EP3030642A1

EP3030642A1 - Washing agent having increased primary washing efficiency

Info

Publication number: EP3030642A1
Application number: EP14747907.5A
Authority: EP
Inventors: André HÄTZELT; Johannes Zipfel; Arnd Kessler; Timothy O'connell
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2013-08-09
Filing date: 2014-07-31
Publication date: 2016-06-15
Anticipated expiration: 2034-07-31
Also published as: PL3030642T3; EP3030642B1; WO2015018728A1; DE102013215810A1

Abstract

The problem addressed by the invention is that of boosting the primary washing efficiency of oxygen-containing washing and cleaning agents. This problem is solved by using a combination of lipase and an acyl hydrazone.

Description

Detergent with increased primary washing power

The present invention relates to the use of a combination of lipase and certain acylhydrazones for enhancing the primary detergency of laundry detergents or cleaners when washing textiles or cleaning hard surfaces against, in particular, bleach or enzyme sensitive stains, and detergents and cleaners containing such a combination.

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.

The invention relates to the use of a combination of lipase with an acylhydrazone of the general formula (I),

in the R represents a CF 3 or represents a C 1-8 -alkyl, C 2-30 alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 -cycloalkenyl, phenyl, naphthyl-, C7-9 aralkyl, C3-2o heteroalkyl or C3-12 cycloheteroalkyl group,

R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-28 -alkyl, C 2-30 -alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 cycloalkenyl, C 7- 9-aralkyl, C3-28-heteroalkyl, C3-i2-cycloheteroalkyl, C5-i6-heteroaralkyl, phenyl, naphthyl or heteroaryl or R2 and R3 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 d-28-alkyl, C 2-18 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3- 2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-i6-heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group

to enhance the primary washing power of peroxygen-containing detergents and 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 Ο-4-alkyl group having a substituent selected from

_R 10 _R 10 _R o _R 10

- HO A-; N ⁺ S A-; ^~ ! A-; -NIA ^"

v __ / \ / \ o - - s 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, C7-9 aralkyl, C3-2o heteroalkyl, C3-i2 cycloheteroalkyl, C5-16 heteroaralkyl group and A ^"represents the anion of an organic or inorganic acid, R ² and R ^{4 represent} the Have the meaning given in 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-d-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)

A lipase is an enzyme that catalyzes the hydrolysis of ester bonds in lipid substrates, especially in fats and oils. Lipases are therefore a subset of esterases. Lipases are generally versatile enzymes that accept a variety of substrates, for example, aliphatic, alicyclic, bicyclic and aromatic esters, thioesters and activated amines. Lipases act against fat residues in the laundry by catalyzing their hydrolysis (lipolysis). Lipases with broad substrate spectra are used in particular where inhomogeneous raw materials or substrate mixtures have to be reacted, for example in detergents and cleaning agents, since soiling usually consists of differently structured fats and oils. The lipases known from the prior art are usually of microbial origin and are usually derived from bacteria or fungi, for example the genera Bacillus, Pseudomonas, Acinetobacter, Micrococcus, Humicola (Thermomyces), Trichoderma or Trichosporon. Lipases are usually produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi. Lipases preferred in the context of the present invention are derived from the fungus Humicola lanuginosa, such as, for example, the commercially available Lipases Lipolase®, Lipolase Ultra®, and in particular Lipex®.

The cleaning-active effects of the lipase are retained in the presence of simultaneously present acylhydrazones. Likewise, the cleaning-active effects of acylhydrazone remain in the presence of simultaneously present lipase. The combined use of lipase and acylhydrazone results in a greater number of improved soilings removed than the sum of improved soilings removed using the two active ingredients individually, 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.

In the context of the inventive use is preferred if the concentration of the compound of formula (I) in 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 amounts. 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. OF PREFERRED Te peroxygen concentrations (calculated as H2O2) in the liquor range from 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l and more 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 lipase 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 containing peroxygen compound, lipase and a compound of formula (I) or a bleach catalyst obtainable from complexing with a transition metal ion thereof in the washing of textiles requiring cleaning. Alternatively, the peroxygen compound and / or the compound of formula (I) and / or a complex obtainable therefrom and / or the lipase may also be added separately to a wash liquor which has a detergent without the particular ingredient mentioned. The same applies to cleaning agents for hard surfaces in the inventive use, for example in the context of a dishwashing process.

Another object of the invention is a detergent or cleaning agent containing a peroxygen bleaching agent and a combination of lipase and a compound of formula (I). 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.

Lipase is preferably contained in agents according to the invention in amounts of from 0.0005% by weight to 0.025% by weight, in particular from 0.0025% by weight to 0.01% by weight, based in each case on active protein.

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). Especially when containing a compound of the formula (I) In addition, 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 one Compound according to formula (I) corresponds contains. 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.

In particular, compounds which give perbenzoic acid optionally substituted perhydrolysis under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms, alone or in mixtures, can be used as the peroxycarboxylic acid-yielding compound. Suitable bleach activators are the O- and / or N-acyl groups, in particular of the stated C atom number and / or, where appropriate bear 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 to or as an alternative to the compounds which form peroxocarboxylic 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 can be linked ring-closing with one another and then preferably form a morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, the C9-i5-alkylbenzenesulfonates, the Ci-20-alkyl sulfates, the C8-22 methyl carboxylate 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 may also be chelated to a transition metal or it may be asymmetric or two transition metal atoms -0-bridging. In addition to the ligands mentioned, the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands. In question are, for example, 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 which may be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, may in principle all known and in addition to the combination of lipase and compound according to formula (I) to be used according to the invention and optionally also the said bleach activators and catalysts such agents contain conventional ingredients. 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 other adjuvants, such as optical brighteners, foam regulators, dyes and fragrances.

An agent can for further enhancing the disinfecting action, for example against specific germs, additionally customary 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, benzamidines, 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, other oxidizing agents and inorganic nitrogen compounds. 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, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and Hydroxyiminodisuccinate, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, especially Aminotris (methylenphosphonic acid), ethylenediaminetetrakis- (methylenephosphonic acid), lysintetra (methylenphosphosäure) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by Oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain copolymerized small amounts of polymerizable substances without carboxylic acid functionality. 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% by weight to 25% by weight of methallylsulphonic acid or methallylsulphonate and as the third monomer 15% by weight to 40% by weight, preferably 20% to 40% by weight 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 metal silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 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 similarly constructed compounds which are suitable instead of the morpholino group, a diethanolamino group, a methylamino group or carry a 2-methoxyethylamino 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 brightener mixtures is generally not more than 1% by weight and preferably in the range from 0.05% by weight to 0.5% by weight.

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 agents 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 lipase- and acylhydrazone-free powdered detergent V1, an otherwise identical lipase-containing detergent V2, an otherwise identical with V1 acylhydrazon-containing detergent V2, and a lipase and acylhydrazon-containing detergent E1 with the in the following Table 1 given composition (ingredients in wt .-%) were at

20 ° C in washing tests at a dosage of 80 g per 17 l of water in a Miele® washing machine tested.

Table 1: Detergent compositions

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

In addition to clean filling laundry, the following standardized soiling was used: Table 2: Stains

Soiling Origin / Art Textile ^a >

Apple banana porridge Hipp, Mild fruit pulp CO

Blueberry juice Rabenhorst CO

Cherry juice Odenwald CO

Curry sauce Kühne fruity-exotic CO

Espresso Espresso Senseo CO

Grass grass CO

Tomato ketchup Heinz CO

Red wine Bordeaux CO

Spinach spinach SPAR CO

Tea Messner, Assam Ceylon 10 CO

Chocolate pudding, powder Oetker CO

Cocoa Bensdorp premium quality with milk CO

Mousse au chocolat, cold dr. Oetker, mixed with water CO

Mousse au chocolat, powder Oetker CO

Sheep blood blood CO

Spaghetti sauce Bariila, Base bolognese PES

Tomato sauce Knorr, Tomato al Gusto PES

Chocolate Ice Cream Lagnese Cremissimo PES

Jam Classic, wildberries PES

Salad Dressing Kühne, Balsamic PES

Machine oil, used Henkels Auto Repair PES

Frying fat, used Henkel's kitchen PES

Garden earth WFK PES

Gravy Knorr PES

Lard, used Lard PES

Lipstick, 453 rose L'Oreal PES

Lipstick, Sweet Nectarine 83 Jade PES

Make up, Loreal K3 Rose Beige LÖREAL, le complexion Perfect Match PES

Make up, Sans Soucis No. 40 Bronze Rose PES

Olive oil Bertolli, Extra Vergine PES

Spaghetti sauce Bariila, Base bolognese CO

Tomato sauce Knorr, Tomato al Gusto CO

Chocolate Ice Cream Lagnese Cremissimo CO

Jam Classic, wildberries CO Salad Dressing Kühne, Balsamico CO

Machine Oil, used Henkels Workshop CO

Frying fat, used Henkels kitchen CO

Garden earth WFK CO

Gravy Knorr CO

Lard, used Lard CO

Lipstick, 453 rose L'Oreal CO

Lipstick, Sweet Nectarine 83 Jade CO

Make up, Loreal K3 Rose Beige L'Oreal L, le teint Perfect Match CO

Make up, Sans Soucis No. 40 Bronze Rose CO

Olive oil Bertolli, Extra-Vergine CO

CFT C03 chocolate milk / carbon black CO

CFT C05 Blood / Milk / Ink CO

CFT CS02 Cocoa CO

CFT CS29 tapioca starch, dyed CO

EMPA 1 1 1 blood CO

EMPA 1 12 Cocoa CO

EMPA 1 17 Blood / Milk / Ink PES / CO

EMPA 160 chocolate cream CO

EMPA 162 corn starch, dyed PES / CO

EMPA 163 Porridge CO

EMPA 165 chocolate pudding CO

H-MR-B Milk / soot CO

WFK 10EG egg yolk CO

WFK 10N egg / pigment CO

WFK 10R corn starch / pigment CO

CFT BC1 tea for medium and high temperature CO

CFT CBC05 Beetroot CO

CFT CS03 red wine, aged CO

EMPA 167 Tea CO

H-K-B Coffee CO

H-T-B Tee CO

WFK 10BB blackberry juice CO

WFK 10JB Black Currant Juice CO

WFK 10U Curry CO

WFK 10WB Blueberry juice CO

CFT BC2 Coffee CO CFT BC3 tea for low temperature CO

CFT CS08 Grass CO

CFT CS103 red wine, fresh CO

CFT CS12 Blackcurrant CO

CFT CS15 Blueberry juice CO

CFT CS06 Salad Dressing / Natural Black CO

CFT CS26 corn starch, dyed CO

CFT CS28 rice starch, dyed CO

CFT CS37 egg / pigment CO

CFT CS44 chocolate drink CO

CFT C01 carbon black / mineral oil CO

CFT C02 Olive oil / carbon black CO

CFT C09 pigment / oil CO

CFT CS05S mayonnaise / carbon black CO

CFT CS17 Makeup CO

CFT CS216 lipstick red CO

CFT CS32 Sebum / Carbon black CO

CFT PCS 16 lipstick, pink PES / CO

WFK 20D pigment / sebum PES / CO CO = cotton; PES = polyester; PES / CO = polyester-cotton blend

In the case of direct comparison of the means V1 and V2, V2 had a higher washing performance on 4 soiling and was the same for 86 soiling within the scope of the measuring accuracy (here and below: 6-fold determination). In a direct comparison of the means V1 and V3, V3 had a higher washing performance on 21 stains and was equal to 69 soiling within the scope of the measuring accuracy. In a direct comparison of the means V1 and E1, E1 had a higher washing performance on 27 soilings and was equal to 63 soiling within the scope of the measuring accuracy. The simultaneous use of both ingredients surprisingly showed a greater number of advantages (27) than the sum of the individually used ingredients (21 +4). The superiority of E1 was especially pronounced on the stains blood / milk / ink and olive oil / soot.

Carrying out the washing tests under otherwise identical conditions at 40 ° C. showed V2 a direct comparison of the agents V1 and V2 with a higher washing power on 6 soils and a lower washing power on 1 soiling and was the same for 83 soils within the measuring accuracy. In direct comparison of the means V1 and V3, V3 had a higher washing performance on 10 soiling and was subject to 80 soiling within the scope of the measuring accuracy equal. In a direct comparison of the means V1 and E1, E1 had a higher washing performance on 19 stains and was equal to 71 soiling within the scope of the measuring accuracy. The simultaneous use of both ingredients surprisingly showed a greater number of advantages (19) than the sum of the individually used ingredients (10 + 6 (-1)). In particular, the soils curry sauce, blood / milk / ink, curry and olive oil / soot, the superiority of the agent E1 was strong.

Claims

claims

1. Use of a combination of lipase with an acylhydrazone of the general formula

in the R represents a CF 3 or a C-28-alkyl, C 2-30 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, phenyl, naphthyl, C7-9 aralkyl, C3-2o heteroalkyl or C3-12 cycloheteroalkyl group,

R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-8 -alkyl, C 2-18 -alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 -cycloalkenyl, C 7- 9-aralkyl, C3-28 heteroalkyl, C3-i2-cycloheteroalkyl, C5-i6 heteroaralkyl, phenyl, naphthyl or heteroaryl group or R2 and R3 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-28-alkyl, C 2-18 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3- 2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl

Use according to claim 1, characterized in that the concentration of the compound of formula (I) in aqueous liquor is 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 is in the range from 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l ,

4. washing or cleaning agent containing a peroxygen bleaching agent and a combination of lipase and a compound of formula (I)

in the R is a CF3 or a Ci-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 group or R2 and R3 together with the carbon atom connecting them for an optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and

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 lipase, in particular of the fungus Humicola lanuginosa dissipative lipase, in amounts of 0.0005 wt .-% to 0.025 wt .-%, in particular 0.0025 wt. % to 0.01 wt .-%, each 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 45 wt.

contains%.

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 Ο-4-alkyl group having 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, 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, C 2-18 alkenyl, C 2-22 alkynyl, C 3- i2-cycloalkyl, C3-i2-cycloalkenyl, C7-9-aralkyl, C3-2o-heteroalkyl, C3-12-cycloheteroalkyl, C5-i6-heteroaralkyl, phenyl or naphthyl group, wherein the substituents are selected are from Ci-4-alkyl, Ci-4-alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, phenyl, phenoxy, naphthoxy, amino, N mono or di-Ci-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 connected to each other.