DE102013215810A1 - Detergent with increased primary washing power - Google Patents

Abstract

The primary washing power of peroxygen-containing detergents and cleaners should be improved. This was achieved by the use of a combination of lipase with an acylhydrazone.

Description

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 soils, 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.

in der R¹ für eine CF₃ oder für eine C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, Phenyl-, Naphthyl-, C_7-9-Aralkyl, C_3-20-Heteroalkyl- oder C_3-12-Cycloheteroalkylgruppe,
R² und R³ unabhängig voneinander für Wasserstoff oder eine gegebenenfalls substituierte C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-28-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkyl-, Phenyl-, Naphthyl- oder Heteroarylgruppe oder R2 und R3 zusammen mit dem sie verbindenden Kohlenstoffatom für einen gegebenenfalls substituierten 5-, 6-, 7-, 8- oder 9-gliedrigen Ring, der gegebenenfalls Heteroatome enthalten kann, und
R⁴ für Wasserstoff oder eine C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkylgruppe oder eine gegebenenfalls substituierte Phenyl- oder Naphthyl- oder Heteroarylgruppe stehen, zur Verstärkung der Primärwaschkraft von persauerstoffhaltigen Wasch- und Reinigungsmitteln. The invention relates to the use of a combination of lipase with an acylhydrazone of the general formula (I)

in the R ^{1 is} a CF ₃ or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl- , Phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl,
R ² and R ³ are each independently hydrogen or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl, or R 2 and R 3 together with them connecting carbon atom for 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 _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 -Aralkyl-, C _3-20 -Heteroalkyl-, C _3-12 -cycloheteroalkyl-, C _5-16 -Heteroaralkylgruppe or an optionally substituted phenyl or naphthyl or heteroaryl group, for enhancing the Primärwaschkraft of oxygen-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 ¹ 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.

in der R¹ für eine C_1-4-Alkylgruppe, die einen Substituenten ausgewählt aus

trägt, in dem R¹⁰ für Wasserstoff oder eine C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkylgruppe und A^– für das Anion einer organischen oder anorganischen Säure steht, R² und R⁴ die für Formel (I) angegebenen Bedeutung haben und
R⁵, R⁶, R⁷ und R⁸ unabhängig voneinander für R¹, Wasserstoff, Halogen, eine Hydroxy-, Amino-, eine gegebenenfalls substituierte N-mono- oder di-C_1-4-alkyl- oder C_2-4-hydroxyalkyl-amino-, N-Phenyl- oder N-Naphthyl-amino-, C_1-28-Alkyl-, C_1-28-Alkoxy-, Phenoxy-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkyl-, Phenyl- oder Naphthylgruppe stehen, wobei die Substituenten ausgewählt werden aus C_1-4-Alkyl-, C_1-4-Alkoxy-, Hydroxy-, Sulfo-, Sulfato-, Halogen-, Cyano-, Nitro-, Carboxy-, Phenyl-, Phenoxy-, Naphthoxy-, Amino-, N-mono- oder di-C_1-4-alkyl- oder C_2-4-hydroxyalkyl-amino-, N-Phenyl- oder N-Naphthyl-aminogruppen, oder
R⁵ und R⁶ oder R⁶ und R⁷ oder R⁷ und R⁸ unter Ausbildung von 1, 2 oder 3 carbocyclischen oder O-, NR¹⁰- oder S-heterocyclischen, gegebenenfalls aromatischen und/oder gegebenenfalls C_1-6-alkylsubstituierten Ringen miteinander verbunden sind. Preferred embodiments of the compounds according to general formula (I) include those of general formula (II),

in the R ^{1 is} a C _1-4 alkyl group having a substituent selected from

in which R ^{10 represents} hydrogen or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl-, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, 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 independently of one another are R ¹ , hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono- or di-C _1-4 -alkyl or C _2-4 -hydroxyalkylamino, N-phenyl or N-naphthylamino, C _1-28 alkyl, C _1-28 alkoxy, phenoxy, C _2-28 alkenyl, C _2-22 Alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl , Phenyl or naphthyl group, wherein the substituents are selected from C _1-4 alkyl, C _1-4 alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, Phenyl, phenoxy, naphthoxy, amino, N-mono- or di-C _1-4 alkyl or C _2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino 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 are interconnected.

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 in 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. In the present invention, preferred lipases are derived from the fungus Humicola lanuginosa, such as the commercially available lipases Lipolase ^®, Lipolase Ultra ^® and Lipex ^® particular.

The cleaning-active effects of the lipase are retained in the presence of simultaneously present acylhydrazone. 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 controlled by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II) - (III) - (IV) - (V), Cu ( I) - (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 are also 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 H ₂ O, NH ₃ , CH ₃ OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C _2-18 -carboxylate, a C _1-18 alkyl sulfate, especially methosulfate, or a corresponding alkanesulfonate, inorganic anions such as halide, especially chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, bisulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.

In the context of the use according to the invention, it is preferred if the concentration of the compound of the formula (I) in an aqueous liquor, as used, for example, in washing machines or dishwashers, is 0.5 μmol / l to 500 μmol / l, in particular 5 μmol / l to 100 .mu.mol / l. 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 H ₂ O ₂ ) 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 of 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 which comprises 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). 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 of formula (I) is preferably in the range of 0.001: 1 to 2: 1, especially 0.01: 1 to 1: 1. In a further preferred embodiment of the compositions, 0.05 to 1% by weight, in particular 0.1 to 0.5% by weight, of bleach-enhancing complex containing a ligand of the formula I) included. Preferred transition metal is Mn.

As peroxygen compounds contained in the agents are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxoacid salts, such as alkali metal or peroxodisulfate Caroate, or Diacylperoxide or Tetraacyldiperoxide, hydrogen peroxide and among the Washing conditions hydrogen peroxide-releasing substances, such as alkali metal perborates, alkali metal peroxides, 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 from 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 H ₂ O ₂ releasing peroxygen compound, a conventional bleach activator is used together with the acylhydrazone 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 give peroxocarboxylic acid under perhydrolysis conditions can in particular be compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, 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, especially nonanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), their formal carbonic ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benzenesulfonate (DECOBS), acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose, acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam.

in der R¹¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_1-24-Alkyl- oder C_2-24-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN und -N⁽⁺⁾-CH₂-CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C_1-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R¹² und R¹³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃,-CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6, R¹⁴ und R¹⁵ unabhängig voneinander eine voranstehend für R¹¹, R¹² oder R¹³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R¹² und R¹³, auch unter Einschluß des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C_9-15-Alkylbenzolsulfonaten, den C_1-20-Alkylsulfaten, den C_8-22-Carbonsäuremethylestersulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden. Auch sauerstoffübertragende Sulfonimine können eingesetzt werden. In addition to 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

in the R ^{11 is} -H, -CH ₃ , a C _2-24 -alkyl or alkenyl radical, a substituted C _1-24 -alkyl or C _2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN and -N ⁽⁺⁾ -CH ₂ -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C _1-24 -alkyl group (s) and optionally further substituents on the aromatic ring, R ¹² and R ^{13 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) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6, R ¹⁴ and R ¹⁵ independently of one another have the meaning given above for R ¹¹ , R ¹² or R ¹³ , where at least 2 of the radicals mentioned, in particular R ¹² and R ¹³ , are also suitable under Einsc Can be linked ring-closing of the nitrogen atom and optionally further heteroatoms and then preferably form a morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, C _9-15 -alkylbenzenesulfonates, C _1-20 -alkyl sulfates, C _8-22 -carboxylic _acid methyl _ester sulfonates, sulfate, hydrogensulfate and whose mixtures are, can be used. Oxygen-carrying sulfonimines can also be used.

In order to avoid the interaction with the peroxygen compounds, the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1.5% by means of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile 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, pyridazine, 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-triazacyclononane, 1.5 , 9-triazacyclododecane and its substituted derivatives such as 1,5,9-trimethyl-1,5,9-triazacyclododecane 1,4,8,11-tetraazacyclotetradecane and its substituted derivatives such as 5,5,7,12,12,14- Hexamethyl-1,4,8,11-tetraazacyclotetradecane, 1,5,8,12-tetraazabicyclo [6.6.2] hexadecane and its substituted derivatives such as 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [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-benzimidazo lylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ', N'-tetrakis (2-benzimidazolylmethyl) -2-hydroxy-1, 3-diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3-bis (bis (2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol, erythritol, 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 bridge two transition metal atoms asymmetrically or η ¹ -O-bridge. 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, for example, nitrate, actetate, 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 binuclear 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 transition metal complex compounds that can be used are Mn (IV) 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-OO-Co (NH ₃ ) ₅ ] Cl ₄ .

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) and optionally also the said bleach activators and catalysts such agents usual ingredients contain. 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 polymer preservatives, and further adjuvants, such as optical brighteners, foam regulators, dyes and fragrances.

An agent may be used to further enhance the disinfecting effect, for example against specific germs, in addition conventional antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bound 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 theirs 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. Furthermore, corresponding ethoxylation and / or propoxylation of N-alkyl-amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl part, and of alkylphenols having 5 to 12 carbon 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 hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), Ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) 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 thereof which may also contain polymerized 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 5000 g / mol and 200000 g / mol, of the copolymers between 2000 g / mol and 200000 g / mol, preferably 50,000 g / mol 120000 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, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content 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 acid Monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, 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, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example 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 Maleinate 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 can also be a derivative of an allylsulfonic acid which is 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 substituted. 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 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat 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 1000 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. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred. 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 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally 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 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 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O 2 _{+ x 1} · yH ₂ O are used in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 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 β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Also produced from amorphous alkali metal silicates, practically anhydrous crystalline Alkali silicates of the abovementioned general formula in which x is an integer 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 1.9 to 3.5 are used in a further embodiment. In a preferred embodiment of such means is a granular compound of alkali metal silicate and alkali, such as is available, for example under the name Nabion ^® 15 commercially.

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 agents in the compositions is generally not more than 2 wt .-%, and is preferably 0.5 wt .-% to 1.5 wt .-%.

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, carry a diethanolamino group, a methylamino group or 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, brighteners of the 1,3-diaryl-2-pyrazolines type, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable. The content of the composition in optical brighteners or brightener 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 preferably being silanated 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, by the mixture of the other components not automatically resulting pH, the agents can system and environmentally acceptable acids, in particular 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 agents 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 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 having the composition given in Table 1 below (Ingredients in% by weight) were tested at 20 ° C in washing trials at a dosage of 80 g per 17 l of water in a ^Miele® washing machine. Table 1: Detergent compositions ingredient V1 V2 V3 E1 LAS-Na 10.6 10.6 10.6 10.6 FA 7 EO 3 3 3 3 C _16/18 Na soap 1.2 1.2 1.2 1.2 HEDP-Na ₄ 0.81 0.81 0.81 0.81 polyacrylate 2.2 2.2 2.2 2.2 Sodium silicate 2.1 5.7 5.7 5.7 5.7 sodium 22 22 22 22 sodium 10 10 10 10 TAED 3 3 3 3 Acylhydrazone ¹⁾ - - 0.09 0.09 carboxymethylcellulose 2.5 2.5 2.5 2.5 defoamers 0.046 0.046 0.046 0.046 Protease / amylase / cellulase 0.61 0.61 0.61 0.61 Lipase (Lipex ^®) - 0.005 - 0.005 Optical brightener 0.183 0.183 0.183 0.183 Perfume 0.3 0.3 0.3 0.3 sodium sulphate on 100 ¹⁾ 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: Soiling soiling Origin / Art Textile ^a) Apple-banana puree Hipp, Mild fruit porridge CO Blueberry juice Rabenhorst CO cherry juice Odenwald CO currysauce Bold 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 Dr. Oetker CO cocoa Bensdorp premium quality with milk CO Mousse au chocolat, cold Dr. Oetker, mixed with water CO Mousse au chocolat, powder Dr. Oetker CO sheep blood blood CO spaghetti sauce Barilla, Base by Bolognese PES Tomato sauce Knorr, Tomato al Gusto PES Chocolate Ice Cream Lagnese Cremissimo PES jam Classic, wildberries PES salad dressing Bold, balsamic PES Machine oil, used Henkel's auto repair shop PES Frying fat, used Henkel's kitchen PES garden soil WFK PES gravy Knorr PES Lard, used Lard PES Lipstick, 453 rose L'Oreal PES Lipstick, Sweet Nectarine 83 jade PES Make up, Lóreal K3 Rose Beige LÒREAL, le teint Perfect Match PES Make up, Sans Soucis No. 40 Bronze Rose PES olive oil Bertolli, extra virgin PES spaghetti sauce Barilla, Base by Bolognese CO Tomato sauce Knorr, Tomato al Gusto CO Chocolate Ice Cream Lagnese Cremissimo CO jam Classic, wildberries CO salad dressing Bold, balsamic CO Machine oil, used Henkel's workshop CO Frying fat, used Henkel's kitchen CO garden soil WFK CO gravy Knorr CO Lard, used Lard CO Lipstick, 453 rose L'Oreal CO Lipstick, Sweet Nectarine 83 jade CO Make up, Lóreal K3 Rose Beige L'Òreal L, le teint Perfect Match CO Make up, Sans Soucis No. 40 Bronze Rose CO olive oil Bertolli, extra virgin CO CFT C03 Chocolate milk / carbon black CO CFT C05 Blood / milk / ink CO CFT CS02 cocoa CO CFT CS29 Tapioca starch, colored CO EMPA 111 blood CO EMPA 112 cocoa CO EMPA 117 Blood / milk / ink PES / CO EMPA 160 chocolate cream CO EMPA 162 Corn starch, colored 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 BUA coffee CO HTB tea CO WFK 10BB blackberry CO WFK 10JB Blackcurrant 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 / Nature blackness CO CFT CS26 Corn starch, colored CO CFT CS28 Rice starch, colored 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 Make up CO CFT CS216 Lipstick red CO CFT CS32 Sebum / Carbon black CO CFT PCS16 Lipstick, pink PES / CO WFK 20D Pigment / sebum PES / CO ^a) CO = cotton; PES = polyester; PES / CO = polyester-cotton blend

In the direct comparison of the means V1 and V2, V2 had a higher washing performance on 4 stains and was the same for 86 soiling within the measuring accuracy (here and in the following: 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 a direct comparison of the means V1 and V3, V3 had a higher washing performance on 10 stains and was equal to 80 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 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 (9)

Use of a combination of lipase with an acylhydrazone of the general formula (I),

in the R ^{1 is} a CF ₃ or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl- , Phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl, R ² and R ³ independently of one another represent hydrogen or an optionally substituted C _1-28 -alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _{3 -12-} cycloheteroalkyl, C _5-16 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 C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 -Aralkyl-, C _3-20 -Heteroalkyl-, C _3-12 -cycloheteroalkyl-, C _5-16 -Heteroaralkylgruppe or an optionally substituted phenyl or naphthyl or heteroaryl group, for enhancing the Primärwaschkraft of oxygen-containing detergents and cleaners. Use according to Claim 1, characterized in that the concentration of the compound of the formula (I) in an aqueous liquor is 0.5 μmol / l to 500 μmol / l, in particular 5 μmol / l to 100 μmol / l. Use according to claim 1 or 2, characterized in that the peroxygen concentration (calculated as H ₂ O ₂ ) 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 lies. Detergents or cleaning compositions containing a persoxy-containing bleaching agent and a combination of lipase and a compound of the formula (I)

in the R ^{1 is} a CF ₃ or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl- , Phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl, R ² and R ³ independently of one another represent hydrogen or an optionally substituted C _1-28 -alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _{3 -12-} cycloheteroalkyl, C _5-16 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 C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _{3- 12} -cycloalkenyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl, C _3-12 -cycloheteroalkyl, C _5-16 -Heteroaralkylgruppe or an optionally substituted ierte phenyl or naphthyl or heteroaryl group. 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). Composition according to claim 4 or 5, characterized in that it lipase, in particular from the fungus Humicola lanuginosa dissipative lipase, in amounts of 0.0005 wt .-% to 0.025 wt .-%, in particular 0.0025 wt .-% bis 0.01 wt .-%, each based on active protein. Agent according to one of claims 4 to 6, characterized in that it contains peroxygen compounds in amounts of up to 50 wt .-%, in particular from 2 wt .-% to 45 wt .-%. Agent 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 .-%. 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 ^{1 is} a C _1-4 alkyl group having a substituent selected from

in which R ^{10 represents} hydrogen or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl-, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, and A ^{- represents} the anion of an organic or inorganic acid; R ² and R ^{4 represent} the Formula (I) and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently R ¹ , hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono- or di-C _1-4 alkyl or C _2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino, C _1-28 alkyl, C _1-28 alkoxy, phenoxy, C _2-28 Alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl, C _3-12 -cycloheteroalkyl- , C _5-16 heteroaralkyl, phenyl or naphthyl, wherein the substituents are selected from C _1-4 alkyl, C _1-4 alkoxy, hydroxy, sulfo, sulfato, halo, cyano , Nitro, carboxy , Phenyl, phenoxy, naphthoxy, amino, N-mono- or di-C _1-4 -alkyl or C _2-4 -hydroxyalkylamino, N-phenyl or N-naphthylamino 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 are interconnected.