-%, preferably 3 to 18 wt .-%, more preferably 3.5 to 17 wt .-%, still more preferably 4 to 15 wt. % and in particular 5 to 10 wt .-% alkylbenzenesulfonate (s), in particular C _9-13 -alkylbenzenesulfonate (s).

Further preferred detergents based on the total amount of the detergent 1 to 15 wt .-%, preferably 2 to 14 wt .-%, more preferably 2.5 to 13 wt .-%, still more preferably 3 to 10 wt .-% and in particular 4 to 9% by weight of fatty alcohol ethoxylate (s).

In addition to the compulsorily contained ingredients, the agent according to the invention may contain further ingredients which further improve the performance and / or aesthetic properties of the agent. In the context of the present invention, the composition according to the invention preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume compositions, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, Silicone oils, soil release polymers, grayness inhibitors, shrinkage inhibitors, anti-wrinkling agents, color transfer inhibitors, other antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, softening components, skin care Agent, detergency-enhancing polymer ("booster polymers") and UV absorbers.

Particularly preferred additional ingredients are builders, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume compositions, fluorescers, dyes, hydrotopes, foam inhibitors, soil release polymers, grayness inhibitors, dye transfer inhibiting agents, plasticizing components, UV absorbers and mixtures thereof.

Suitable builders which may be present in the composition are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Organic builders which may be present in the composition are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

However, preference is given to using soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol in the liquid detergents or cleaners.

An agent of the invention may contain particles dispersed as an additional ingredient, the diameter of which is preferably from 1 to 2000 μm along its greatest spatial extent. For the purposes of this invention, particles may be capsules, abrasives as well as powders, granules or compounds of compounds which are insoluble in the composition, with capsules being preferred.

The term "capsule" on the one hand understood aggregates with a core-shell structure and on the other hand aggregates with a matrix. Core-shell capsules contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s).

The agent according to the invention may contain, in addition to the hydrolytic enzyme necessarily contained according to the invention, an enzyme different therefrom or a mixture of such enzymes. Particularly suitable are those from the class of oxidases, peroxidases, mannanases, perhydrolases, Oxireduktasen and / or laccases. The amount of enzyme or of the enzymes is preferably 0.01 to 10 wt .-%, preferably 0.12 to about 3 wt .-%, based on the total agent. The enzymes are preferably used as enzyme liquid formulation (s).

The preparation of an agent according to the invention is carried out by means of customary and known methods and processes. Thus, for example, the constituents of the compositions can be simply mixed in stirred tanks, wherein water, nonaqueous solvent, acidic components such as alkylarylsulfonic acid, citric acid, boric acid or phosphonic acid, fatty alcohol ether sulfates, if present, as well as the nonionic surfactant according to the invention are advantageously presented. Subsequently, the fatty acid, if present, is added and saponification of the fatty acid moiety occurs at 50 to 60 ° C. Subsequently, the other ingredients, preferably in portions added.

A second subject of the invention relates to the use of an agent of the first subject of the invention for the washing, cleaning and / or pretreatment of textiles. For the purposes of the present invention, textiles are in particular textile fabrics, such as, for example, clothing, bath or laundry textiles. These may include natural and / or synthetic fibers, such as silk, linen, cotton, polyester, polyamide or acetate chamois. The fibers can be treated or untreated. Furthermore, such textile fabrics are comprised, which consist of woven or non-woven materials, such as nonwovens.

A third subject of the invention relates to the use of at least one steroid acid of the formula (I) or its salt for increasing the cleaning power (detergency) of an agent, in particular a laundry detergent, comprising at least one hydrolytic enzyme.

A fourth subject of the invention relates to the use of at least one steroid acid of the formula (I) of the first subject of the invention ( vide supra ) or its salt for increasing the cleaning performance (detergency) of an agent, in particular a laundry detergent containing at least one hydrolytic enzyme, in a temperature range between 10 ° C and 50 ° C, between 10 ° C and 40 ° C, and preferably between 10 ° C and 30 ° C and 10 ° C and 25 ° C.

1. a) Bereitstellen einer Waschlösung umfassend ein Mittel des ersten Erfindungsgegenstandes, und
2. b) In Kontakt bringen eines Textils mit der Waschlösung gemäß (a).

A fifth subject of the invention relates to a method comprising the method steps

1. a) providing a washing solution comprising a means of the first subject of the invention, and
2. b) bringing into contact a textile with the washing solution according to (a).

Examples:

Various means were prepared in which, if taurocholic acid, sodium salt was added, an equivalent weight amount of alkyl benzene sulfonate was removed to keep the amount of anionic surfactant constant. The composition of the invention E1 (steroid acid and hydrolytic enzyme), compositions V1 (steroid acid but no hydrolytic enzyme) and V2 (no steroid acid but hydrolytic enzyme) were each compared with the reference composition V3 (no steroid acid and no hydrolytic enzyme).

For the washing tests, household washing machines (Miele W1514 Novotronic) with 3.5 kg accompanying laundry as well as the soiled cloth rags were loaded. In addition, 80 g / 75 ml of the detergent to be tested were added and washed at 20 ° C in the cotton program.

After hanging drying and mangling of the cloth rags their whiteness was determined spectrophotometrically (Minolta CR400-1).

The results are given in Table 2 and are averages of 5 determinations. The measured values are given as a difference to the reference formulation V3. Shown are therefore the differences of the remission values. Positive values show an improvement in the washing performance and a stronger leaching of the stain.

The soiled textiles were bought or self-made. Table 2: Comparison of detergency with composition V3 Detergent E1 Detergent V1 Detergent V2 sheep blood 4.5 2.7 0.4

Table 2 clearly shows that the combination of taurocholic acid salt and hydrolytic enzyme leads to a synergistic improvement.

Claims (15)

Detergents and cleaners containing at least one hydrolytic enzyme and - At least one steroid acid of the formula (I) or its salt

wherein
R ¹ , R ² and R ³ independently represent a hydrogen atom or a hydroxyl group,
R ^{4 is} a hydroxyl group, a group * -NH-CH ₂ -COOH or a group * -NH-CH ₂ -CH ₂ -SO ₃ H. Composition according to claim 1, characterized in that the hydrolytic enzyme is selected from at least one protease, amylase or lipase and mixtures thereof, preferably from at least one protease and / or at least one amylase, more preferably from at least one protease and at least one amylase. Composition according to claim 1 or 2, characterized in that as the hydrolytic enzyme at least one endopeptidase (EC 3.4.21), in particular at least one protease of the subtilisin type, is contained as a protease Agent according to one of claims 1 to 3, characterized in that at least one α-amylase is contained as a hydrolytic enzyme. Composition according to one of claims 1 to 4, characterized in that the hydrolytic enzyme, based on the weight of the agent in a total amount of 0.001 to 5 wt .-%, more preferably from 0.01 to 5 wt .-%, even more preferred from 0.05 to 4 wt .-% and particularly preferably from 0.075 to 3.5 wt .-%. Composition according to one of claims 1 to 5, characterized in that said steroid acid or its salt in a total amount of 0.1 to 5.0 wt .-%, particularly preferably from 1.0 to 3.0 wt .-%, respectively is contained based on the weight of the agent. Composition according to one of claims 1 to 6, characterized in that the steroid acid according to formula (I) is selected from one or more compounds of formula (I), which as a possible combination of R ¹ , R ² and R ³ one of the following combinations having: R ¹ R ² R ³ OH H OH OH H H H H OH H H H H OH OH H OH H Composition according to one of claims 1 to 7, characterized in that the radical R ⁴ according to formula (I) represents a group * -NH-CH ₂ -CH ₂ -SO ₃ H. Composition according to one of claims 1 to 8, characterized in that as steroid acid at least taurocholic acid (in formulas (I) or (Ia): R ¹ = OH, R ² = H, R ³ = OH, R ⁴ = * -NH- CH ₂ -CH ₂ -SO ₃ H) or its salt is contained. Agent according to one of claims 1 to 9, characterized in that additionally contain at least one anionic and / or at least one nonionic surfactant. Agent according to one of claims 1 to 10, characterized in that it is liquid. Use of a composition according to any one of claims 1 to 11 for the washing, cleaning and / or pretreatment of textiles. Use of at least one steroid acid of the formula (I) or its salt

wherein
R ¹ , R ² and R ³ independently represent a hydrogen atom or a hydroxyl group,
R ^{4 is} a hydroxyl group, a group * -NH-CH ₂ -COOH or a group * -NH-CH ₂ -CH ₂ -SO ₃ H,
for increasing the cleaning performance of an agent, in particular a laundry detergent, containing at least one hydrolytic enzyme. Use according to claim 13, characterized in that the cleaning performance increase at temperatures between 10 ° C and 50 ° C, in particular between 10 ° C and 40 ° C, preferably between 10 ° C and 30 ° C, more preferably between 10 ° C and 25 ° C, takes place. Method comprising the method steps a) providing a washing solution comprising an agent according to any one of claims 1 to 11, and b) bringing into contact a textile with the washing solution according to (a).