EP1084223B1 - Detergents containing amylase and transition metal compound activating bleaching - Google Patents

Abstract

The invention aims at improving the cleaning performance of detergents containing enzymes, especially in relation to starch-containing and dyed stains. This is substantially achieved in that the detergent contains alpha -amylase from Bacillus amyloliquefaciens and a transition metal compound activating bleaching, in addition to other usual ingredients compatible with said constituents.

Description

The present invention relates to enzyme-containing detergents and cleaning agents which, in addition to usual components a naturally occurring amylase from Bacillus amyloliquefaciens and certain contain bleach-activating agents.

Detergents contain the ingredients that are essential for the washing process such as surfactants and builder materials, usually other components that can be found under the term washing aids can summarize and the different groups of active ingredients such as foam regulators, graying inhibitors, bleach, Bleach activators and color transfer inhibitors include. To such hill fabrics also include substances that affect the surfactant performance due to the enxymatic degradation support from soiling on the textile. The same applies analogously also for cleaning agents for hard surfaces. Besides that comes the Proteases supporting the protein removal and the fat-splitting lipases Amylases are of particular importance. Amylases have the task of removing Starchy soiling due to the catalytic hydrolysis of the starch polysaccharide to facilitate and have been in for this purpose for a long time Detergents for dishes, but also in detergents for use in the Textile laundry used To date, the vast majority of these have been used a thermostable amylase from Bacillus lichenifonnis, for example, under the Termamyl® is commercially available. More recently come in such means Increased genetically modified amylases, that is, compared to natural occurring amylases with the aid of genetic engineering methods modified amino acid sequence, for use. In addition to increasing its performance, the Genetic modification of amylases essentially increases the stability of the Enzyme, especially against the attack of oxidizing agents. An approach to To achieve this goal, which is proposed in international patent application WO 94/18314 consists in removing amino acids that are particularly susceptible to oxidation, such as methionine, tryptophan, cysteine or tyrosine, from the amino acid sequence of the Amylase, or its replacement by other, more oxidation stable amino acids. On A similar procedure is also used in international patent application WO 95/21247 suggested that recommends at least one in the amylase amino acid sequence Exchange methionine with an amino acid that is neither methionine nor cysteine.

Although such genetic modifications lead to improved amylase stability can lead under certain application conditions, but do not wear them to increase the contribution of amylase to the washing or Cleaning performance of appropriate agents in which the amylase is contained.

Surprisingly, it has now been found that the combination of a naturally occurring α-Amylase with certain bleach-activating agents to unexpected synergistic performance improvements results when you are in essence or Uses cleaning agents.

The invention therefore relates to an amylase-containing washing or cleaning agent, which is a naturally occurring α-amylase from Bacillus amyloliquefaciens and a bleach-enhancing transition metal complex compound in addition to usual compatible with such components Contains ingredients.

Another object of the invention is the use of a corresponding Combination to increase the cleaning performance of detergents and cleaning agents, especially against starchy and / or colored, in particular tea-based soiling, when used in aqueous washing and cleaning solutions, which contain a peroxygen compound. The cleaning performance compared colored stains are to be understood and included in their broadest meaning both the bleaching of dirt on the textile, the bleaching of dirt in the wash liquor, detached from the textile as well as that oxidative destruction of textile dyes in the wash liquor, which are under detach the washing conditions from textiles before moving onto textiles of different colors can raise. Also when used in cleaning solutions for hard surfaces under this term both the bleaching of what is on the hard surface Dirt, especially tea, as well as bleaching in the dishwashing liquor dirt that is detached from the hard surface.

α-Amylase from Bacillus amyloliquefaciens has long been, for example, from the United States Patent US 1,227,374 known. For example, it is under the Description Amylase BAN® commercially available.

An agent according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of amylolytic protein per gram of the total agent. The protein concentration can be determined using known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (AG Gomall, CS Bardawill and MM David, J. Biol. Chem. 177 , 751-766, 1948).

The bleach-enhancing transition metal complex compound is preferably obtained from the Complex compounds of Mn, Fe, Co, Cu, Mo, V, Ti or Ru or their mixtures selected. Concerning the bleach-reinforcing transition metal complex compounds in question include in particular those from the international patent application WO 97/07192 known manganese, iron, cobalt, ruthenium or molybdenum salt complexes and those known from international patent application WO 97/44430 N-analog connections, which are derived from German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the in the international patent application WO 97/30144 manganese, iron, Cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogenous tripod ligands derived from the international Patent application WO 97/36988 known cobalt, iron, copper and ruthenium amine complexes, the in the German patent applications DE 197 57 918 and DE 198 09 713 complexes with dendrimer ligands described in the German Patent application DE 44 16 438 described manganese, copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent application EP 0 693 550, the manganese, iron, cobalt and known from European patent EP 0 392 592 Copper complexes which are derived from international patent applications WO 96/23859, WO 96/23860 and WO 96/23861 known cobalt complexes and / or those in the European patent EP 0 443 651 or the European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and Manganese complexes described in EP 0 544 519. Bleach-activating transition metal complex compounds are preferably used in an amount of up to 1% by weight, in particular from 0.001% by weight to 0.25% by weight and particularly preferably from 0.015 wt .-% to 0.1 wt .-%, each based on transition metal, in the invention Funds used.

in der

UM

fiir Mangan, Eisen, Cobalt, Ruthenium oder Molybdän steht,

R

für einen Alkylen-, Alkenylen-, Phenylen- oder Cycloalkylenrest steht, welcher zusätzlich zum Substituenten X gegebenfalls alkyl- und/oder arylsubstituiert sein kann, mit insgesamt 1 bis 12 C-Atomen, wobei innerhalb R der kürzeste Abstand zwischen den mit UM komplexierenden N-Atomen 1 bis 5 C-Atome beträgt,

X

für -H, -OR³, -NO₂, -F, -Cl, -Br oder -J steht,

R¹, R² und R³

unabhängig voneinander fiir Wasserstoff oder einen Alkylrest mit 1 bis 4 C-Atomen stehen,

Y¹ und Y²

unabhängig voneinander für Wasserstoff oder einen elektronenverschiebenden Substituenten stehen, wobei Y¹ und Y² nicht gleichzeitig Wasserstoff sind, wenn R Alkylen oder Cyclohexylen ist,

Z¹ und Z²

unabhängig voneinander für Wasserstoff, -CO₂M, -SO₃M oder -NO₂ stehen,

M

für Wasserstoff oder ein Alkalimetall wie Lithium, Natrium oder Kalium steht und

A

für einen ladungsausgleichenden Anionliganden steht,

oder Komplexen der Übergangsmetalle Mangan, Eisen, Cobalt, Ruthenium, Molybdän, Titan, Vanadium und/oder Kupfer, die einen oder mehrere der Liganden III

in denen R eine direkte Bindung oder eine gegebenenfalls aminogruppen-substituierte Alkylengruppe mit 1 bis 4 C-Atomen ist, A fiir ein kondensiertes oder nichtkondensiertes Ringsystem steht, welches mindestes ein Stickstoffatom enthält, und B Wasserstoff, eine OH-Gruppe oder A ist, oder der allgemeinen Formel IV besitzen

in denen A und R die für Formel III gegebene Bedeutung haben und X ein gegebenenfalls hydroxy- und/oder C_1-4-alkylsubstiuierter Phenylenring oder eine gegebenenfalls hydroxysubstituierte C_1-4-Alkylengruppe ist, ausgewählt. In einer bevorzugten Ausgestaltung erfmdungsgemäßer Mittel weist die Übergangsmetallkomplexverbindung mindestens einen gegebenenfalls N-alkylierten Triazacyclononan-Liganden auf. Eine weitere bevorzugte Ausgestaltung erfindungsgemäßer Mittel enthält die bleichverstärkende Übergangsmetallkomplexverbindung in Form einer Wirkstoffkombination, die durch inniges Vermischen eines wasserlöslichen Salzes eines zweiwertigen Übergangsmetalles, ausgewählt aus Cobalt, Eisen, Kupfer und Ruthenium sowie deren Mischungen, eines wasserlöslichen Ammoniumsalzes und gegebenenfalls eines Oxidationsmittels auf Persauerstoffbasis sowie inerten Trägermaterials erhältlich ist und in der europäischen Patentanmeldung EP 0 832 969 beschrieben wurde.The bleach-enhancing transition metal complex compound is preferably composed of the compounds of the general formula I [M (NH ₃ ) _6-x-2y L _x (L ² ) _y ] A _n in which M is a transition metal. selected from cobalt, iron, copper and ruthenium, L is a ligand bound via one coordination point and L ^{2 is} a ligand bound via two coordination points, x is a number from 0 to 5, y is a number from 0 to 2 with the proviso that x + 2y is at most 5, A is a acid-forming anion and n is a number such that the compound of the formula (I) has no charge, or from complex compounds of the general formula (II),

in the

AROUND

stands for manganese, iron, cobalt, ruthenium or molybdenum,

R

stands for an alkylene, alkenylene, phenylene or cycloalkylene radical, which may optionally be alkyl and / or aryl substituted in addition to the substituent X, with a total of 1 to 12 carbon atoms, with R being the shortest distance between the N complexing with UM Atoms is 1 to 5 carbon atoms,

X

represents -H, -OR ³ , -NO ₂ , -F, -Cl, -Br or -J,

R ¹ , R ² and R ³

independently of one another represent hydrogen or an alkyl radical having 1 to 4 carbon atoms,

Y ¹ and Y ²

independently represent hydrogen or an electron-shifting substituent, where Y ¹ and Y ^{2 are} not simultaneously hydrogen if R is alkylene or cyclohexylene,

Z ¹ and Z ²

independently represent hydrogen, -CO ₂ M, -SO ₃ M or -NO ₂ ,

M

represents hydrogen or an alkali metal such as lithium, sodium or potassium and

A

represents a charge-balancing anion ligand,

or complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper, which contain one or more of the ligands III

in which R is a direct bond or an optionally amino-substituted alkylene group having 1 to 4 C atoms, A represents a condensed or uncondensed ring system which contains at least one nitrogen atom, and B is hydrogen, an OH group or A, or have the general formula IV

in which A and R have the meaning given for formula III and X is an optionally hydroxy- and / or C _1-4 -alkyl-substituted phenylene ring or an optionally hydroxy-substituted C _1-4 alkylene group. In a preferred embodiment of agents according to the invention, the transition metal complex compound has at least one optionally N-alkylated triazacyclononane ligand. A further preferred embodiment of agents according to the invention contains the bleach-enhancing transition metal complex compound in the form of a combination of active ingredients, which by intimately mixing a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and their mixtures, a water-soluble ammonium salt and optionally an oxidizing agent based on peroxygen and inert Backing material is available and has been described in European patent application EP 0 832 969.

The detergents and cleaning agents according to the invention, which are particularly powdery solids, in densified particle form, as homogeneous solutions or Suspensions can be present in addition to those used according to the invention Active ingredient combination in principle all known ingredients that are common in such agents contain. The agents according to the invention can in particular builder substances, surfactants, bleaching agents based on organic and / or inorganic peroxygen compounds, additional bleach activators, water-miscible organic solvents, additional enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, Color transfer inhibitors, foam regulators, silver corrosion inhibitors and Dyes and fragrances included.

The agents according to the invention can contain one or more surfactants, wherein in particular anionic surfactants, nonionic surfactants and their mixtures, but also cationic, zwitterionic and amphoteric surfactants come into question.

Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or Propoxylation products of alkyl glycosides or linear or branched Alcohols each with 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10 alkyl ether groups. Corresponding ethoxylation and / or propoxylation products are also of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, as well as of alkylphenols with 5 to 12 carbon atoms in the alkyl radical.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. Extremely low-foaming compounds are usually used in particular in cleaning agents for use in machine dishwashing processes. These preferably include C ₁₂ -C ₁₈ alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule. However, it is also possible to use other known low-foam nonionic surfactants, such as, for example, C ₁₂ -C ₁₈ alkyl polyethylene glycol polybutylene glycol ether, each having up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and also end-capped alkyl polyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in European patent application EP 0 300 305, so-called hydroxy mixed ethers. The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (V) in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:

in der R³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁴ für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R⁵ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO 95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO 90/13533 beschriebenen Verfahren hergestellt werden. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten "Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, daß die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden unter dem Ausdruck Gemini-Tenside nicht nur derartig "dimere", sondern auch entsprechend "trimere" Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether gemäß der deutschen Patentanmeldung DE 43 21 022 oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate gemäß der deutschen Patentanmeldung DE 195 03 061. Endgruppenverschlossene dimere und trimere Mischether gemäß der deutschen Patentanmeldung DE 195 13 391 zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so daß sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide, wie sie in den internationalen Patentanmeldungen WO 95/19953, WO 95/19954 und WO 95/19955 beschrieben werden.The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (VI)

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₁ -C ₄ -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are usually separated from one another by a so-called "spacer". This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is understood not only to mean "dimeric" but also "trimeric" surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061. End group-blocked dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are particularly characterized by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes. Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides, as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can also be used.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates of the kind obtained, for example, from C ₁₂ -C ₁₈ monoolefins having an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are obtained by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 ° C -Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are particularly preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 EO. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols. which are non-ionic surfactants. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are also suitable as further anionic surfactants. The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred. Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.

The anionic surfactants, including the soaps, can be in the form of their sodium, Potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine. The anionic surfactants are preferably in Form of their sodium or potassium salts, especially in the form of the sodium salts.

In detergents according to the invention, surfactants are preferred in quantitative proportions 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, whereas Agents for cleaning hard surfaces, in particular for machine cleaning of dishes, lower surfactant contents of up to 10% by weight, in particular up to 5% by weight and preferably in the range from 0.5% by weight to 3% by weight.

An agent according to the invention 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 methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid and ethylenediaminephosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of European patent EP 0 625 992 or the international patent application WO 92/18542 or European patent EP 0 232 202, which are accessible by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids , Maleic acids and copolymers of these, which also contain small amounts of polymerizable substances without carboxylic acid functionality can. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 30,000 to 100,000. Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl ester, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer. The first acidic 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, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000. Other preferred copolymers are those. which are described in German patent applications DE 43 03 320 and DE 44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used, in particular for the production 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.

Such organic builder substances can, if desired, in amounts up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight be included. Amounts close to the above upper limit are preferably in paste-like or liquid, in particular water-containing agents according to the invention used.

Alkali silicates, in particular, come as water-soluble inorganic builder materials, Alkali carbonates and alkali phosphates, in the form of their alkaline, neutral or acidic Sodium or potassium salts can be considered. examples for this are Trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric Trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, as well as the corresponding potassium salts or mixtures of sodium and Potassium salts. As water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in particular in liquid agents from 1% by weight to 5% by weight. Among them are the crystalline ones Sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the Zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta S.p.A.), prefers. Amounts close to the above limit are preferably in solid, particulate Funds used. Suitable aluminosilicates in particular have none Particles with a grain size above 30 microns and preferably exist at least 80 wt .-% of particles with a size below 10 microns. Your calcium binding capacity, that can be determined according to the information in German patent DE 24 12 837 usually in the range of 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Those with a Na ₂ O: SiO ₂ molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. Crystalline phyllosilicates of the general formula Na ₂ Si _x O _{2x + 1} .yH ₂ O are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number of 1, 9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and are preferred values for x 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ • y H ₂ O) are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. δ-sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 described, can be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0 294 753, are used in a further preferred embodiment of agents according to the invention. Crystalline layered silicates of the above formula (I) are sold by Clariant GmbH under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ • xH ₂ O, Kenyait), Na-SKS- 2 (Na ₂ Si ₁₄ O ₂₉ • xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ • xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ • xH ₂ O , Makatit). Of these, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ) are particularly suitable • 3H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ • 3H ₂ O, Kanemit), Na-SKS-11 (γ-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). An overview of crystalline layered silicates is given, for example, in "Hoechst High Chem Magazine 14/1993" on pages 33 - 38 and in "Soap-oil-fat waxes, 116 year, No. 20/1990" on pages 805 - 808 published articles. In a preferred embodiment of agents according to the invention, a granular compound composed of crystalline layered silicate and citrate, of crystalline layered silicate and the (co) polymeric polycarboxylic acid mentioned above, as described, for example, in German patent application DE 198 19 187, or of alkali silicate and alkali carbonate such as is described, for example, in international patent application WO 95/22592 or as is commercially available, for example, under the name Nabion® 15.

Builder substances can optionally be present in amounts in the agents according to the invention up to 90 wt .-% can be included. They are preferably in amounts up to 75% by weight. contain. Detergents according to the invention have builder contents of in particular 5 wt% to 50 wt%. Harder in cleaning agents according to the invention Surfaces, especially for the automatic cleaning of dishes, is the content of builder substances in particular 5% by weight to 88% by weight, with such agents preferably no water-insoluble builder materials are used. In a preferred embodiment of means according to the invention for in particular mechanical Cleaning dishes is 20 wt .-% to 40 wt .-% more water-soluble organic Builder, especially alkali citrate, 5 wt .-% to 15 wt .-% alkali carbonate and Contain 20 wt .-% to 40 wt .-% alkali disilicate.

As peroxygen compounds suitable for use in agents according to the invention come especially organic peracids or peracid salts of organic Acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, Hydrogen peroxide and under the washing conditions hydrogen peroxide releasing inorganic salts, to which perborate, percarbonate, persilicate and / or Persulfate like Caroat belong. into consideration. Sofem solid peroxygen compounds to be used, they can be used in the form of powders or granules that can also be encased in a manner known in principle. If an inventive Agents containing peroxygen compounds are preferred in amounts of up to 50% by weight, in particular from 5% by weight to 30% by weight, is present. The addition of small amounts of known bleach stabilizers such as Phosphonates, borates or metaborates and metasilicates as well as magnesium salts like magnesium sulfate may be useful.

In addition to the bleach activating transition metal complex compound, below Perhydrolysis conditions Peroxocarboxylic acid-releasing compounds, so-called Bleach activators. Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the international patent applications WO 97/36987 and WO 95/27775 are known. Can be used as bleach activators especially compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydrb-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic. especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known are. The hydrophilically substituted known from German patent application DE 196 16 769 Acylacetale and those in German patent application DE 196 16 770 and the international patent application WO 95/14075 described acyllactams also preferably used. Even those from the German patent application DE 44 43 177 known combinations of conventional bleach activators can be used. Such bleach activators can be used in the usual quantity range, preferably in amounts of 0.5% by weight to 10% by weight, in particular 1% by weight to 8% by weight, based on the total average, may be present. In addition to the conventional bleach activators or in their place can also those from the European patent specifications EP 0 446 982 and EP 0 453 003 known sulfonimines be included.

As enzymes which can be used in the compositions in addition to the amylase essential to the invention come from the class of proteases, lipases, cutinases, pullulanases, Hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof in question. Optionally, amylase other than the invention essential in addition to this. From fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus enzymatic substances obtained. The Amylase essential to the invention and the optionally additionally used enzymes can, as for example in the European patent EP 0 564 476 or in the International patent application WO 94/23005 described, adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation protect. They are preferred in the washing or cleaning agents according to the invention in amounts up to 5% by weight, in particular from 0.2% by weight to 4% by weight, contain. If the agent according to the invention contains protease, it preferably has one proteolytic activity in the range from about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If there are several enzymes in the agents according to the invention can be used by incorporating the two or more separate or separately in a known manner packaged enzymes or by two or more together in one granulate made-up enzymes, such as those from international patent applications WO 96/00772 or WO 96/00773 known.

To those in the agents according to the invention, especially when they are in liquid or pasty form, in addition to water usable organic solvents include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and those derived from the compound classes mentioned Ether. Such water-miscible solvents are in the agents according to the invention preferably in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.

In addition, the agents can be further customary in detergents and cleaning agents Components included. These optional components include in particular Enzyme stabilizers, graying inhibitors, color transfer inhibitors, foam inhibitors, and optical brighteners as well as colors and fragrances. To one Silver corrosion protection can cause in cleaning agents according to the invention for Tableware silver corrosion inhibitors are used. An inventive Hard surface cleaners can also be abrasive Components, in particular from the group comprising quartz flours, wood flours, Plastic flours, chalks and micro glass balls and their mixtures. Abrasives are preferably not present in the cleaning agents according to the invention 20 wt .-%, in particular from 5 wt .-% to 15 wt .-%, contain.

To set a desired, by mixing the other components the agents according to the invention cannot be systemic and environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, malic acid. Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, however also mineral acids, especially sulfuric acid, or bases, especially ammonium or Alkali hydroxides included. Such pH regulators are in the invention Agents in amounts of preferably not more than 20% by weight, in particular of 1.2% by weight to 17% by weight.

Regarding those suitable for use in textile detergents according to the invention Color transfer inhibitors include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinyl pyridine-N-oxide) and copolymers of Vinyl pyrrolidone with vinyl imidazole.

Graying inhibitors are responsible for the dirt detached from the textile fiber to keep suspended in the fleet. For this purpose, water-soluble colloids are usually more organic Suitable in nature, for example starch, glue, gelatin, salts of ether carboxylic acids or Ether sulfonic acids of starch or cellulose or salts of acidic Sulfuric acid esters of cellulose or starch. Also water-soluble, acidic groups containing polyamides are suitable for this purpose. Furthermore, other than use the starch derivatives mentioned above, for example aldehyde starches. Prefers cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition.

Textile detergents according to the invention can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid are suitable or similarly constructed connections that instead the morpholino group a diethanolamino group, a methylamino group, a Wear anilino group or a 2-methoxyethylamino group. Can continue Brighteners of the substituted diphenylstyryl type may be present, for example those Alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical brighteners can be used.

In particular when used in machine processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.

The preparation of solid compositions according to the invention presents no difficulties and can in a known manner, for example by spray drying or granulation, where the enzymes and any other thermally sensitive ingredients such as Example bleach may be added separately later if necessary. For the production of the invention Agents with increased bulk density, especially in the range of 650 g / l to 950 g / l, is a known from European patent EP 0 486 592, a method having an extrusion step is preferred. Another preferred Production using a granulation process is in the European patent specification EP 0 642 576.

For the preparation of agents according to the invention in tablet form which are single-phase or multi-phase, single-color or multi-color and in particular from one layer or from more, especially two layers, can be preferred in such a way that all components - possibly one layer each - in a mixer mixed together and the mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range of about 50 to 100 kN, preferably pressed at 60 to 70 kN. Especially at multilayer tablets it can be beneficial if at least one layer is pre-pressed. This is preferred for press forces between 5 and 20 kN, performed in particular at 10 to 15 kN. You get unbreakable and so easily nevertheless with tablets that dissolve sufficiently quickly under conditions of use Breaking and bending strengths of normally 100 to 200 N, but preferably above 150 N. A tablet produced in this way preferably has a weight of 10 g to 50 g, in particular from 15 g to 40 g. The shape of the tablets is arbitrary and can be round, oval or angular, with intermediate shapes also possible. Corners and edges are advantageously rounded. Round tablets preferably have one Diameters from 30 mm to 40 mm. In particular the size of angular or cuboid tablets, which are predominantly via the metering device for example, the dishwasher is dependent on the Geometry and volume of this dosing device. Exemplary preferred Embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), especially from 26x36 mm or from 24x38 mm.

Liquid or pasty washing or cleaning agents according to the invention in Forms of common solvent-containing solutions are usually simple Mixing the ingredients in bulk or as a solution in an automatic Mixers can be made.

Examples example 1

A cleaning agent ( V1 ) for the automatic cleaning of dishes, containing 55% by weight sodium tripolyphosphate (calculated as anhydrous), 4% by weight amorphous sodium disilicate (calculated as anhydrous), 22% by weight sodium carbonate, 9% by weight Sodium perborate, 2% by weight of TAED, 2% by weight of nonionic surfactant and 2% by weight of amylase granules (Termamyl® 60T) and 1.4% by weight of a protease granulate (activity 200,000 PU / g) with the Bacillus lentus protease (remainder to 100% by weight water, perfume and dye), an agent V2, which was otherwise composed like V1 , but additionally contained so much of a Co-containing active ingredient combination according to EP 0 832 969 that the Co Content was 100 ppm, as well as agents according to the invention ( M1 or M2 ), which were otherwise composed like V1 , but instead of Termamyl® protein-identical amounts of amylase from Bacillus amyloliquefaciens and additionally as much of a Co-containing active ingredient combination according to EP 0 832,969 contained that the Co content at 50 ppm and 100 ppm were tested as follows:

In a Miele® G 575 dishwasher (doses of 20 g each of the agent to be tested in the universal program, water hardness 14-16 ° dH, operating temperature 55 ° C), 6 plates with standardized starch stains or bleachable stains were washed and the remaining residue of the stains determined gravimetrically and in relation to the initial value before rinsing (= 100%). The table below shows the percentage of soiling removed. Cleaning performance [% starch removal] medium cleaning performance V1 57 V2 83 M1 98 M2 99

It can be seen that the agents according to the invention are not the agents according to the invention in are significantly superior to cleaning performance. Essentially the same results were obtained when the Co-containing in the inventive agents Active ingredient combination by chloropentammine cobalt (III) chloride in such amounts, that the Co concentration remained the same replaced.

Claims (14)

1. An amylase-containing detergent, characterized in that it contains naturally occurring α-amylase from Bacillus amyloliquefaciens and bleach-boosting transition metal complex compound besides typical ingredients compatible with such constituents.
2. A detergent as claimed in claim 1, characterized in that it contains amylase in quantities of 0.001 mg to 0.5 mg and more particularly 0.02 mg to 0.3 mg per gram of the detergent as a whole.
3. A detergent as claimed in claim 1 or 2, characterized in that the bleach-boosting transition metal complex compound is selected from the complex compounds of Mn, Fe, Co, Cu, Mo, V, Ti or Ru or mixtures thereof.
4. A detergent as claimed in any of claims 1 to 3, characterized in that the bleach-boosting transition metal complex compound is selected from compounds corresponding to general formula I: [M(NH₃)_6-x-2yL_x(L²)_y]A_n in which M is a transition metal selected from cobalt, iron, copper and ruthenium, L is a ligand attached through one coordination site and L² a ligand attached through two coordination sites, x is a number of 0 to 5, y is a number of 0 to 2, with the proviso that x + 2y is at most 5, A is salt-forming anion and n is a number with such a value that the compound of formula (I) does not have a charge.
5. A detergent as claimed in any of claims 1 to 3, characterized in that the bleach-boosting transition metal complex compound is an active-substance combination obtainable by thoroughly mixing a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally a peroxygen-based oxidizing agent and inert carrier material.
6. A detergent as claimed in any of claims 1 to 3, characterized in that the transition metal compound contains at least one optionally N-alkylated triazacyclononane ligand.
7. A detergent as claimed in any of claims 1 to 3, characterized in that the bleach-boosting transition metal compound is selected from compounds corresponding to general formula (II):

   

   in which

   UM

   stands for manganese, iron, cobalt, ruthenium or molybdenum,

   R

   is an alkylene, alkenylene, phenylene or cycloalkylene group which may optionally be alkyl- and/or arylsubstituted and which has a total of 1 to 12 carbon atoms, the shortest distance in R between the N atoms complexing with UM being 1 to 5 carbon atoms,

   X

   stands for -H, -OR³, -NO₂, -F, -Cl, -Br or -I,

   R¹, R² and R³

   independently of one another represent hydrogen or an alkyl group containing 1 to 4 carbon atoms,

   Y¹ and Y²

   independently of one another represent hydrogen or an electron-shifting substituent, Y¹ and Y² not both being hydrogen where R is alkylene or cyclohexylene,

   Z¹ and Z²

   independently of one another represent hydrogen, -CO₂M, -SO₃M or -NO₂,

   M

   stands for hydrogen or an alkali metal and

   A

   is a charge-compensating anion ligand.

8. A detergent as claimed in any of claims 1 to 3, characterized in that the bleach-boosting transition metal complex compound is selected from the complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and/or copper which have one or more ligands corresponding to general formula III:

   

   in which R is a direct bond or an optionally amino-group-substituted alkylene group containing 1 to 4 carbon atoms, A is a condensed or noncondensed ring system containing at least one nitrogen atom and B is hydrogen, an OH group or has the same meaning as A.
9. A detergent as claimed in any of claims 1 to 3, characterized in that the bleach-boosting transition metal complex compound is selected from the complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and/or copper which have one or more ligands corresponding to general formula IV:

   

   in which R is a direct bond or an optionally amino-group-substituted alkylene group containing 1 to 4 carbon atoms, A is a condensed or noncondensed ring system containing at least one nitrogen atom and X is an optionally hydroxy- and/or C_1-4-alkyl-substituted phenylene ring or an optionally hydroxysubstituted C_1-4 alkylene group.
10. A detergent as claimed in any of claims 1 to 9, characterized in that it contains the transition metal complex compound in a quantity, based on transition metal, of up to 1% by weight and more particularly 0.001% by weight to 0.25% by weight.
11. A detergent as claimed in any of claims 1 to 10, characterized in that it contains up to 50% by weight and more particularly 5% by weight to 30% by weight of peroxygen compound.
12. A detergent as claimed in any of claims 1 to 11, characterized in that it contains 0.5% by weight to 10% by weight and more particularly 1% by weight to 8% by weight of a compound which yields peroxocarboxylic acid under perhydrolysis conditions.
13. The use of a combination of naturally occurring α-amylase from Bacillus amyloliquefaciens and transition metal complex compound for boosting the cleaning performance of detergents used in aqueous washing solutions containing a peroxygen compound.
14. The use claimed in claim 13, characterized in that the cleaning performance against starch-containing and/or coloured, more particularly tea-based soils, is increased.