WO2015173055A1

WO2015173055A1 - Detergent and cleaning agent with increased bleaching power

Info

Publication number: WO2015173055A1
Application number: PCT/EP2015/059766
Authority: WO
Inventors: André HÄTZELT; Timothy O'connell
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2014-05-15
Filing date: 2015-05-05
Publication date: 2015-11-19
Also published as: DE102014209241A1; EP3143115B1; EP3143115A1; PL3143115T3

Abstract

The problem addressed by the invention is that of improving the bleaching power of acylhydrazones in detergents and cleaning agents that contain peroxygen. This was achieved through the use of a protease.

Description

Detergents and cleaners with increased bleaching performance

The present invention relates to the use of a particular protease to enhance the bleaching performance of certain acylhydrazones, to wash textiles or to clean hard surfaces, and to detergents and cleaners containing such a protease and such acylhydrazone.

Conventional bleaching agents based on active oxygen, even in the presence of stoichiometric activators (such as TAED, NOBS, DECOBS, DOBA), show good performance at use temperatures of 40 ° C and above. At low temperatures, however, the bleaching performance is limited.

An increase in the bleaching performance by increasing the amount of bleach or the use of particularly effective bleaching agents often leads to a reduction in the performance of the enzymes used such as protease and lipase, which then leads in particular to a reduced removal of proteinaceous and greasy stains.

International patent applications WO 2009/124855 A1 and WO 2012/080088 A1 disclose the bleach-enhancing effect of acylhydrazones.

Surprisingly, it has been found that the presence of certain proteases further enhances the bleaching performance of such acylhydrazones.

The invention relates to the use of a protease selected from

a) Proteases comprising an amino acid sequence corresponding to the amino acid sequence given in SEQ ID NO: 1 over at least 70% of its total length and increasingly preferably at least 75%, 80%, 81%, 82%, 83%, 84%, 85% , 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94, 5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99%, and counting in accordance with SEQ ID NO: 1 the position 193 has the amino acid V and / or the amino acid L at position 21 1,

b) proteases comprising an amino acid sequence corresponding to the amino acid sequence given in SEQ ID NO: 2 over at least 70% of its total length and increasingly preferably at least 75%, 80%, 81%, 82%, 83%, 84%, 85% , 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94, 5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99% and in the count according to SEQ ID NO: 2 at position 9 amino acid R and / or at position 15 amino acid T and / or at position 66 amino acid A. and / or at position 212 amino acid D and / or at position 239 has the amino acid R, and

c) mixtures thereof,

for enhancing the bleaching performance of acylhydrazones of general formula (I),

in the R is a CF3 or a Ci-28-alkyl, C2-alkenyl, C2-22-alkynyl, -i2-cycloalkyl, -12-cycloalkenyl, phenyl, naphthyl, -9-aralkyl , -2o-heteroalkyl or -12-cycloheteroalkyl group,

R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-28 -alkyl, C 2-6 alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -i 2 -cycloalkenyl, -9-aralkyl-, Heteroalkyl, -i2-cycloheteroalkyl, -i6-heteroaralkyl, phenyl, naphthyl or heteroaryl or R ² and R ³ together with the carbon atom connecting them to an optionally substituted 5-, 6-, 7 -, 8- or 9-membered ring, which may optionally contain heteroatoms, and

R ^{4 is} hydrogen or a C 1 -28-alkyl, C 2 -alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -12-cycloalkenyl, -9-aralkyl, -2o-heteroalkyl-, i2-cycloheteroalkyl, -i6-heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group

when washing textiles or cleaning hard surfaces in the presence of peroxygen-containing detergents or cleaners.

The acylhydrazones may be in E or Z configuration; when R ^{2 is} hydrogen, the compound of general formula (I) may be in one of its tautomeric forms or as a mixture of these.

In the compounds of general formula (I), R ^{2 is} preferably hydrogen. R and / or R ³ is preferably an electron-withdrawing group-substituted methyl, phenyl or naphthyl group. R ⁴ is preferably hydrogen. As the electron-withdrawing group is preferably an ammonium group in question, which optionally carries alkyl or hydroxyalkyl groups or is formed with the inclusion of the N-atom carrying an alkyl group as optionally hetero-heteroatom-carrying heteroatom group.

Preferred embodiments of the compounds according to general formula (I) include those of general formula (II),

in the R for a Ci-4-alkyl group, which is a substituent selected from

in which R ^{0 is} hydrogen or a Ο-28-alkyl, C 2-30 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, Cz-g-aralkyl -, C3-2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl and A ^"represents the anion of an organic or inorganic acid, R ² and R ^{4 have} the meaning given for formula (I) and

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently R, hydrogen, halogen, hydroxy, amino, optionally substituted N-mono or di-O-4-alkyl or C 2-4 hydroxyalkylamino -, N-phenyl or N-naphthyl-amino, Ci-28-alkyl, Ci-28-alkoxy, phenoxy, C2-28-alkenyl, C2-22-alkynyl, C3-i2-cycloalkyl -, C3-i2-cycloalkenyl, C7-9 aralkyl, C3-2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl, phenyl or naphthyl group, wherein the substituents are selected from C - alkyl, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, phenyl, phenoxy, naphthoxy, amino, N-mono or di-Ci-4-alkyl - or C2 ^ -hydroxyalkyl-amino, N-phenyl or N-naphthyl-amino groups, or

R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ⁷ and R ⁸ to form 1, 2 or 3 carbocyclic or O, NR ¹⁰ - or S-heterocyclic, optionally aromatic and / or optionally C 1-6 alkyl-substituted rings connected to each other.

The anion A ^" is preferably carboxylate, such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, Bromide, bicarbonate or carbonate, wherein for polyvalent anions, the charge balance can be achieved by the presence of additional cations such as sodium or ammonium ions.

Particular preference is given to the acylhydrazone of the formula (III)

Proteases are enzymes that catalyze the hydrolysis of amide bonds in protein substrates. The protease used according to the invention has preferably the amino acid V in the counting according to SEQ ID NO: 1 at the position 193 and preferably the amino acid L at the position 21 1, or it has in the counting according to SEQ ID NO: 2 at the position 9 the amino acid R, at the position 15 the amino acid T, at the position 66 the amino acid A, at the position 212 the amino acid D and / or at the position 239 the amino acid R, whereby also several, for example 2, 3, 4 or 5, such proteases can be used. In addition to or instead of the proteases mentioned above under a) and b), those of the subtilisin type may also be used. 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 thermotase, proteinase K, which can no longer be assigned to the subtilisins in the narrower sense and the proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase®, and 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® and Kannase® from Novozymes, which are sold under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase And Properase.RTM. From Genencor, sold under the trade name Biotouch.RTM. ROC 250 L by AB Enzymes, Darmstadt, under the trade name Protosol.RTM. By Advanced Biochemicals Ltd., Thane, India Trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, sold under the trade names Proleather® and Protease P® by Amano Pharmaceuticals Ltd., Nagoya, Japan, under the trade name Biogent® 900 G from Ishaan Bio Private Limited, Ahmedabad, India, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Particular preference is also given to using the proteases from Bacillus gibsonii and Bacillus pumilus, which are disclosed in international patent applications WO2008 / 086916 and WO2007 / 131656. The effect according to the invention of increasing the bleaching performance is not observed when using the protease according to SEQ ID NO: 3 or according to SEQ ID NO: 4. The identity of nucleic acid or amino acid sequences is determined by a sequence comparison. This sequence comparison is based on the BLAST algorithm established and commonly used in the prior art (see, for example, Altschul, SF, Gish, W., Miller, W., Myers, EW & Lipman, DJ. (1990) "Basic local alignment search Biol. 215: 403-410; and Altschul, Stephan F., Thomas L. Madden, Alejandro A. Schaffer, Jinghui Zhang, Hheng Zhang, Webb Miller, and David J. Lipman (1997): "Gapped BLAST and PSI-BLAST: a new generation of protein database search programs"; Nucleic Acids Res., 25, pp.3389-3402) and is in principle effected by similar sequences of nucleotides or amino acids in the nucleic acid or nucleic acid sequences Amino acid sequences are assigned to each other. A tabular assignment of the respective positions is referred to as alignment. Another algorithm available in the prior art is the FASTA algorithm. Sequence comparisons (alignments), in particular multiple sequence comparisons, are created with computer programs. For example, the Clustal series (see, for example, Chenna et al., 2003: Multiple sequence alignment with the Clustal series of programs, Nucleic Acid Research 31, 3497-3500), T-Coffee (see, for example, Notredame et al (2000): T-Coffee: A novel method for multiple sequence alignments, J. Mol. Biol. 302, 205-217) or programs based on these programs or algorithms. In this patent application, all sequence comparisons (a lignments) were made using the Vector NTI® Suite 10.3 computer program (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the default default parameters and its AlignX module for sequence comparisons ClustalW is based.

Such a comparison also allows a statement about the similarity of the compared sequences to each other. It is usually given in percent identity, that is, the proportion of identical nucleotides or amino acid residues at the same or in an alignment corresponding positions. The broader concept of homology involves conserved amino acid substitutions in the consideration of amino acid sequences, that is, amino acids with similar chemical activity, as these usually perform similar chemical activities within the protein. Therefore, the similarity of the sequences compared may also be stated as percent homology or percent similarity. Identity and / or homology information can be made about whole polypeptides or genes or only over individual regions. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by matches in the sequences. Such areas often have identical functions. They can be small and comprise only a few nucleotides or amino acids. Often, such small regions exert essential functions for the overall activity of the protein. It may therefore be useful to relate sequence matches only to individual, possibly small areas. Unless otherwise indicated, identity or homology information in the present application, however, refers to the total length of the particular nucleic acid or amino acid sequence indicated. The weight of the protease relative to active protein in the total weight of detergents or cleaners according to the invention is preferably 0.005 to 1.0% by weight, in particular 0.01 to 0.5% by weight and more preferably 0.02 to 0.2% by weight .-%. 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 this regard, the determination of the active protein concentration was carried out by titration of the active sites using a suitable irreversible inhibitor (for proteases, for example phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (see M. Bender et al., J. Am. Chem , 24 (1966), pp. 5890-5913).

The cleaning-active effects of the protease are retained in the presence of the simultaneously present acylhydrazone. However, the detergent-active effects of the acylhydrazone are enhanced in the presence of co-present protease, if one selects the protease among the above-mentioned enzymes. The combined use of such protease and acylhydrazone also results in a greater number of improved soilings removed than the sum of enhanced soilings on use of each of the two active ingredients, especially at low wash temperatures of, for example, 40 ° C and below, and even at room temperature.

The performance of compounds of general formula (I) may optionally be enhanced by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II) - (III) - (IV) - (V), Cu ( l) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Ti (II) - (III) - (IV), and particularly preferably those selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III ), Fe (I) - (II) - (III) - (IV) and Co (I) - (II) - (III); If desired, the acylhydrazone can also be used in the form of complex compounds of said metal central atoms with ligands of general formula (I) and in particular of general formula (II). A bleach-enhancing complex which has a ligand with a skeleton of the formula (I) may have the corresponding ligand once or more than once, in particular twice. It may be one or possibly two or more nuclear. It may also contain other neutral, anion or cationic ligands such as H2O, NH3, CH3OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C2-is carboxylate, a C18-alkyl sulfate , in particular methosulfate, or a corresponding alkanesulfonate, inorganic anions such as, for example, halide, in particular chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogensulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.

Within the scope of the use according to the invention, it is preferred if the concentration of the Binding according to formula (I) in an aqueous liquor, as used for example in washing machines or dishwashers, 0.5 μιηοΙ / Ι to 500 μιηοΙ / Ι, in particular 5 μιηοΙ / Ι to 100 μιηοΙ / Ι. The above-mentioned complex-forming metal ions are preferably not intentionally added, but they may be present from possible sources of such metal ions, which include, in particular, the tap water, the washing machine itself, adhesions to textiles, and stains on the fabrics. Optionally, metal ions inadvertently introduced with other detergent ingredients may also be considered. Preferred peroxygen concentrations (calculated as H2O2) in the liquor are in the range from 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l and particularly preferably from 0.2 g / l to 0, 5 g / l. The use according to the invention is preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 20 ° C. to 40 ° C., and particularly preferably at temperatures below 30 ° C. The water hardness of the water used for preparing the aqueous liquor is preferably in the range from 0 ° dH to 21 ° dH, in particular 0 ° dH to 3 ° dH. In the wash liquor, the water hardness is preferably in the range of 0 ° dH to 16 ° dH, in particular 0 ° dH to 3 ° dH, which can be achieved for example by the use of conventional builder materials or water softeners. The use according to the invention is preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.

The use according to the invention is preferably carried out by allowing a peroxygen compound and a detergent containing an acylhydrazone of the general formula (I) and the abovementioned protease to act on a contaminated textile in the course of a machine or hand washing operation. The use according to the invention can be realized particularly simply by the use of a detergent, the peroxygen compound, said protease and a compound of the formula (I) or, if desired, a bleach catalyst obtainable therefrom by complex formation with a transition metal ion mentioned, in the washing of textiles requiring cleaning. Alternatively, the peroxygen compound and / or the compound of the formula (I) and / or a complex obtainable therefrom and / or the protease may also be added separately to a wash liquor which has a detergent without the respective stated ingredient. The same applies to cleaning agents for hard surfaces in the inventive use, for example in the context of a dishwashing process.

A further subject of the invention is therefore a washing or cleaning agent containing a persoxy-containing bleaching agent, a compound of the formula (I) and a protease selected from a) proteases comprising an amino acid sequence corresponding to the amino acid sequence given in SEQ ID NO: 1 their total length being at least 70%, and more preferably at least 75%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5 %, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99% is identical and in the count according to SEQ ID N0: 1 at position 193 the amino acid V and / or at the position 21 1 has the amino acid L,

b) proteases comprising an amino acid sequence corresponding to the amino acid sequence given in SEQ ID NO: 2 over at least 70% of its total length and increasingly preferably at least 75%, 80%, 81%, 82%, 83%, 84%, 85% , 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94, 5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99% and in the count according to SEQ ID NO: 2 at position 9 amino acid R and / or at position 15 amino acid T and / or at position 66 amino acid A and / or at position 212 amino acid D and / or at position 239 amino acid R, and

c) their mixtures. Preferred embodiments also apply to the category of detergents or cleaners; in particular, the compound of formula (I) may also be present in the form of a bleach catalyst obtainable by complexation with a transition metal ion thereof from said agent.

For example, lipases or cutinases can be used as further enzymes, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those having the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

The agents according to the invention may also contain cellulases or hemicellulases such as mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases or β-glucanases.

If desired, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect. Advantageously, it is additionally preferable to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the electron flow at greatly varying redox potentials between the oxidizing enzymes and the soils (mediators). ,

With particular preference, the cleaning agents according to the invention contain as further enzyme at least one amylase. An amylase is an enzyme as described in the introduction. For amylases, synonymous terms may be used, for example, 1,4-alpha-D-glucan glucanohydrolase or glycogenase. Amylases preferred according to the invention are α-amylases. Crucial for determining whether an enzyme is an α-amylase according to the invention is its ability to hydrolyze α (1-4) -glycoside bonds in the amylose of the starch.

Exemplary amylases are the α-amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens or from Bacillus stearothermophilus and, in particular, also their improved developments for use in detergents or cleaners. The enzyme from Bacillus licheniformis is available from the company Novozymes under the name Termamyl® and from the company Danisco / Genencor under the name Purasta DST. Further development products of this α-amylase are available from the company Novozymes under the trade names Duramyl® and Termamy Dultra, from the company Danisco / Genencor under the name Purasta DOxAm and from the company Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The Bacillus amyloliquefaciens α-amylase is sold by the company Novozymes under the name BAN®, and variants derived from the Bacillus stearothermophilus α-amylase under the names BSG® and Novamyl®, also from the company Novozymes. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the further developments of the α-amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are suitable. Further advantageously usable commercial products are, for example, the amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter also from the company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred amylases are disclosed in International Publication WO 00/60060, WO 03/00271 1, WO 03/054177 and WO07 / 079938.

In summary, preferred cleaning agents according to the invention are characterized in that at least one enzyme from the group of amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, xyloglucanases, β-glucosidases, pectinases, carrageenases, perhydrolases, oxidases, oxidoreductases or a lipase, and mixtures thereof, preferably from the group of amylases. The proportion by weight of the further enzymes in the total weight of the detergents and cleaners relative to active protein is preferably from 0.0005 to 1.0% by weight, in particular from 0.001 to 0.5% by weight and more preferably from 0.002 to 0.2% by weight. -%.

Preferably, in detergents or cleaners 0.001 wt .-% to 5 wt .-%, in particular 0.05 wt .-% to 0, 15 wt .-% and particularly preferably 0.03 wt .-% to 0.09 wt .-% of the compound according to formula (I). In particular, when a compound of the formula (I) is present, it is preferred that the agent additionally comprises a manganese, titanium, cobalt, nickel or copper salt and / or a manganese, titanium, cobalt, nickel or copper complex without a ligand which corresponds to a compound according to formula (I). Then, the molar ratio of said transition metal or the sum of said transition metals to the compound according to formula (I) is preferably in the range of 0.001: 1 to 2: 1, in particular 0.01: 1 to 1: 1. In a further preferred embodiment of Agents are contained in these 0.05 wt .-% to 1 wt .-%, in particular 0, 1 wt .-% to 0.5 wt .-% of bleach-enhancing complex having a ligand according to formula (I) included. Preferred transition metal is Mn.

As peroxygen compounds contained in the compositions, in particular organic peracids or persistent salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxo acid salts, such as alkali metal perulfates or peroxodisulfates or caroates, or diacyl peroxides or tetraacyldiperoxides, Hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing substances, such as alkali metal perborates, alkali metal peracids, alkali metal peracidates and urea perhydrate, into consideration. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide. Preferably, peroxygen compounds are present in the compositions in amounts of up to 50% by weight, more preferably from 2% to 45% and more preferably from 5% to 20% by weight.

In a further preferred embodiment of the invention, in particular in the presence of H2O2 releasing peroxygen compound, a conventional bleach activator is used together with the acyl hydrazone of the general formula (I), the general formula (II) and in particular the formula (III). In detergents such bleach activators are preferably present in amounts of up to 10 wt .-%, in particular from 1, 5 wt .-% to 5 wt .-%. Preference is given to using peroxycarboxylic acid-forming compound and acylhydrazone in molar ratios in the range from 4: 1 to 100: 1, in particular from 25: 1 to 50: 1, under perhydrolysis conditions.

Compounds which can be added under perhydrolysis conditions to give peroxocarboxylic acid are, in particular, compounds which have perbenzoic acid optionally substituted under perhydrolysis conditions and / or aliphatic peroxocarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms. Atoms arise, used alone or in mixtures. Suitable are bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nano-nanoyl or isononanoyl or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), whose formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benzenesulfonate (DECOBS), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and acylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, acetyl ertes, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam.

In addition or as an alternative to the compounds which form peroxycarboxylic acids under perhydrolysis conditions, further bleach-activating compounds, such as, for example, nitriles, from which perimides acids are formed under perhydrolysis conditions, may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula

R ¹¹

I

R ² -N ( ⁺ ) - (CR ⁴ R ⁵ ) -CN X (-)

I

_R 13 in the R represents -H, -Chta, a C 2-24 -alkyl or -alkenyl radical, a substituted C-24-alkyl or C 2- 24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH2, -CN and -N ⁽⁺⁾ -CH2-CN, an alkyl or alkenylaryl radical having a Ci-24-alkyl group, or for a substituted alkyl or alkenylaryl radical having at least one, preferably two, optionally substituted Ci -24-alkyl group (s) and optionally further substituents on the aromatic ring, R ² and R ^{3 are} independently selected from -CH 2-CN, -CH 3, -CH 2 -CH 3, -CH 2 -CH 2 -CH 3, -CH (CH ₃₎ -CH _3, -CH ₂ -OH, -CH 2 -CH 2 OH, -CH (OH) _-CH3, -CH2-CH2-CH2-OH, -CH 2 CH (OH) -CH _3, -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) n H with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another for R, R ² or R ³ have the meaning given, wherein at least 2 of the radicals mentioned, in particular R ² and R ³ , also with the inclusion of the nitrogen atom and optionally white tertiary heteroatoms may be linked to one another in a ring-closing manner and then preferably form a morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfo N, the C9-i5-Alkylbenzolsulfonaten, the Ο-20-alkyl sulfates, the C8-22-carboxylic acid methyl ester sulfonates, sulfate, hydrogen sulfate and mixtures thereof, can be used. Oxygen-carrying sulfonimines can also be used.

To avoid interaction with the peroxygen compounds, the bleach activators may have been coated or granulated in known manner with coating substances, granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, granulated by means of carboxymethylcellulose 1, 5-diacetyl-2,4-dioxo-hexahydro-1, 3,5-triazine, and / or formulated in particulate form Trialkylammoniumacetonitrile is particularly preferred.

In addition to the combination to be used according to the invention, it is also possible to use customary bleach-activating transition metal complexes. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Suitable ligands in such transition metal complexes are both inorganic and organic compounds, which in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions such as pyridine, pyridine, pyrimidine, pyrazine, imidazole , pyrazole, triazole, 2,2 ^{'-bispyridylamine,} tris (2-pyridylmethyl) amine, 1, 4,7-triazacyclononane and its substituted derivatives such as 1, 4,7-trimethyl-1, 4,7-nonane triazacyclo- , 1, 5,9-triazacyclododecane and its substituted derivatives such as 1, 5,9-trimethyl-1, 5,9-triazacyclododecane 1, 4,8,1-tetraazacyclotetradecane and its substituted derivatives such as

5, 5, 7, 12, 12, 14-hexamethyl-1, 4, 8, 1-tetraazacyclotetradecane, 1, 5, 8, 12-tetraazabicyclo [6.6.2] hexadecane and its substituted derivatives such as 5, 12 -Diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane, (bis ((1-methylimidazol-2-yl) -methyl)) - (2-pyridylmethyl) -amine, N, N ^' - (bis (1-methylimidazol-2-yl) methyl) ethylenediamine, N-bis (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4 -methylphenol, N, N, N ^', ^N' tetrakis- (2-benzimi- dazolylmethyl) -2-hydroxy-1, 3-diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) - 4-methylphenol, 1, 3-bis (bis (2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol, erythethol, adonitol, inositol, lactose, and optionally substituted salene, porphins, and porphyrins. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO 2) ^- group, that is, a nitro ligand or a nitrito ligand. The (NO 2) ^" group can also be chelated to a transition metal, or it can asymmetrically or bridged two transition metal atoms In addition to the ligands mentioned, the transition metal complexes can also contain further, generally simpler ligands, in particular on or polyvalent anion ligands. As nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands should provide charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise. In the case of bridged, dinuclear complexes, both metal atoms in the complex need not be the same. The use of dinuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate. Examples of usable transition metal complex compounds are Μη (ΐν) 2 (μ-O) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) di-hexafluorophosphate, [N, N'-bis [(2 -hydroxy-5-vinylphenyl) - methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) -methylene] -1, 2 diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1, 2-phenylenediamine] manganese (III) acetate, [N, N'- Bis [(2-hydroxyphenyl) methylene] -1, 2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1, 2-diaminoethane ] - manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-sulfonatophenyl) -methylene] -1,2-diaminoethane] manganese (III) chloride, manganese oxalato complexes, nitropentammine cobalt (III) chloride, nitrite pentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride, and the peroxo complex [(NH ₃ ) 5 Co-O -0-Co (NH ₃₎ 5] Cl4.

Detergents containing peroxygen compounds, which may be in the form of homogeneous solutions or suspensions, especially in powdered solids, in densified particle form, may in principle all be known, apart from the combination of protease and compound of formula (I) and optionally also the said bleach activators and catalysts and contain conventional ingredients in such agents. The agents may in particular be builders, surface-active surfactants, water-miscible organic solvents, other enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle-reducing polymeric agents and form-retaining polymeric agents, and others Excipients, such as optical brighteners, foam regulators, dyes and fragrances included.

An agent can for further enhancing the disinfecting action, for example against specific germs, additionally conventional antimicrobial agents, such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bonded to organic frameworks O-acetates and O-formals, benzamidi- ne, isothiazolines, phthalimide derivatives, pyridine derivatives, amines, quaternary ammonium compounds, guanidines, amphoteric compounds, quinolines, benzimidazoles, IPBC, dithiocarbamates, metals and metal compounds such as silver and silver salts, halogens such as chlorine, iodine and their compounds, others Oxidizing agents and inorganic nitrogen compounds contained. Such antimicrobial additives are preferably present in amounts of up to 10 wt .-%, in particular from 0.01 wt .-% to 5 wt .-%, each based on the total agent included; in a preferred embodiment, however, they are free of such additional disinfecting agents.

The agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be included. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 C atoms in the alkyl radical.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are present in detergents in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight,

A detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycidyl cindiacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and Hydroxyiminodisuccinate, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular Aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), Lysintetra (methylenphosphosäure) and 1-hydroxyethane-1, 1-diphosphonic acid , polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, especially by oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. The relative average molecular weight (here and below: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, though less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cs-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt may be a derivative of a C4-Cs-dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, vinyl alcohol derivatives are preferred which represent an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol. Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or

(Meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt may also be a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15% to 25% by weight of methallyl sulfonic acid or methallyl sulfonate and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. As water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used. Of these, preference is given to the detergent-grade crystalline sodium aluminosilicates, in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 μm, and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding inhibitor is usually in the range of 100 to 200 mg CaO per gram.

In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to S1O2 below 0.95, in particular from 1: 1, 1 to 1:12 and may be amorphous or crystalline. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of from 1: 2 to 1: 2.8. Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2.sup.x + H.sub.2O.sub.2, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both .beta. And .delta.-sodium disilicates (Na.sub.2Si.sub.20.sub.y H.sub.2O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1, 9 to 2.1, can be used in the compositions. In a further preferred embodiment, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another embodiment. In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15.

Suitable enzymes in the detergents are, in particular, those from the class of proteases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase and / or cellulase being particularly preferred is. The proportion is preferably 0.2 wt .-% to 1, 5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.

Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and / or soil-release active ingredients in the compositions is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight.

As optical brighteners for particular textiles made of cellulose fibers (for example cotton), detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or compounds of similar construction are suitable. fertilize, which carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group instead of the morpholino group. Further, brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. For polyamide fibers are particularly well brighteners of the type of 1, 3-diaryl-2-pyrazolines, for example, 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similarly structured compounds. The content of the composition in optical brighteners or whitener mixtures is generally not more than 1 wt .-%, and preferably in the range of 0.05 wt .-% to 0.5 wt .-%.

The customary foam regulators which can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein being preferably signed or otherwise rendered hydrophobic. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C 16- to C 18 -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.

The agents may contain water as a solvent. Among the organic solvents which can be used in the compositions, in particular if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers. Such water-miscible solvents are present in the compositions in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight.

To establish a desired, not by itself resulting from the mixture of the other components of the pH, the agents systemic and environmentally friendly acids, especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but Also, mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, included. The preparation of solid compositions presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, thermally-sensitive ingredients optionally being added separately later.

Compositions in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

The compositions are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and bleach-activating agents Active ingredients are expected to be produced. For the production of compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200 10 ⁵ Pa to 1 500 10 ⁵ Pa pressed. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strength of usually over 150 N. Preferably, a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

Examples

A protease-free and acylhydrazone-containing powdered detergent V1, the otherwise identical with V1 protease-containing and acylhydrazone-free detergent V2, V3, V4 and V5 and the protease and acylhydrazone-containing detergent E1 and E2 having the compositions given in Table 1 below ( Ingredients in% by weight) were tested at 20 ° C in washing tests at a dosage of 67.5 g per 17 l of water in a Miele® W1935 washing machine. For comparison, agents V6 and V7 were used which contained other proteases and otherwise in their composition corresponded to the agents E1 and E2. The proteases were used in the same activity in each case.

Table 1: Detergent compositions

) Morpholinium 4- (2- (2 - ((2-hydroxyphenylmethyl) methylene) hydrazinyl) -2-oxoethyl) -4-methyl chloride

²⁾ lipase / amylase / cellulase granules

³ > granules with protease BLAP X as described in section [0045] of EP 2 395 071 A1 ⁴⁾ Granules with a protease according to SEQ ID NO: 3 ⁵ > granules with protease BLAP R as described in section [0045] of EP 2 395 071 A1 ⁶⁾ Granules with a protease according to SEQ ID NO: 4

In addition to clean linen, standardized soiling of tea on cotton (A1), blackcurrant juice on cotton (A2) and blueberry juice on cotton (A3) was used.

After drying, the following values were found for the differences in the degrees of whiteness (dY value) compared with the acylhydrazone-free compositions with the corresponding acylhydrazone-containing agents

Table 2: Washing performance differences

Soiling Y (E1) - Y (V2) Y (E2) - Y (V3) Y (V6) - Y (V4) Y (V7) - Y (V5)

A1 2.0 1, 5 1, 0 1, 1

A2 1, 2 1, 0 0.0 0.6

A3 1, 1 0.6 0.4 0, 1

Claims

claims

1. Use of a protease selected from

a) proteases comprising an amino acid sequence which is at least 70% identical to the amino acid sequence given in SEQ ID NO: 1 over the entire length thereof and in the counting according to SEQ ID NO: 1 at position 193 the amino acid V and / or at the position

21 1 has the amino acid L,

b) proteases comprising an amino acid sequence which is at least 70% identical to the amino acid sequence given in SEQ ID NO: 2 over the entire length thereof and in the counting according to SEQ ID NO: 2 at position 9 the amino acid R and / or at the position 15 the amino acid T and / or at position 66 the amino acid A and / or at the position

212 has the amino acid D and / or at position 239 the amino acid R, and c) mixtures thereof,

in the R represents a CF3 or a Ο-28-alkyl, C2-alkenyl, C2-22-alkynyl, -i2-cycloalkyl, -i2-cycloalkenyl, phenyl, naphthyl, -9-aralkyl , -2o-heteroalkyl or -12-cycloheteroalkyl group,

R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-8 -alkyl, C 2-6 alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -i 2 -cycloalkenyl, -9-aralkyl-, Heteroalkyl, -i2-cycloheteroalkyl, -i6-heteroaralkyl, phenyl, naphthyl or heteroaryl or R ² and R ³ together with the carbon atom connecting them to an optionally substituted 5-, 6-, 7 , 8- or 9-membered ring, which may optionally contain heteroatoms, and

R ^{4 is} hydrogen or a C 1 -28-alkyl, C 2 -alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -12-cycloalkenyl, -9-aralkyl, -2o-heteroalkyl-, i2-cycloheteroalkyl, -16-heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group

2. Use according to claim 1, characterized in that the concentration of the compound of formula (I) in aqueous liquor 0.5 μιηοΙ / Ι to 500 μιηοΙ / Ι, in particular 5 μιηοΙ / Ι to 100 μιηοΙ / Ι. Use according to claim 1 or 2, characterized in that the peroxygen concentration (calculated as H2O2) in the liquor in the range of 0.001 g / l to 10 g / l, in particular from 0, 1 g / l to 1 g / l ,

Detergents containing a peroxygen-containing bleach, a protease selected from

21 1 has the amino acid L,

and a compound of the formula (I)

R ⁴ is hydrogen or a Ci-28-alkyl, C2 alkenyl, C 2-22 alkynyl, -i2 cycloalkyl, cycloalkenyl -12-, -9-aralkyl, -2O-heteroalkyl, - i2-cycloheteroalkyl, -16-heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group

stand.

5. Composition according to claim 4, characterized in that it contains 0.001 wt .-% to 5 wt .-%, in particular 0.05 wt .-% to 0.15 wt .-% of the compound according to formula (I).

6. Composition according to claim 4 or 5, characterized in that it protease in amounts of 0.005 wt .-% to 1, 0 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-%, respectively based on active protein.

7. Composition according to one of claims 4 to 6, characterized in that it peroxygen compounds in amounts of up to 50 wt .-%, in particular from 2 wt .-% to

Contains 45 wt .-%.

8. Composition according to one of claims 4 to 7, characterized in that it contains bleach activators in amounts of up to 10 wt .-%, in particular from 1, 5 wt .-% to 5 wt .-%.

9. Use according to one of claims 1 to 3 or agent according to one of claims 4 to 8, characterized in that the compound of the general formula (I) corresponds to the general formula (II),

in the R for a Ci-4-alkyl group, which is a substituent selected from

A ^"

in which R ^{0 is} hydrogen or C 1 -C 28 -alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl -, C3-2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl and A ^"represents the anion of an organic or inorganic acid, R ² and R ^{4 have} the meaning given for formula (I) and

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently R, hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-O-4-alkyl or C 2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino, Ci- 28 -alkyl-, Ci- 28 -alkoxy-, phenoxy-, C2-28- Alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3-30 heteroalkyl, C 3-12 cycloheteroalkyl, C 5-16 heteroaralkyl -, phenyl or naphthyl group, wherein the substituents are selected from Ο-4-alkyl, Ci-4-alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, phenyl -, phenoxy, naphthoxy, amino, N-mono or di-O-4-alkyl or C2-4-hydroxyalkyl-amino, N-phenyl or N-naphthyl-amino groups, or R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ⁷ and R ⁸ to form 1, 2 or 3 carbocyclic or O, NR ¹⁰ - or S-heterocyclic, optionally aromatic and / or optionally Ci-6-alkyl-substituted rings are interconnected.

Use or agent according to one of the preceding claims, characterized in that the protease is selected from

a) Proteases comprising an amino acid sequence which is increasingly preferably at least 75%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87 of the amino acid sequence given in SEQ ID NO: 1 over the entire length thereof %, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95% , 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99% is identical,

b) Proteases comprising an amino acid sequence which, at the amino acid sequence given in SEQ ID NO: 2, is increasingly more preferably at least 75%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87 over the entire length thereof %, 88%, 89%, 90%, 90.5%, 91%, 91, 5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95% , 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99% is identical, and

c) their mixtures.