DE102015217816A1 - Use of highly concentrated enzyme granules to increase the storage stability of enzymes - Google Patents

Abstract

The invention relates to the use of highly concentrated enzyme granules in enzyme-containing detergents or cleaners to increase the stability of enzymes and an enzyme-containing detergent or cleaner, in particular a detergent in tablet form with improved enzyme stability.

Description

The invention relates to the use of highly concentrated enzyme granules in enzyme-containing detergents or cleaners for increasing the stability of enzymes and an enzyme-containing detergent or cleaner, in particular a liquid detergent or cleaning agent with improved enzyme stability.

Common detergents or cleaners on the market contain surfactants to remove dirt and stains. As a rule, combinations of a plurality of surfactants, in particular from the group of anionic, nonionic, cationic and amphoteric surfactants, are used here. These surfactants alone are often unable to remove dirt and stains sufficiently, so that in modern detergents or cleaning agents, other auxiliaries are used. These other excipients include enzymes of various types such as proteases, amylases, cellulases, mannanases, pectate lyases. The skilled worker is aware of other classes of enzymes. In particular, hydrolytic enzymes such as proteases, amylases or lipases are part of numerous textile or dishwashing detergents because of their direct cleaning action.

The decisive for the end user cleaning effect of the enzymes used in detergents or cleaning agents is determined in addition to the enzyme structure to a considerable extent by the nature of the preparation of these enzymes and their stabilization against environmental influences. Detergents or cleaning enzymes are formulated both in solid and in liquid form. The group of solid enzyme preparations includes, in particular, the enzyme granules consisting of several ingredients, which in turn are preferably incorporated into solid washing or cleaning agents. In contrast, liquid or gel detergents or cleaners frequently contain liquid enzyme preparations, which, unlike the enzyme granules, are much less protected against external influences.

To increase the stability of such enzyme-containing detergents or cleaners, a number of different protective measures have been proposed. For example, the German patent application teaches DE 20 38 103 (Henkel) the stabilization of enzyme-containing dishwashing detergents by saccharides, while in the European patent EP 646 170 B1 (Procter & Gamble) Propylene glycol for enzyme stabilization in liquid detergents is disclosed.

As reversible protease inhibitors in the prior art polyols, especially glycerol and 1,2-propylene glycol are described. A corresponding technical disclosure can be found, for example, in the international application WO 02/08398 A2 (Genencor).

The stabilization of enzymes in aqueous detergents by calcium salts such as calcium formate, calcium acetate or calcium propionate describes the U.S. Patent 4,318,818 (Procter & Gamble). However, salts of polyvalent cations, such as calcium cations, often result in turbidity during storage in aqueous systems, especially in manual dishwashing detergents. This negative effect intensifies during storage at low temperatures. As a result, the possible use concentrations are limited, so that a sufficient enzyme-stabilizing effect can not be guaranteed.

A second group of known stabilizers form borax, boric acids, boronic acids or their salts or esters. These include, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA) or the salts or esters of the abovementioned compounds. The latter compounds as enzyme stabilizers are disclosed, for example, in the international patent application WO 96/41859 A1 (Novo Nordisk). However, boric acids and boric acid derivatives, for example, often have the disadvantage that they form unwanted by-products with other ingredients of a composition, in particular detergent ingredients, so that they are no longer available for the desired cleaning purpose or even as an impurity in the compositions concerned stay behind on the laundry. Furthermore, boric acids or borates are considered to be disadvantageous from an environmental point of view.

The present invention is therefore based on the object to provide a stabilization route for enzymes, which avoids the disadvantages of the prior art as much as possible.

Surprisingly, it has been found that highly concentrated enzyme granules in enzyme-containing detergents or cleaning agents can increase the stability of the enzymes contained.

The present invention therefore relates to the use of highly concentrated enzyme granules in enzyme-containing detergents or cleaners to increase the stability of enzymes.

Preferably, the washing or cleaning agent is a solid washing or cleaning agent, preferably a solid, tablet-formulated machine dishwashing detergent.

The enzyme is preferably a protease, especially a subtilisin.

The advantages to be achieved by this invention are illustrated by Examples 1 to 3 of the present application, without the invention and its embodiments being limited thereto. There it has been proven that, when using a highly concentrated enzyme granulate according to the invention within a machine dishwashing detergent formulation after several weeks storage at elevated temperature and humidity, a better cleaning performance can be achieved than with lower concentrated granules. This effect is surprisingly independent of the final concentration of the enzyme in question in the agent in question.

Conversely, in corresponding agents, the same performance can be achieved with a lower absolute amount of enzyme, whereby a substance saving can be achieved and, given a given volume of such an agent, more volume is available for other active substances.

Furthermore, it has been observed that the use according to the invention of a highly concentrated enzyme granulate leads to an improved processability, in particular to an improved compressibility and thus to an increased hardness and stability of pressed detergent tablets.

According to the invention, enzyme granules are understood to mean any solid form of preparation of enzymes, for example PrNIs, granules, extrudates or particles obtainable by dripping, in each case in uncoated or mono- or multi-coated form.

A preferred embodiment according to the invention is the use of a highly concentrated enzyme granulate, wherein the enzyme is a hydrolytic and / or an oxidative enzyme, preferably one or more of the following group: protease, amylase or CGTase, lipase, hemi-cellulase, in particular β-glucanase or mannanase, cellulase, in particular endoglucanase, cellobiohydrolase or a mixture thereof, and / or oxidoreductase, in particular choline oxidase and / or perhydrolase. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly.

Very particularly preferred is the use of a highly concentrated enzyme granules, wherein the enzyme to those in the application WO 2012/171980 A1 as Protease 4 according to SEQ ID NO.3 characterized protease.

According to the invention, highly concentrated enzyme granules are understood as meaning enzyme granules which contain enzymes, in particular proteases, in amounts of from 0.1% by weight to 20% by weight, particularly preferably from 6% by weight to 19% by weight

Preferred amounts of the highly concentrated enzyme granules in amounts of 0.05 wt .-% to 9 wt .-%, in particular in amounts of 0.1 wt .-% to 4.0 wt .-%, particularly preferably in amounts of 3.0 Wt .-% used to 4.0 wt .-%. Particularly in cleaning agents, amounts of from 0.5% by weight to 9% by weight, more preferably from 3.0% by weight to 4.0% by weight, are used.

All facts, objects and embodiments described for uses according to the invention are also applicable to the following washing or cleaning agents. Therefore, reference is made at this point expressly to the disclosure in the appropriate place, with the statement that this disclosure also applies to the washing or cleaning agents according to the invention.

A further subject of the present invention is an enzyme-containing washing or cleaning agent, which is characterized in that it contains enzymes stabilized by highly concentrated enzyme granules.

An inventive composition contains at least one enzyme from the group of known, commonly used in detergents or cleaning agents enzymes. In a preferred embodiment of the invention, an agent according to the invention comprises at least one protease, particularly preferably at least one protease and at least one amylase.

Suitable proteases are all known proteases of the prior art. Among them, subtilisin-type ones are preferable. Examples are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus (BLAP), subtilisin DY and the subtilases, but no longer the subtilisins in the narrower sense attributable Enzymes thermitase, proteinase K and the proteases TW3 and TW7. More preferably, the protease is a BLAP-type subtilisin. The subtilisin BPN ', which is derived from Bacillus amyloliquefaciens, or B. subtilis, is from the work of Vasantha et al. (1984) in J. Bacteriol., Volume 159, pp. 811-819 and JA Wells et al. (1983) in Nucleic Acids Research, Volume 11, pp. 7911-7925 known. Subtilisin BPN 'serves as a reference enzyme of the subtilisins, in particular with regard to the numbering of the positions. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. It is published in the publications of EL Smith et al. (1968) in J. Biol. Chem., Volume 243, pp. 2184-2191 , and from Jacobs et al. (1985) in Nucl. Acids Res., Vol. 13, pp. 8913-8926 and is naturally produced by Bacillus licheniformis. The protease PB92 is naturally derived from the alkaliphilic bacterium Bacillus nov. spec. 92 and Gist-Brocades, Delft, The Netherlands, available under the trade name was Maxacal ^® by the company.. In its original sequence, it is in the patent application EP 283075 A2 described. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. They are originally from Bacillus strains with the application GB 1243784 A be revealed. From the protease from Bacillus lentus DSM 5483 ( WO 91/02792 A1 ) derive from the name under the name BLAP ^® variants, which in particular in WO 92/21760 A1 . WO 95/23221 A1 . WO 02/088340 A2 and WO 03/038082 A2 to be discribed. Subtilisin DY is originally from Nedkov et al. 1985 in Biol. Chem Hoppe-Seyler, volume 366, pp. 421-430 described. Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozyme ^® from Novozymes, the ^® under the trade names Purafect ^®, Purafect ^® OxP, Purafect Prime and Properase.RTM ^® from Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, the P under the trade names Proleather® ^® and protease ^® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzymes available under the name proteinase K-16 from Kao Corp., Tokyo, Japan.

The proteases used in the compositions according to the invention are either originally derived from microorganisms, for example from microorganisms of the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi.

For amylases, synonymous terms may be used, for example, 1,4-alpha-D-glucan glucanohydrolase or glycogenase. Preparable amylases according to the invention are preferably .alpha.-amylases. Crucial for determining whether an enzyme is an α-amylase according to the invention is its ability to hydrolyze α (1-4) -glycoside bonds in the amylose of the starch. Amylases which can be synthesized according to the invention are, for example, the α-amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens or from Bacillus stearothermophilus, and in particular also their further developments improved for use in detergents or cleaners. The enzyme from Bacillus licheniformis is available from the company Novozymes under the name Termamyl ^® and by the company Danisco / Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from the company Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, by the company Danisco / Genencor under the name Purastar® ^® OxAm and from the company Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^® available. The α-amylase from Bacillus amyloliquefaciens is marketed by the company Novozymes under the name BAN ^®, and variants derived from the α-amylase from Bacillus stearothermophilus under the names BSG ^® and Novamyl ^®, also from the company Novozymes. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the enhancements available under the trade names Fungamyl.RTM ^® by the company Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Other advantageous commercial products are for example the Amylase-LT ^® and Stainzyme® ^® or ultra Stainzyme® ^® or Stainzyme® plus ^®, the latter also from the company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred amylases are disclosed in International Publications WO 00/60060 . WO 03/002711 . WO 03/054177 and WO 07/079938 , whose disclosure is therefore expressly referred to, or its relevant disclosure content is therefore expressly incorporated into the present patent application.

Detergents or cleaning agents preferred according to the invention contain, based on their total weight, between 0.002 and 9.0% by weight, preferably between 0.02 and 6.0% by weight and in particular between 0.1 and 5.0% by weight. % Protease preparations. Particularly preferred are detergents or cleaners which, based on their total weight, contain between 0.1 and 4.0% by weight of protease preparations.

Detergents or cleaning agents preferred according to the invention contain, based on their total weight, between 0.001 and 5.0% by weight, preferably between 0.01 and 4.0% by weight and in particular between 0.05 and 3.0% by weight. % Amylase preparations. Particularly preferred are detergents or cleaners which, based on their total weight, contain between 0.07 and 2.0% by weight of amylase preparations.

In one preferred embodiment, the enzyme-containing washing or cleaning agent according to the invention is a detergent in tablet form, in another preferred embodiment a detergent in tablet form for cleaning hard surfaces, in particular dishes.

For the purposes of the present application, an enzyme is to be understood as meaning a protein which has a specific biocatalytic function. For the purposes of the present application, protease is understood as meaning an enzyme which catalyzes the hydrolysis of peptide bonds and is thereby able to cleave peptides or proteins. For the purposes of the present application, a protein is a polypeptide composed largely of linear structure composed of the natural amino acids and generally assuming a three-dimensional structure in order to perform its function. A peptide consists of amino acids that are covalently linked to each other via peptide bonds. The term polypeptide clarifies in this regard the fact that this peptide chain usually consists of many amino acids, which are connected to each other via peptide bonds. Amino acids may be in an L and a D configuration, with the amino acids that make up proteins in the L configuration. They are called proteinogenic amino acids. In the present application, the proteinogenic, naturally occurring L-amino acids are designated by the internationally used 1- and 3-letter codes. Numerous proteins are formed as so-called pre-proteins, ie together with a signal peptide. By this is meant the N-terminal part of the protein, the function of which is usually to ensure the discharge of the protein formed from the producing cell into the periplasm or the surrounding medium and / or its correct folding. Subsequently, the signal peptide is cleaved under natural conditions by a signal peptidase from the rest of the protein, so that this exerts its actual catalytic activity without the initially present N-terminal amino acids. Pro-proteins are inactive precursors of proteins. Their signal sequence precursors are referred to as pre-pro proteins. For technical applications, because of their enzymatic activity, the fats, i. mature peptides, i. preference is given to the enzymes processed after their preparation in preference to the preproteins.

The proteins may be modified by the cells producing them after production of the polypeptide chain, for example, by attachment of sugar molecules, formylations, aminations, etc. Such modifications are referred to as post-translational modifications. These post-translational modifications may or may not have an effect on the function of the protein.

Proteases or enzymes in general can be prepared by various methods, e.g. targeted genetic modification by mutagenesis, further developed and optimized for specific uses or specific properties such as catalytic activity, stability, etc.

It is also well known in the art that beneficial properties of individual mutations, e.g. single point mutations, can complement. An already optimized with respect to certain properties protease, for example, in terms of their stability to surfactants or other components, according to the invention can be further developed.

Fragments are understood as meaning all proteins or peptides which are smaller than natural proteins and, for example, can be obtained synthetically. Due to their amino acid sequences, they can be assigned to the relevant complete proteins. For example, they may adopt the same structures or perform proteolytic or partial activities, such as the complexation of a substrate. Fragments and deletion variants of starting proteins are in principle similar; while fragments tend to be smaller fragments, the deletion mutants tend to lack only short regions, and thus only individual subfunctions.

For the purposes of the present application, chimeric or hybrid proteins are understood as meaning those proteins whose sequence comprises the sequences or partial sequences of at least two starting proteins includes. The source proteins may be derived from different or from the same organism. Chimeric or hybrid proteins may be obtained, for example, by recombinant mutagenesis. For example, the purpose of such recombination may be to induce or modify a particular enzymatic function using the fused protein portion. For the purposes of the present invention, it is irrelevant whether such a chimeric protein consists of a single polypeptide chain or several subunits to which different functions can be distributed.

By proteins obtained by insertion mutation are meant those variants obtained by inserting a protein fragment into the starting sequences. They are due to their principle similarity to the chimeric proteins. They differ from those only in the size ratio of the unchanged protein part to the size of the entire protein. In such insertionsmutierten proteins, the proportion of foreign protein is lower than in chimeric proteins.

Inversion mutagenesis, ie a partial sequence reversal, can be regarded as a special form of both the deletion and the insertion. The same applies to a new grouping of different parts of the molecule which deviates from the original amino acid sequence. It can be regarded as a deletion variant, as an insertion variant, as well as a shuffling variant of the original protein. For the purposes of the present application, derivatives are understood as meaning those proteins whose pure amino acid chain has been chemically modified. Such derivatizations can be carried out, for example, biologically in connection with protein biosynthesis by the host cell. For this molecular biological methods can be used. However, they can also be carried out chemically, for example by the chemical transformation of a side chain of an amino acid or by covalent binding of another compound to the protein. Such a compound may, for example, also be other proteins which are bound, for example via bifunctional chemical compounds, to proteins according to the invention. Such modifications may, for example, affect the substrate specificity or binding strength to the substrate or cause a temporary blockage of the enzymatic activity when the coupled substance is an inhibitor. This can be useful, for example, for the period of storage. Also, derivatization is understood to mean covalent attachment to a macromolecular carrier, as well as noncovalent inclusion in suitable macromolecular cage structures.

In a further embodiment of the invention, the enzyme-containing agent is thus characterized in that the enzyme, preferably the protease, is present in the agent as a fragment, deletion variant, chimeric protein or derivative, the protease furthermore being catalytically active.

For the purposes of the present invention, all enzymes, proteins, fragments, chimeric proteins and derivatives, unless they need to be addressed explicitly as such, are summarized under the generic term proteins.

Compositions of the invention comprise all types of enzyme-containing agents, in particular mixtures, formulations, solutions, etc., whose enzyme stability is improved by adding the above-described highly concentrated enzyme granules. Depending on the field of use, these may be, for example, solid mixtures, for example powders with freeze-dried or encapsulated proteins, or preferably gelatinous or liquid agents. In particular, this appropriation is to be understood as the areas of application set out below. Further fields of application emerge from the prior art and are described, for example, in the manual "Industrial Enzymes and their Applications" by H. Uhlig, Wiley-Verlag, New York, 1998 shown.

In preferred embodiments of the invention, an agent according to the invention is characterized in that it is a detergent, hand wash, rinse, hand dishwashing, machine dishwashing, cleaning, denture or contact lens care, rinse aid, disinfectant and especially a laundry detergent or dishwashing detergent.

This invention includes all conceivable types of detergents or cleaners, both concentrates and undiluted agents to be used on a commercial scale, in the washing machine or in hand washing or cleaning. These include, for example, detergents for textiles, carpets, or natural fibers, for which according to the present invention the term laundry detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather; for such according to the present invention, the term cleaning agent is used.

An agent according to the invention can be either a means for large consumers or technical users as well as a product for the private consumer, wherein all types of detergents and cleaning agents established in the prior art also constitute embodiments of the present invention.

The washing or cleaning agents according to the invention may in principle comprise all known ingredients customary in such agents, at least one further ingredient being present in the composition.

The agents according to the invention may in particular be builders, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as optical brighteners, grayness inhibitors, foam regulators and dyes and fragrances and combinations thereof.

The compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 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 on average 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 may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are 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 of these, 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 means which, for a particular product, may be an integer or a fractional number. 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 include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. In particular, agents for use in mechanical processes usually extremely low-foam compounds are used. These include preferably C ₁₂ -C ₁₈ -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol 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 ethers having in each case up to 8 mol of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in the European patent application EP 0 300 305 are described, so-called Hydroxymischether. 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 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (III) 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 having 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 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. 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 oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate. Endgruppenverschlossene dimere und trimere Mischether 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. Geeignet sind auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C₇-C₂₁-Alkohole, wie 2-Methylverzweigte C₉-C₁₁-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C₁₂-C₁₈-Fettalkohole mit 1 bis 4 EO. Zu den bevorzugten Aniontensiden gehören auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden, und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C₈- bis C₁₈-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen. Als weitere anionische Tenside kommen Fettsäure-Derivate von Aminosäuren, beispielsweise von N-Methyltaurin (Tauride) und/oder von N-Methylglycin (Sarkoside) in Betracht. Insbesondere bevorzugt sind dabei die Sarkoside beziehungsweise die Sarkosinate und hier vor allem Sarkosinate von höheren und gegebenenfalls einfach oder mehrfach ungesättigten Fettsäuren wie Oleylsarkosinat. Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind insbesondere gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierten Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische. Zusammen mit diesen Seifen oder als Ersatzmittel für Seifen können auch die bekannten Alkenylbernsteinsäuresalze eingesetzt werden. Die anionischen Tenside, einschließlich der Seifen, können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor. The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)

in the R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also obtained here preferably 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 be converted into the desired polyhydroxy fatty acid amides, for example by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferred nonionic surfactants 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 from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof. Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. 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 not only such "dimer", but also corresponding to "trimeric" surfactants understood. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality. Thus, 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. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides. Also suitable are the sulfuric acid monoesters of straight-chain or branched C ₇ -C ₂₁ -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol 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 of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate. As further anionic surfactants are particularly soaps into consideration. Are suitable in particular saturated fatty acid soaps, 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. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts. The anionic surfactants, including soaps, may 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 present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Surfactants are present in inventive compositions in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%. The use of builders (builders) such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, may be advantageous.

In a preferred embodiment according to the invention, the use of phosphates (including polyphosphates) is largely or completely omitted. The agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). Most preferably, in this embodiment, the agent is completely phosphate-free, i. the agents contain less than 0.1% by weight of phosphate (s).

The builders include in particular carbonates, citrates, phosphonates, organic builders and silicates. The proportion by weight of the total builders in the total weight of compositions according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.

Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule. Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, for example nitrilotriacetic acid (NTA), glutamine-N, N -diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA)) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

In addition to their builder effect, the free acids also typically have the property of an acidifying component and can thus, if desired, also serve to set a lower pH. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwasher detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to Contain 20 wt .-%, each based on the total weight of the composition.

Also particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate (soda), in amounts of 2 to 50 wt .-%, preferably from 4 to 40 wt. -% and in particular from 10 to 30 wt .-%, most preferably 10 to 24 wt .-%, each based on the weight of the composition.

Particularly preferred cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized in that they comprise at least two builders the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, wherein the weight fraction of these builders, based on the total weight of the cleaning agent according to the invention, preferably 5 to 70 wt .-%, preferably 15 to 60 wt .-% and in particular 20 to 50 Wt .-% is. The combination of two or more builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents. In addition to the builders mentioned here, one or more other builders may additionally be present.

Preferred cleaning agents, in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate.

In a very particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight. and the amount of citrate is preferably from 5 to 35 wt .-%, in particular 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total amount of the cleaning agent, wherein the total amount of these two Builders preferably 20 to 65 wt .-%, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is. In addition, one or more further builders may additionally be included.

The detergents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, may in particular contain phosphonates as further builder. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are preferably present in compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight, in each case based on the total weight of the agent.

Particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-% Phosphonate used.

Further particularly preferred cleaning agents, in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized in that in addition to citrate and (hydrogen) carbonate and optionally phosphonate they contain at least one further phosphorus-free builder. In particular, it is selected from among the aminocarboxylic acids, wherein the further phosphorus-free builder is preferably selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), more preferably MGDA or GLDA.

A particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.

The percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight. Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules. Advantageous in this case are those MGDA granules which contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder. The combination of at least three, in particular at least four, builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwasher detergents. In addition, other builders may be included.

As organic builders, polymeric polycarboxylates are furthermore suitable; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol. Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility can from this group, in turn, the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and more preferably from 3000 to 5000 g / mol, preferably be.

The content of the cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, of (homo) polymeric polycarboxylates is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight.

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. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. 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 may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with 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. Such polymers generally have a molecular weight between 1000 and 200,000. Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. Detergents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can furthermore comprise, as builder, crystalline stratiform silicates of the general formula NaMSixO.sub.2.sup. + 1 .yH.sub.2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4 where particularly preferred values for x are 2, 3 or 4 and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and secondary wash properties.

In certain detergents according to the invention, in particular dishwashing detergents, preferably dishwasher detergents, the content of silicates, based on the total weight of the detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight ,

Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, the crystalline sodium aluminosilicates in detergent quality, more particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystals of zeolites A and X (VEGOBOND ^® AX, a commercial product of Condea Augusta SpA), preferably , 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, according to the information of the German Patent DE 24 12 837 can be determined, is usually in the range of 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. 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 22, in particular 1.9 to 4 and y is a number from 0 to 33 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 prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in inventive compositions. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another preferred embodiment employed agent according to the invention. Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), 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, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , Natrosilit), Na-SKS-9 (NaHSi ₂ O ₅ · 3H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-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 ). In a preferred embodiment of inventive compositions is a granular compound of crystalline phyllosilicate and citrate, of crystalline layered silicate and aforementioned (co) polymeric polycarboxylic acid or of alkali silicate and alkali metal as it is available, for example under the name Nabion ^® 15 commercially , The builder substances are contained in the compositions according to the invention, in particular in detergents, preferably in amounts of up to 75% by weight, in particular 5% by weight to 50.

In addition to the abovementioned builders, the washing or cleaning agents according to the invention may furthermore comprise alkali metal hydroxides. These alkali carriers are preferably present only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably in the detergents or cleaners and in particular in the second phases 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the detergent or cleaning agent used. Alternative cleaning agents according to the invention are free of alkali metal hydroxides.

As for the use in agents according to the invention suitable peroxygen compounds are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration. 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. If an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters and also acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoyl-caprolactam. The hydrophilic substituted acyl acetals and the acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-producing bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.

In addition to the conventional bleach activators or in their place, sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes may also be present as so-called bleach catalysts.

Among the solvents according to the invention, in particular when they are in liquid or pasty form, organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and those from the said classes of compounds dissipative ether. Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

In order to establish a desired pH, which does not result from the mixture of the other components, the compositions according to the invention can contain system- and environmentally compatible 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 bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

Detergents according to the invention may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned optical brightener can be used.

In particular, when used in mechanical processes, it may be advantageous to add conventional foam inhibitors to the compositions. As 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 foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, 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. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

In further embodiments of compositions according to the invention, in particular washing or cleaning agents, the enzymes to be stabilized, preferably proteases, and the highly concentrated enzyme granules are combined, for example, with one or more of the following ingredients: nonionic, anionic and / or cationic surfactants, (if appropriate further) bleaches, Bleach activators, bleach catalysts, builders and / or cobuilders, acids, alkaline substances, hydrotropes, solvents, thickeners, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, corrosion inhibitors, in particular silver protectants (silver corrosion inhibitors), disintegration aids, soil release agents, color transfer (or Transfer) inhibitors, foam inhibitors, abrasives, dyes, perfumes, perfumes, antimicrobial agents, UV protectants or absorbents, antistatic agents, pearlescing agents and skin protection agents, further enzymes such as, for example protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, β-glucosidase, carrageenase, oxidase, oxidoreductase, pectin degrading enzyme or a lipase, other stabilizers, especially other enzyme stabilizers, and other components known in the art known in the art.

In a further embodiment of the invention, an agent according to the invention is therefore characterized in that it contains at least one further component selected from the group consisting of surfactants, builders, acids, alkaline substances, hydrotropes, solvents, thickeners, bleaching agents, dyes, perfumes, corrosion inhibitors , Sequestering agents, electrolytes, optical Brighteners, grayness inhibitors, silver corrosion inhibitors, dye transfer inhibitors, foam inhibitors, disintegration aids, abrasives, UV absorbers, solvents, antistatic agents, pearlescers and skin protectants.

The ingredients to be selected as well as the conditions under which the agent is used, such as temperature, pH, ionic strength, redox ratios or mechanical influences, should be optimized for the respective cleaning problem. For example, normal temperatures for detergents and cleaners range from 10 ° C for manual agents above 40 ° C and 60 ° C up to 95 ° for mechanical or technical applications. Since the temperature is usually infinitely adjustable in modern washing machines and dishwashers, all intermediate stages of the temperature are included. Preferably, the ingredients of the respective agents are coordinated.

• – 5 Gew.-% bis 70 Gew.-%, insbesondere 5 Gew.-% bis 30 Gew.-% Tenside und/oder
• – 10 Gew.-% bis 65 Gew.-%, insbesondere 12 Gew.-% bis 60 Gew. -% wasserlösliches oder wasserdispergierbares anorganisches Buildermaterial und/oder
• – 0,5 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 8 Gew.-%, wasserlösliche organische Buildersubstanzen und/oder
• – 0,01 bis 15 Gew.-% feste anorganische und/oder organische Säuren beziehungsweise saure Salze und/oder
• – 0,01 bis 5 Gew.-% Komplexbildner für Schwermetalle und/oder
• – 0,01 bis 5 Gew.-% Vergrauungsinhibitor und/oder
• – 0,01 bis 5 Gew. -% Farbübertragungsinhibitor und/oder
• – 0,01 bis 5 Gew.-% Schauminhibitor.

In a further embodiment, an agent according to the invention, in particular a washing or cleaning agent, further comprises

• - 5 wt .-% to 70 wt .-%, in particular 5 wt .-% to 30 wt .-% of surfactants and / or
• From 10% by weight to 65% by weight, in particular from 12% by weight to 60% by weight, of water-soluble or water-dispersible inorganic builder material and / or
• From 0.5% by weight to 10% by weight, in particular from 1% by weight to 8% by weight, of water-soluble organic builders and / or
• 0.01 to 15% by weight of solid inorganic and / or organic acids or acid salts and / or
• 0.01 to 5% by weight complexing agent for heavy metals and / or
• 0.01 to 5% by weight of grayness inhibitor and / or
• 0.01 to 5% by weight of color transfer inhibitor and / or
• - 0.01 to 5 wt .-% foam inhibitor.

Optionally, the agent may further comprise optical brighteners, preferably from 0.01% to 5% by weight.

Frame formulation of the cleaning agents according to the invention, in particular dishwashing detergent, preferably automatic dishwashing detergent: Wt .-% Preferred% by weight Citrate, Na salt 10-25 15-20 Phosphonate (eg HEDP) 0-10 2.5-7.5 MGDA, Na salt 0-40 0-25 Disilicate, Na salt 0-40 5-35 soda 10-30 10-25 Percarbonate, Na salt 5.0-20.0 10-15 Bleach catalyst (preferably Mn-based) 0.0 to 0.8 0.02-0.5 Bleach activator (eg TAED) 1.0-4.0 1-3 Nio-surfactant, eg fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 1.5 to 15.0 2.5-10 polycarboxylate 0.5-15 4-10 Cationic copolymer 0.0-1.0 0-0.75 Disintegrant - (eg Crosslinked PVP) 0.0-3.0 0-1.5 Protease preparation (tq) 1.0 to 7 1.5-5 Amylase preparation (tq) 0.2-6 0.5-3 Silver protection (benzotriazole) 0.0-1.0 0-0.5 Perfume 0.0-0.5 0.05-0.25 dye solution 0.0 to 1.5 0.0 to 1 Zn salt (eg acetate) 0.01-0.5 0.1-0.3 sodium sulphate 0.0 to 25 0.0 to 10 water 0.0 to 3 0.0 to 1.5 pH-adjusting agent (eg citric acid) 0.0-5 0-1.5 processing aids 0-10 0-5

The preparation of solid compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later. For the preparation of inventive 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 according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) × (34 to 40 mm), in particular of 26 × 36 mm or of 24 × 38 mm.

Liquid or pasty compositions according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer. Embodiments of the present invention thus comprise all such solid, powdered, liquid, gelatinous or paste-like administration forms of the agents, which if appropriate can also consist of several phases and can be present in compressed or uncompressed form. A further embodiment of the invention therefore represents agents which are characterized in that they are present as a one-component system. Such means preferably consist of one phase. Of course, means according to the invention may also consist of several phases. In a further embodiment of the invention, the washing or cleaning agent is therefore characterized in that it is divided into several components.

The solid dosage forms according to the invention also include extrudates, granules, tablets or pouches, which may be present both in large packages and in portions. Alternatively, the agent is present as a free-flowing powder, in particular with a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l or 600 g / l to 850 g / l.

The agent according to the invention, in particular washing or cleaning agent, can be packaged in a container, preferably an air-permeable container, from which it is released shortly before use or during the washing process.

Agents according to the invention may also contain further proteases or other enzymes in a concentration which is appropriate for the effectiveness of the agent. A further subject of the invention thus represents agents which further comprise one or more further enzymes, wherein in principle all enzymes established in the prior art for these purposes can be used. As other enzymes preferably used are all enzymes that can develop a catalytic activity in the agent of the invention, in particular proteases, amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, ß-glucosidases, carrageenases, oxidases, oxidoreductases, pectin-degrading Enzymes (pectinases) or lipases, and preferably mixtures thereof. These enzymes are basically of natural origin; outgoing Of the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly.

^{Compositions according} to the invention preferably contain enzymes in total amounts of 1 × 10 ^-8 to 5 percent by weight based on active protein. Preferably, the enzymes are from 0.00001 to 5 wt%, more preferably from 0.0001 to 2.5 wt%, even more preferably from 0.0001 to 1 wt%, and most preferably from 0.0001 to 0.072 wt .-% in inventive compositions, wherein each enzyme contained may be present in the proportions mentioned.

The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ). The further enzymes particularly preferably support the effect of the agent, for example the cleaning performance of a washing or cleaning agent, with regard to certain stains or stains. Particularly preferably, the enzymes show synergistic effects with respect to their action against certain stains or stains, ie the enzymes contained in the middle composition mutually support each other in their cleaning performance. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the composition according to the invention. In a further preferred embodiment of the invention, the agent according to the invention is therefore characterized in that it contains at least one further enzyme which comprises a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, β-glucosidase, carrageenase, oxidase, oxidoreductase , Pectin degrading enzyme or lipase.

When comparing the performance of two enzymes, a distinction must be made between protein-like and activity-like use. Particularly in the case of genetically engineered, largely side-activity-free preparations, the use of the same protein is appropriate. Because this is a statement on whether the same amounts of protein - for example, as a measure of the yield of a fermentative production - lead to comparable results. If the respective ratios of active substance to total protein (the values of the specific activity) diverge, then an activity-equivalent comparison is recommended because this compares the respective enzymatic properties. In general, a low specific activity can be compensated by adding a larger amount of protein. This is ultimately an economic consideration.

The protease activity in such agents may be as described in U.S. Pat Surfactants, Vol. 7 (1970), pp. 125-132 method described. It is given in PE (protease units) accordingly. Alternatively, the protease activity can be determined via the release of the chromophore para-nitroaniline (pNA) from the substrate suc-L-Ala-L-Ala-L-Pro-L-Phe-p-Nitroanilide (AAPF). The protease cleaves the substrate and releases pNA. The release of pNA causes an increase in absorbance at 410 nm, the time course of which is a measure of the enzymatic activity. The measurement is carried out at a temperature of 25 ° C, at pH 8.6, and a wavelength of 410 nm. The measuring time is 5 min and the measuring interval 20s to 60s.

The enzymes used in the compositions according to the invention are either originally derived from microorganisms, such as the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi ,

A further subject of the invention is a process for the cleaning of textiles or of hard surfaces, in which an enzyme-containing detergent or cleaning agent according to the invention is active in at least one process step. The process for the cleaning of textiles or hard surfaces is accordingly characterized in that an agent according to the invention is used in at least one process step.

This includes both manual and mechanical processes, with mechanical processes being preferred on account of their more precise controllability, for example with regard to the quantities and reaction times used.

Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent. The same goes for procedures for cleaning all the others Materials as textiles, which are summarized by the term hard surfaces. All conceivable washing or cleaning methods can be enriched in at least one of the method steps by an agent according to the invention, and then represent embodiments of the present invention.

Preferably, the enzymes are used in an amount of from 40 μg to 4 g, preferably from 50 μg to 3 g, more preferably from 100 μg to 2 g and most preferably from 200 μg to 1 g per application.

A further subject of the invention is a process for the treatment of textile raw materials or for textile care, in which an enzyme-containing detergent or cleaning agent according to the invention is active in at least one process step.

Among these, methods for textile raw materials, fibers or textiles with natural components are preferred, and especially for those with wool or silk.

These may be, for example, processes in which materials for processing in textiles are prepared, for example for anti-fungal finishing, or, for example, for processes which enrich the cleaning of worn textiles with a nourishing component. Because of the above-described effect of proteases on natural, proteinaceous raw materials, in preferred embodiments, they are processes for the treatment of textile raw materials, fibers or textiles with natural constituents, in particular with wool or silk.

The following examples illustrate the invention without, however, limiting it to:

Example 1: recipe

A commercial automatic dishwashing detergent in the form of a dishwashing tablet containing 15% by weight of sodium percarbonate as the source of hydrogen peroxide (bleach), 0.03% by weight of bleach catalyst and 2.2% by weight of TAED as a bleach activator was used. The tablet weight was 20g.

In addition, two differently highly concentrated enzyme granules were used, both of which are in the application WO 2012/171980 A1 as Protease 4 according to SEQ ID NO.3 characterized protease. The granules are available under the name Blaze Evity 100T and Blaze Evity 125T from Novozymes.

The quantities used were:
Blaze Evity 100T: 0.8g = 4% of tablet weight
Blaze Evity 125T: 0.64g = 3.2% of tablet weight

Example 2 Determination of the Cleaning Performance of Dishwashing Products According to the Invention

The cleaning performance describes the ability of a dishwashing detergent, in particular a dishwasher detergent, to partially or completely remove an existing soiling.

The cleaning performance of the composition of Formulation Example 1 was tested on a total of six different stubborn stains. Protease granules with different protease concentrations according to Example 1 were added to the agent used.

The determination of the cleaning performance was carried out after a storage period of the protease granules containing agent of 8 weeks at 30 ° C and 80% humidity.

The dishwashing process was carried out in the dishwasher Miele GSL (program: 50 ° C, program duration 57 min, water hardness 21 ° German hardness). The dishwasher tablet was added to the dosing device before the start of the cleaning program.

The evaluation of the cleaning performance was carried out visually according to a scale of 1 to 10, with the value 10 being the best grade (no discernible residue). The results are shown in Table 2 below. Table 2: Assam tea minced meat egg yolk spaghetti Strength Creme brulee Formula with Blaze 100T 7.3 10.0 5.9 4.2 8.1 5.5 Formula with Blaze 125T 7.3 10.0 6.5 4.2 8.4 6.0

As can be seen from Table 2, the use of Blaze 125T on three soils improves the cleaning performance.

Example 3: Determination of the proteolytic enzyme activity of the samples

The activity of the samples was determined by a test procedure in which the enzyme-containing sample is incubated under standardized conditions with the substrate N, N-dimethylcasein. By proteolysis in sodium sulfite solution at 50 ° C thereby primary amino groups are formed, which react with 2,4,6-trinitrobenzenesulfonic acid to a stable, yellow dye. The detection then takes place at 420 nm in the flow, as in AFSA HABEEB, Determination of Amino Groups in Proteins by Trinitrobenzenesulfonic Acid, Analy. Biochemistry 14, 328-336 (1966 ). For this method a coefficient of variation of approx. 2% was determined. The determination was carried out in enzyme activity units (CPE). Table 3: CPE / g According to theory Quantity in the RL trial CPE Blaze Evity 100T 456 0.8 g 365 Blaze Evity 125T 541 570 0.64 g 346

Theoretically, the cleaning performance should have been the same when using 0.8 times Blaze 125T to Blaze 100T. However, there is an increase. To explain this, the activity of the two enzyme samples was measured, and it was found that Blaze 125T was less active than expected. Therefore, not the same active content was used in the cleaning performance test, but a smaller amount Blaze 125T (Table 3 right column). This makes the result even more surprising.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 2038103 [0004]
• EP 646170 B1 [0004]
• WO 02/08398 A2 [0005]
• US 4318818 [0006]
• WO 96/41859 A1 [0007]
• WO 2012/171980 A1 [0018, 0107]
• EP 283075 A2 [0024]
• GB 1243784A [0024]
• WO 91/02792 A1 [0024]
• WO 92/21760 A1 [0024]
• WO 95/23221 A1 [0024]
• WO 02/088340 A2 [0024]
• WO 03/038082 A2 [0024]
• WO 00/60060 A [0026]
• WO 03/002711 [0026]
• WO 03/054177 [0026]
• WO 07/079938 [0026]
• EP 0300305 [0048]
• DE 2412837 [0070]

Cited non-patent literature

• Vasantha et al. (1984) in J. Bacteriol., Volume 159, pp. 811-819 and JA Wells et al. (1983) in Nucleic Acids Research, Volume 11, pp. 7911-7925 [0024]
• EL Smith et al. (1968) in J. Biol. Chem., Volume 243, pp. 2184-2191 [0024]
• Jacobs et al. (1985) in Nucl. Acids Res., Vol. 13, pp. 8913-8926 [0024]
• Nedkov et al. In Biol. Chem. Hoppe-Seyler, Vol. 366, pp. 421-430 [0024]
• "Industrial Enzymes and their Applications" by H. Uhlig, Wiley-Verlag, New York, 1998. [0040]
• Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 [0094]
• Surfactants, Vol. 7 (1970), pp. 125-132 [0096]
• AFSA HABEEB, Determination of Amino Groups in Proteins by Trinitrobenzenesulfonic Acid, Analy. Biochemistry 14, 328-336 (1966) [0115]

Claims (11)

 Use of highly concentrated enzyme granules in enzyme-containing detergents or cleaners to increase the stability of enzymes. Use according to Claim 1, characterized in that the enzyme is a hydrolytic and / or an oxidative enzyme, preferably a protease, in particular the protease 4 as shown in the application WO 2012/171980 A1 according to SEQ ID NO. 3 characterized protease. Use according to claim 1 or 2, characterized in that the highly concentrated enzyme granules enzymes, in particular proteases, in amounts of 0.1 wt .-% to 20 wt .-%, particularly preferably from 6 wt .-% to 19 wt .-% contain. Use according to one of the preceding claims, characterized in that the washing or cleaning agent is a solid washing or cleaning agent, preferably a solid machine dishwashing detergent in tablet form. Use according to one of the preceding claims, characterized in that the highly concentrated enzyme granules in amounts of 0.05 wt .-% to 9 wt .-%, in particular in amounts of 0.1 wt .-% to 4.0 wt .-% , particularly preferably used in amounts of 3.0 wt .-% to 4.0 wt .-%. Enzyme-containing washing or cleaning agent, characterized in that it contains enzymes stabilized by highly concentrated enzyme granules. Enzyme-containing washing or cleaning agent according to claim 6, characterized in that it is the enzyme is a hydrolytic and / or an oxidative enzyme, preferably a protease, in particular to those in the application WO 2012/171980 A1 as protease 4 according to SEQ ID NO.3 characterized protease. Enzyme-containing washing or cleaning agent according to claim 6 or 7, characterized in that it is a detergent in tablet form. Enzyme-containing detergent or cleaner according to claim 6 or 7, characterized in that it is a detergent in tablet form for cleaning hard surfaces, in particular dishes. An enzyme-containing washing or cleaning agent according to any one of claims 6 to 9, characterized in that it contains highly concentrated enzyme granules in amounts of 0.05 wt .-% to 9 wt .-%, in particular in amounts of 0.1 wt .-% to 4 , 0 wt .-%, particularly preferably in amounts of 3.0 wt .-% to 4.0 wt .-% are used. Process for the cleaning of textiles or hard surfaces, characterized in that in at least one process step an enzyme-containing detergent or cleaner according to one of claims 6 to 10 is active.