AMYLASE FOR DETERGENT AND CLEANING APPLICATIONS

Description

[0001] The invention lies in the field of enzyme technology. The invention relates to agents, preferably washing or cleaning agents, particularly preferably liquid washing or cleaning agents, containing an amylase with improved storage stability. The invention further relates to methods for cleaning textiles and hard surfaces and to uses of these washing or cleaning agents.

[0002] Amylases are among the technically important enzymes. Their use in detergents and cleaning agents is industrially established, and they can be found in modern, high-performance detergents and cleaning agents. Amylases are divided into α-, β-, γ-, and isoamylases. Amylases are classified as hydrolases (an enzyme that cleaves hydrolytically) or glycosidases (an enzyme that cleaves polysaccharides). α-amylases (EC 3.2.1.1) cleave internal α(1-4) glycoside bonds of amylose, but not terminal or α(1-6) glycoside bonds. This produces maltose, maltotriose, and branched oligosaccharides. β-amylases (EC 3.2.1.2) cleave one maltose molecule from the end of each chain in saccharides. γ-Amylases (EC 3.2.1.3) cleave a β-D-glucose molecule from the end of each saccharide chain. Isoamylases (EC 3.2.1.68) occur only in plants and bacteria and cleave the 1,6-glycosidic branchings of glycogen and amylopectin.The amylases used in the washing or cleaning agents known from the state of the art are usually of microbial origin and usually come from bacteria or fungi, for example of the genera . Bacillus, Pseudomonas, Acinetobacter, Micrococcus, Humicola, Trichoderma or Trichosporon, in particular Bacillus. Amylases are usually produced by suitable microorganisms using known biotechnological processes, for example by transgenic expression hosts of the genera Bacillus or by filamentous fungi.

[0003] A particularly extensively characterized alpha-amylase is a derivative of the alkalophilic Bacillus sp. Stamm TS-23 derived enzyme that hydrolyzes at least five types of starch (Lin et al., Biotechnol Appl Biochem, 28: 61-68, 1998). The alpha-amylase from Bacillus sp. Stamm TS- 23 has a pH optimum of 9, although it is stable over a wide pH range (i.e., pH 4.7 to 10.8). Its optimal temperature is 45°C, although the enzyme also exhibits activity at lower temperatures, for example, 15-20°C.

[0004] US patent applications US 7407677 B2 and US 8852912 B2 also disclose specific alpha-amylases and their fragments for use in detergents and cleaning agents. Amylase-containing detergents and cleaning agents are known from DE 102005062984 A1, WO 2014 / 183921, WO 2015 / 189372, WO 2015 / 150457, WO 2000 / 060058, and WO 2016 / 180748.

[0005] In general, only selected amylases are suitable for use in surfactant-containing preparations. Many amylases do not exhibit sufficient catalytic performance or stability in such preparations. Especially when used in detergents, which are normally purchased by consumers in quantities such that several weeks or months may pass before the detergent is finally used (i.e., the detergents must be stored by the consumer for weeks or months), many amylases exhibit instability, which in turn leads to insufficient catalytic activity during the washing process.

[0006] Consequently, prior art amylase-containing formulations have the disadvantage that they often do not exhibit satisfactory hydrolytic activity after storage of the formulation and therefore do not demonstrate optimal cleaning performance on amylase-sensitive soils.

[0007] Surprisingly, it has now been found that an amylase according to SEQ ID NO:1 or a sufficiently similar amylase is improved in terms of (storage) stability compared to a reference amylase and is therefore particularly suitable for use in detergents or cleaning agents.

[0008] Therefore, in a first aspect, the present invention is directed to an agent, preferably a washing or cleaning agent, particularly preferably a liquid washing or cleaning agent, characterized in that it contains at least one amylase which comprises an amino acid sequence which, over its entire length, has at least 98% sequence identity with the amino acid sequence given in SEQ ID NO:1, wherein the agent contains, based on the total weight, 0.0001 to 1% by weight, preferably 0.006 to 0.6% by weight of the amylase and wherein the following agents are excluded if they contain the amylase in a concentration of 0.2 mg / l active protein content or 0.05 mg / l active protein content: Compound Content of compound (% w / w) % active component (% w / w) LAS (linear alkylbenzene sulfonates) 5,15 5,00 AS (alkylbenzene sulfonates) 5,00 4,50 AEOS (alkyl ethoxy sulfate) 14,18 10,00 Coco fatty acid 1,00 1,00 AEO (alkyl ethoxylate) 5,00 5,00 MEA (monoethanolamine) 0,30 0,30 MPG (monopropylene glycol) 3,00 3,00 Ethanol 1,50 1,35 DTPA (as Na5 salt) pentasodium diethylenetriaminepentaacetic acid 0,25 0,10 Sodium citrate 4,00 4,00 Sodium formate 1,00 1,00 Sodium hydroxide 0,66 0,66 H2O, ion exchanged 58,95 58,95 and Compound Content of compound (% w / w) % active component (% w / w) LAS (linear alkylbenzene sulfonates) 12,00 11,60 AEOS (alkyl ethoxy sulfate), SLES (sodium lauryl ether sulfate) 17,63 4,90 Soy fatty acid 2,75 2,48 Coco fatty acid 2,75 2,80 Sodium hydroxide 1,75 1,80 Ethanol / Propan-2-ol 3,00 2,70 / 0,30 MPG (monopropylene glycol) 6,00 6,00 Glycerol 1,71 1,70 TEA (triethanolamine) 3,33 3,30 Sodium formate 1,00 1,00 Sodium citrate 2,00 2,00 DTMPA (diethylenetriaminepentaacetic acid) 0,48 0,20 PCA (polycarboxylic acid type polymer) 0,46 0,18 Phenoxy ethanol 0,50 0,50 H2O, ion exchanged 33,64 33,64

[0009] In a further aspect, the present invention is directed to the use of the agent according to the invention for removing starch-containing soils.

[0010] In another aspect, the present invention is further directed to a washing method comprising the method steps a) providing a washing or cleaning solution comprising an agent according to the invention, and b) bringing a textile or a hard surface into contact with the washing or cleaning solution according to (a).

[0011] For the purposes of the invention, the definition of a numerical range that is supposed to lie "between" two range boundaries is generally understood to mean that the range boundaries are not included. Numerical ranges defined from one range boundary to another include the range boundaries.

[0012] "At least one" as used herein includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more.

[0013] Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein refer to % by weight, in each case based on the mixture / composition in question.

[0014] In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. In particular, the fatty acids or fatty alcohols or their derivatives, for example, according to Roelenschen Oxo alcohols or their derivatives available from oxo synthesis can be used accordingly. Whenever alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is naturally present in only half the amount of the anion—sufficient to balance the charge.

[0015] The agents described herein are washing or cleaning agents, particularly preferably liquid washing or cleaning agents. According to the invention, a cleaning agent is understood to mean all agents suitable for cleaning solid surfaces, such as, for example, dishwashing detergents, in particular hand dishwashing detergents. According to the invention, a washing agent is understood to mean all agents suitable for cleaning or treating textiles, including specialty washing agents and washing aids. Further suitable ingredients of such agents are described in detail below.

[0016] "Liquid" as used herein with reference to the described compositions includes all compositions that flow at room temperature and also encompasses, for example, gels.

[0017] The present invention is based on the inventors' surprising discovery that an amylase according to SEQ ID NO:1 or a sufficiently similar amylase exhibits improved (storage) stability. This is particularly surprising given that the aforementioned amylase has not previously been associated with increased stability in surfactant compositions.

[0018] The amylases relevant to the invention exhibit increased stability in detergents or cleaning agents, particularly when stored for 2 or more days, 4 or more days, 10 or more days, 2 or more weeks, 4 or more weeks, or 8 or more weeks. Such agents with enhanced performance amylases enable improved washing results on starch-sensitive soils over a wide temperature range.

[0019] The amylases relevant to the invention exhibit enzymatic activity, i.e., they are capable of hydrolyzing starch, particularly in a washing or cleaning agent. An amylase relevant to the invention is therefore an enzyme that catalyzes the hydrolysis of glycosidic bonds in starch substrates and is thus capable of cleaving starch. Furthermore, an amylase relevant to the invention is preferably a mature amylase, i.e., the catalytically active molecule without signal and / or propeptide(s). Unless otherwise stated, the sequences indicated also refer to mature (processed) enzymes.

[0020] In various embodiments, the agent, preferably a washing or cleaning agent, particularly preferably a liquid washing or cleaning agent, is characterized in that (a) the amylase is obtainable from an amylase according to the invention as a starting molecule by single or multiple conservative amino acid substitution; and / or (b) the amylase is obtainable from an amylase according to the invention as a starting molecule by fragmentation, deletion, insertion or substitution mutagenesis and comprises an amino acid sequence which corresponds to the starting molecule over a length of at least 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480 or 482 contiguous amino acids.

[0021] In a further embodiment of the invention, the amylase comprises an amino acid sequence which is at least 98.5%, 98.8%, 99%, 99.5% or 100% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length.

[0022] In further embodiments of the invention, the agent according to the invention does not contain the following composition: a) a total amount of 2.0 to 8.0 wt.% C 9 -C 20 alkylbenzenesulfonate, and b) a total amount of 10.0 to 18.0 wt.% R 1< -O-(CH 2 CH 2 O) n -SO 3 M, wherein R 1< stands for a C 12-18 alkyl group, n stands for a number from 2 to 3 and M stands for a monovalent cation, and c) a total amount of 1.0 to 6.0 wt.% R 2< -O-(CH 2 CH 2 O) m -SO 3 M', wherein R 2< stands for a C 12-18 alkyl group, m stands for a number from 7 to 8 and M' stands for a monovalent cation, and d) a total amount of 2.0 to 10.0 wt.%, preferably 2.5 to 7.5 wt.%, more preferably 4.0 to 6.0 wt.%.-% fatty alcohol ethoxylate(s), and e) water and f) at least one amylase, wherein the amylase comprises an amino acid sequence which has at least 70% sequence identity with the amino acid sequence given in SEQ ID NO:1 over its entire length, wherein the wt% information relates to the total weight of the composition.

[0023] The composition according to the invention necessarily contains at least one amylase. This amylase is an α-amylase and comprises an amino acid sequence that has at least 98% sequence identity with the amino acid sequence given in SEQ ID NO:1 over its entire length. α-Amylases (EC 3.2.1.1) act as enzymes to hydrolyze internal α-1,4-glycosidic bonds of starch and starch-like polymers.

[0024] The amount of such amylase is typically 0.01 to 1 wt% based on active protein.

[0025] Preferred embodiments of said agents with said amylase achieve the advantageous cleaning performance at low temperatures between 10°C and 60°C, between 15°C and 50°C, and between 20°C and 40°C. Consequently, particularly preferred embodiments of said agents with said amylase are provided, the cleaning performance of which is advantageous specifically with regard to one soiling or several soilings of a similar type, in particular at temperatures of at most 25°C, particularly preferably at temperatures of at most 20°C.

[0026] Furthermore, preferred embodiments of the amylase used in the composition according to the invention have particular stability in washing or cleaning agents, for example towards surfactants and / or bleaching agents and / or towards temperature influences, in particular towards high temperatures, for example between 50 and 65°C, in particular 60°C, and / or towards acidic or alkaline conditions and / or towards pH changes and / or towards denaturing or oxidizing agents and / or towards proteolytic degradation and / or towards a change in redox conditions. Such advantageous embodiments of amylases according to the invention consequently enable improved washing results on amylase-sensitive soils over a wide temperature range.

[0027] For the purposes of the invention, cleaning performance is understood to mean the brightening performance of one or more types of soil, particularly on laundry or dishes. Within the scope of the invention, both the washing or cleaning agent comprising the amylase or the washing or cleaning liquor formed by this agent, as well as the amylase itself, have a respective cleaning performance. The cleaning performance of the enzyme thus contributes to the cleaning performance of the agent or the washing or cleaning liquor formed by the agent. The cleaning performance is preferably determined as specified below.

[0028] The identity of nucleic acid or amino acid sequences is determined by sequence comparison. This sequence comparison is based on the state-of-the-art and commonly used BLAST algorithm (see, for example, Altschul, SF, Gish, W., Miller, W., Myers, EW & Lipman, DJ (1990) "Basic local alignment search tool." J. Mol. Biol. 215:403-410, and Altschul, Stephan F., Thomas L. Madden, Alejandro A. Schaffer, Jinghui Zhang, Hheng Zhang, Webb Miller, and David J. Lipman (1997): "Gapped BLAST and PSI-BLAST: a new generation of protein database search programs"; Nucleic Acids Res., 25, pp. 3389-3402) and is essentially performed by matching similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences. A tabular assignment of the relevant positions is called alignment. Another algorithm available in the state of the art is the FASTA algorithm.Sequence alignments, especially multiple sequence alignments, are created using computer programs. Commonly used programs include the Clustal series (see, for example, Chenna et al. (2003): Multiple sequence alignment with the Clustal series of programs. Nucleic Acid Research 31, 3497-3500), T-Coffee (see, for example, Notredame et al. (2000): T-Coffee: A novel method for multiple sequence alignments. J. Mol. Biol. 302, 205-217), or programs based on these programs or algorithms. In the present patent application, all sequence alignments were created using the computer program Vector NTI ®< Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the specified standard parameters. The AlignX module for sequence comparisons is based on ClustalW.

[0029] Such a comparison also allows a statement to be made about the similarity of the compared sequences to one another. This is usually expressed as percent identity, i.e. the proportion of identical nucleotides or amino acid residues at the same positions or corresponding positions in an alignment. The broader term homology in amino acid sequences includes conserved amino acid substitutions, i.e. amino acids with similar chemical activity, since these usually exert similar chemical activities within the protein. Therefore, the similarity of the compared sequences can also be expressed as percent homology or percent similarity. Identity and / or homology statements can be made for entire polypeptides or genes, or just for individual regions. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by similarities in the sequences.Such regions often exhibit identical functions. They can be small and comprise only a few nucleotides or amino acids. Such small regions often perform essential functions for the overall activity of the protein. It may therefore be useful to refer sequence matches only to individual, possibly small regions. Unless otherwise stated, however, statements of identity or homology in this application refer to the entire length of the respective nucleic acid or amino acid sequence.

[0030] In a particularly preferred embodiment of the invention, the amylase is characterized in that its cleaning performance corresponds at least to that of an amylase which comprises an amino acid sequence which corresponds to the amino acid sequence given in SEQ ID NO: 1, wherein the cleaning performance is determined in a washing system which contains a detergent in a dosage of between 4.5 and 7.0 grams per liter of wash liquor and the amylase, wherein the amylases to be compared are used in the same concentration (based on active protein), and the cleaning performance is determined by measuring the degree of whiteness of the washed textiles, the washing process is carried out for 70 minutes at a temperature of 40°C, and the water has a water hardness of between 15.5 and 16.5° (German hardness). The concentration of amylase in the detergent intended for this washing system is from 0.001 to 0.1% by weight, preferably from 0.01 to 0.06% by weight.-%, based on active protein.

[0031] In addition to the amino acid modifications explained above, amylases according to the invention may exhibit further amino acid modifications, in particular amino acid substitutions, insertions, or deletions. Such amylases are further developed, for example, by targeted genetic modification, i.e., by mutagenesis methods, and optimized for specific applications or with regard to specific properties (e.g., with regard to their catalytic activity, stability, etc.). Furthermore, nucleic acids according to the invention can be incorporated into recombinant approaches and thus used to generate completely novel amylases or other polypeptides.

[0032] The aim is to introduce targeted mutations such as substitutions, insertions, or deletions into the known molecules in order, for example, to improve the cleaning performance of enzymes according to the invention. For this purpose, in particular, the surface charges and / or the isoelectric point of the molecules and thus their interactions with the substrate can be altered. For example, the net charge of the enzymes can be altered in order to influence substrate binding, particularly for use in detergents and cleaning agents. Alternatively or additionally, one or more corresponding mutations can increase the stability of the amylase and thereby improve its cleaning performance. Advantageous properties of individual mutations, e.g., individual substitutions, can complement each other.An amylase that has already been optimized with regard to certain properties, for example with regard to its stability towards surfactants and / or bleaching agents and / or other components, can therefore be further developed within the scope of the invention.

[0033] The following convention is used to describe substitutions that affect exactly one amino acid position (amino acid exchanges): first, the naturally occurring amino acid is named using the internationally accepted one-letter code, followed by the corresponding sequence position, and finally the inserted amino acid. Multiple exchanges within the same polypeptide chain are separated by slashes. In the case of insertions, additional amino acids are named according to the sequence position. In the case of deletions, the missing amino acid is replaced by a symbol, such as an asterisk or a dash. For example, A95G describes the substitution of alanine at position 95 with glycine, A95AG the insertion of glycine after the amino acid alanine at position 95, and A95* the deletion of alanine at position 95. This nomenclature is familiar to those skilled in the art in the field of enzyme technology.

[0034] The present invention therefore further provides a washing and cleaning agent containing an α-amylase, wherein the α-amylase is characterized in that it is obtainable from an amylase according to the invention as the starting molecule by single or multiple conservative amino acid substitution. The term "conservative amino acid substitution" means the exchange (substitution) of one amino acid residue for another amino acid residue, wherein this exchange does not lead to a change in the polarity or charge at the position of the exchanged amino acid, e.g., the exchange of one nonpolar amino acid residue for another nonpolar amino acid residue. Conservative amino acid substitutions within the scope of the invention include, for example: G=A=S, I=V=L=M, D=E, N=Q, K=R, Y=F, S=T, G=A=I=V=L=M=Y=F=W=P=S=T.

[0035] A further subject matter of the present invention is therefore a washing and cleaning agent containing an α-amylase, wherein the α-amylase is characterized in that it is obtainable from an amylase according to the invention as starting molecule by fragmentation, deletion, insertion or substitution mutagenesis and comprises an amino acid sequence which corresponds to the starting molecule over a length of at least 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 475, 476, 477, 478, 479, 480, 481 or 482 contiguous amino acids.

[0036] For example, it is possible to delete individual amino acids at the termini or in the loops of the enzyme without losing or reducing enzymatic activity. Furthermore, such fragmentation, deletion, insertion, or substitution mutagenesis can also reduce the allergenicity of the enzyme in question, thus improving their overall usability. Advantageously, the enzymes retain their enzymatic activity even after mutagenesis, i.e., their enzymatic activity is at least equivalent to that of the parent enzyme. Substitutions can also have beneficial effects. Both individual and multiple contiguous amino acids can be exchanged for other amino acids.

[0037] An enzyme according to the invention can be additionally stabilized, in particular by one or more mutations, for example substitutions, or by coupling to a polymer. This is because increasing stability during storage and / or use, for example during the washing process, leads to longer-lasting enzymatic activity and thus improved cleaning performance. In principle, all stabilization options described and / or expedient in the prior art are contemplated. Preference is given to stabilizations achieved via mutations of the enzyme itself, since such stabilizations do not require any further steps following the isolation of the enzyme. Suitable sequence modifications for this purpose are known from the prior art.

[0038] Other stabilization options include: Alteration of the binding of metal ions, in particular of the calcium binding sites, for example by exchanging one or more of the amino acids involved in calcium binding for one or more negatively charged amino acids and / or by introducing sequence changes in at least one of the sequences of the two amino acids arginine / glycine; protection against the influence of denaturing agents such as surfactants by mutations that cause a change in the amino acid sequence on or at the surface of the protein; replacement of amino acids located close to the N-terminus for those that presumably come into contact with the rest of the molecule via non-covalent interactions and thus contribute to maintaining the globular structure.

[0039] Preferred embodiments are those in which the enzyme is stabilized in several ways, since several stabilizing mutations act additively or synergistically.

[0040] The invention further relates to an agent as described above, which is characterized in that the amylase has at least one chemical modification. An enzyme with such a modification is referred to as a derivative, i.e., the enzyme is derivatized.

[0041] For the purposes of the present application, derivatives are understood to mean proteins whose pure amino acid chain has been chemically modified. Such derivatizations can, for example, occur in vivo by the host cell expressing the protein. Coupling of low-molecular-weight compounds such as lipids or oligosaccharides is particularly noteworthy in this regard. Derivatizations can also be carried out in vitro, for example, by chemically converting a side chain of an amino acid or by covalently binding another compound to the protein. For example, coupling amines to carboxyl groups of an enzyme is possible to alter the isoelectric point. Such another compound can also be another protein, which is bound to a protein according to the invention, for example, via bifunctional chemical compounds.Derivatization also refers to covalent binding to a macromolecular carrier or noncovalent inclusion in suitable macromolecular cage structures. Derivatizations can, for example, influence substrate specificity or binding strength to the substrate, or temporarily block enzymatic activity if the coupled substance is an inhibitor. This can be useful, for example, during storage. Such modifications can also influence stability or enzymatic activity. They can also serve to reduce the allergenicity and / or immunogenicity of the protein and thus, for example, increase its skin compatibility. For example, coupling with macromolecular compounds, such as polyethylene glycol, can improve the protein's stability and / or skin compatibility.

[0042] Derivatives of a protein according to the invention can, in the broadest sense, also be understood as preparations of these proteins. Depending on the method of extraction, processing, or preparation, a protein can be associated with various other substances, for example, from the culture of the producing microorganisms. A protein can also be deliberately mixed with other substances, for example, to increase its storage stability. Therefore, all preparations of a protein according to the invention are also according to the invention. This is independent of whether or not it actually exhibits this enzymatic activity in a specific preparation. It may be desired that it has no or only low activity during storage and only exhibits its enzymatic function at the time of use. This can be controlled, for example, via appropriate accompanying substances.

[0043] In various embodiments, the agent according to the invention can further contain at least one further component selected from the group consisting of surfactants, further enzymes, enzyme stabilizers, complexing agents for heavy metals, builders, bleaching agents, builders, electrolytes, non-aqueous solvents, pH adjusters, odor absorbers, deodorizing substances, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, shrinkage inhibitors, further crease protection agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and slip-resistant agents, softening components and UV absorbers.

[0044] In addition to amylase, the agent according to the invention may also contain a compound from the class of anionic surfactants of the formula (I) R-SO 3 -< Y +< (I).

[0045] In this formula (I), R represents a linear or branched unsubstituted alkylaryl radical. Y represents a monovalent cation or the nth part of an n-valent cation, preferred being alkali metal ions, including Na+< or K+<, with Na+< being most preferred. Further cations Y+< can be selected from NH4+<, ½Zn2+<, ½Mg2+<, ½Ca2+<, ½Mn2+<, and mixtures thereof.

[0046] "Alkylaryl," as used herein, refers to organic radicals consisting of an alkyl radical and an aromatic radical. Typical examples of such radicals include, but are not limited to, alkylbenzene radicals such as benzyl, butylbenzene radicals, nonylbenzene radicals, decylbenzene radicals, undecylbenzene radicals, dodecylbenzene radicals, tridecylbenzene radicals, and the like.

[0047] In various embodiments, such surfactants are selected from linear or branched alkylbenzenesulfonates of the formula A-1 in which R' and R" together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 C atoms. A particularly preferred representative can be described by the formula A-1a:

[0048] In various embodiments, the compound of formula (I) is preferably the sodium salt of a linear alkylbenzenesulfonate.

[0049] In agents according to the invention, the at least one compound from the class of anionic surfactants of formula (I) can be present in the washing or cleaning agent in an amount of 0.001 to 30 wt.%, preferably 1 - 30 wt.%, further preferably 2 - 25 wt.%, even more preferably 3 - 20 wt.%, in each case based on the total weight of the washing or cleaning agent.

[0050] In various embodiments, the agent may contain at least one other surfactant in addition to the at least one compound of formula (I) or alternatively thereto. Alternative or additional surfactants include, in particular, other anionic surfactants, nonionic surfactants, and mixtures thereof, but also cationic, zwitterionic, and amphoteric surfactants.

[0051] In various embodiments, the agents according to the invention preferably contain at least one anionic surfactant from the group of alkyl ether sulfates.

[0052] Alkyl ether sulfates (fatty alcohol ether sulfates, INCI Alkyl Ether Sulfates) are products of sulfation reactions on alkoxylated alcohols. In this context, the skilled person generally understands alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably within the meaning of the present invention with longer-chain alcohols, i.e., with aliphatic straight-chain or singly or multiply branched, acyclic or cyclic, saturated or singly or multiply unsaturated, preferably straight-chain, acyclic, saturated alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16, and particularly preferably 12 to 14 carbon atoms. As a rule, depending on the reaction conditions, a complex mixture of addition products with different degrees of ethoxylation (n = 1 to 30, preferably 1 to 20, in particular 1 to 10, particularly preferably 2 to 4) is formed from n moles of ethylene oxide and one mole of alcohol.A further embodiment of the alkoxylation consists in the use of mixtures of alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.

[0053] In various embodiments, the alkyl ether sulfate is in particular an anionic surfactant of the formula R 1< -O-(AO) n -SO 3 -< X +< (II).

[0054] In this formula (II), R 1< represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R 1< are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, with preference being given to representatives with an even number of carbon atoms. Particularly preferred radicals R 1< are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.

[0055] AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 1 to 10. Very particularly preferably, n stands for the numbers 1, 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions and among them Na +< or K +< , with Na +< being extremely preferred. Further cations X+ can be selected from NH 4 +< , ½ Zn 2+< , ½ Mg 2+< , ½ Ca 2+< , ½ Mn 2+< , and mixtures thereof.

[0056] Particularly preferred are fatty alcohol ether sulfates of the formula A-2 with k = 11 to 19, n = 1, 2, 3 or 4. Particularly preferred representatives are Na-C 12-14 fatty alcohol ether sulfates with 1 to 2 EO (k = 11-13, n = 1 or 2 in formula A-2), especially 2 EO.

[0057] The agent according to the invention, in particular a cleaning agent for hard surfaces, such as in particular a manual dishwashing agent, contains in a preferred embodiment one or more alkyl ether sulfates in an amount of 10 to 40 wt.%, preferably 13 to 35 wt.%, in particular 15 to 30 wt.%.

[0058] Alkylsulfonates (INCI Sulfonic Acids) can also be used as anionic surfactants. These typically have an aliphatic straight-chain or mono- or polybranched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical with 6 to 22, preferably 9 to 20, in particular 11 to 18, and particularly preferably 14 to 17 carbon atoms.

[0059] Suitable alkylsulfonates are accordingly saturated alkanesulfonates, unsaturated olefinsulfonates, and ethersulfonates—formally derived from the alkoxylated alcohols on which alkyl ether sulfates are based. A distinction is made between terminal ethersulfonates (n-ethersulfonates) with a sulfonate function bonded to the polyether chain and internal ethersulfonates (i-ethersulfonates) with a sulfonate function linked to the alkyl radical. Preferred according to the invention are alkanesulfonates, in particular alkanesulfonates with a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na-C 13-17 alkanesulfonate (INCI Sodium C14-17 Alkyl Sec Sulfonate).

[0060] The agent according to the invention, in particular a manual dishwashing agent, contains one or more secondary alkylsulfonates in an amount of usually 1 to 15 wt.%, preferably 3 to 10 wt.%, in particular 4 to 8 wt.%.

[0061] Other possible anionic surfactants are known to the person skilled in the art from the relevant prior art for detergents and cleaning agents. These include, in particular, aliphatic sulfates such as monoglyceride sulfates and ester sulfonates (sulfofatty acid esters), lignin sulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids, and alkyl (ether) phosphates.

[0062] Other suitable anionic surfactants are also anionic gemini surfactants with a diphenyl oxide basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings according to the formula -< O 3 S(C 6 H 3 R)O(C 6 H 3 R')SO 3 -< , in which R is an alkyl radical with, for example, 6, 10, 12 or 16 carbon atoms and R' is R or H (Dowfax ®< Dry Hydrotrope Powder with C 16 alkyl radical(s); INCI Sodium Hexyldiphenyl Ether Sulfonate, Disodium Decyl Phenyl Ether Disulfonate, Disodium Lauryl Phenyl Ether Disulfonate, Disodium Cetyl Phenyl Ether Disulfonate) and fluorinated anionic surfactants, in particular perfluorinated alkylsulfonates such as ammonium C 9 / 10 perfluoroalkylsulfonate (Fluorad ®< FC 120) and perfluorooctanesulfonic acid potassium salt (Fluorad ®< FC 95), whereby a content of fluorine compounds in the washing or cleaning agents according to the invention is less preferred.

[0063] Particularly preferred further anionic surfactants are the anionic sulfosuccinic acid surfactants sulfosuccinates, sulfosuccinamates, and sulfosuccinamides, in particular sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates. The sulfosuccinates are the salts of the mono- and diesters of sulfosuccinic acid HOOCCH(SO 3 H)CH 2 COOH, while the sulfosuccinamates are understood to be the salts of the monoamides of sulfosuccinic acid, and the sulfosuccinamides are understood to be the salts of the diamides of sulfosuccinic acid. The salts are preferably alkali metal salts, ammonium salts, and mono-, di-, or trialkanolammonium salts, for example mono-, di-, or triethanolammonium salts, in particular lithium, sodium, potassium, or ammonium salts, particularly preferably sodium or ammonium salts, most preferably sodium salts.

[0064] In a particular embodiment, the agent according to the invention contains as anionic sulfosuccinic acid surfactants one or more sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or sulfosuccinamates, in particular sulfosuccinates, in an amount of usually 0.001 to 5 wt.%, preferably 0.01 to 4 wt.%, in particular 0.1 to 3 wt.%, particularly preferably 0.2 to 2 wt.%, extremely preferably 0.5 to 1.5 wt.%, for example 1 wt.%.

[0065] Other anionic surfactants that can be used are the alkyl sulfates of the formula R 2< -O-SO 3 -< X +< (III).

[0066] In this formula (III), R 2< represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred R 2< radicals are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals, and mixtures thereof, with preference given to those having an even number of carbon atoms. Particularly preferred R 2< radicals are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from C 10 -C 20 oxo alcohols. Y represents a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions and among them Na +< or K +< , with Na +< being most preferred.Further cations Y+ can be selected from NH 4 +< , ½ Zn 2+< ,½ Mg 2+< ,½ Ca 2+< ,½ Mn 2+< , and mixtures thereof.

[0067] In various embodiments, these surfactants are selected from fatty alcohol sulfates of the formula A-3 with k = 11 to 19. Particularly preferred representatives are Na-C 12-14 fatty alcohol sulfates (k = 11-13 in formula A-3).

[0068] The anionic surfactants are typically used as alkali metal, alkaline earth metal, and / or mono-, di-, or trialkanolammonium salts and / or in the form of their corresponding acid, which is neutralized in situ with the corresponding alkali metal hydroxide, alkaline earth metal hydroxide, and / or mono-, di-, or trialkanolamine. Preferred alkali metals are potassium and especially sodium; preferred alkaline earth metals are calcium and especially magnesium; and preferred alkanolamines are mono-, di-, or triethanolamine. The sodium salts are particularly preferred.

[0069] The amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) that can be used according to the invention include alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the betaines are preferred within the scope of the teaching according to the invention.

[0070] Suitable betaines, which are mainly used in manual dishwashing detergents, are the alkyl betaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy formula IV, R 1< -[CO-X-(CH 2 ) n ] x -N +< (R 2< )(R 3< )-(CH 2 ) m -[CH(OH)-CH 2 ] y -Y -< (IV)

[0071] in which R 1< is a saturated or unsaturated C 6-22 alkyl radical, preferably C 8-18 alkyl radical, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical, XNH, NR 4< with the C 1-4 alkyl radical R 4< , O or S, n is a number from 1 to 10, preferably 2 to 5, in particular 3, x0 or 1, preferably 1, R 2< , R 3< independently of one another are a C 1-4 alkyl radical, optionally hydroxy-substituted such as a hydroxyethyl radical, but in particular a methyl radical, my number from 1 to 4, in particular 1, 2 or 3, y0 or 1 and YCOO, SO 3 , OPO(OR 5< )O or P(O)(OR 5< )O, where R 5< is a hydrogen atom, H or a C 1-4 alkyl radical.

[0072] The alkyl and alkylamidobetaines, betaines of formula I with a carboxylate group (Y -< = COO -< ), are also called carbobetaines.

[0073] Preferred betaines are the alkyl betaines of the formula (Ia), the alkylamidobetaines of the formula (IVb), the sulfobetaines of the formula (IVc) and the amidosulfobetaines of the formula (IVd), R 1< -N +< (CH 3 ) 2 -CH 2 COO -< (IVa) R 1< -CO-NH-(CH 2 ) 3 -N +< (CH 3 ) 2 -CH 2 COO -< (IVb) R 1< -N +< (CH 3 ) 2 -CH 2 CH(OH)CH 2 SO 3 -< (IVc) R 1< -CO-NH-(CH 2 ) 3 -N +< (CH 3 ) 2 -CH 2 CH(OH)CH 2 SO 3 -< (IVd) in which R 1< has the same meaning as in formula I.

[0074] Particularly preferred betaines are the carbobetaines, in particular the carbobetaines of formula (IVa) and (IVb), most preferably the alkylamidobetaines of formula (IVb).

[0075] The agent according to the invention may contain one or more betaines in an amount of usually 1 to 15 wt.%, preferably 3 to 10 wt.%, in particular 4 to 8 wt.%.

[0076] The alkylamidoalkylamines (INCI Alkylamido Alkylamines) are amphoteric surfactants of the formula (V), R 9< -CO-NR 10< -(CH 2 ) i -N(R 11< )-(CH 2 CH 2 O) j -(CH 2 ) k -[CH(OH)] l -CH 2 -Z-OM (V) in which R 9< is a saturated or unsaturated C 6-22 alkyl radical, preferably C 8-18 alkyl radical, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical, R 10< is a hydrogen atom, H or a C 1-4 alkyl radical, preferably H, i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3, R 11< is a hydrogen atom, H or CH 2 COOM (for M see below), j is a number from 1 to 4, preferably 1 or 2, in particular 1, no number from 0 to 4, preferably 0 or 1, l0 or 1, where k = 1 when l = 1, ZCO, SO 2 , OPO(OR 12< ) or P(O)(OR 12< ), where R 12< is a C 1-4 alkyl radical or M (see below), and M is hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine.

[0077] Preferred representatives satisfy the formulas Va to Vd, R 9< -CO-NH-(CH 2 ) 2 -N(R 11< )-CH 2 CH 2 O-CH 2 -COOM (Va) R 9< -CO-NH-(CH 2 ) 2 -N(R 11< )-CH 2 CH 2 O-CH 2 CH 2 -COOM (Vb) R 9< -CO-NH-(CH 2 ) 2 -N(R 11< )-CH 2 CH 2 O-CH 2 CH(OH)CH 2 -SO 3 M (Vc) R 9< -CO-NH-(CH 2 ) 2 -N(R 11< )-CH 2 CH 2 O-CH 2 CH(OH)CH 2 -OPO 3 HM (Vd) in which R 11< and M have the same meaning as in formula (V).

[0078] Preferred alkyl-substituted amino acids according to the invention (INCI Alkyl-Substituted Amino Acids) are monoalkyl-substituted amino acids according to formula (VI), R 13< -NH-CH(R 14< )-(CH 2 ) u -COOM' (VI) in which R 13< is a saturated or unsaturated C 6-22 alkyl radical, preferably C 8-18 alkyl radical, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical, R 14< is a hydrogen atom H or a C 1-4 alkyl radical, preferably H, u is a number from 0 to 4, preferably 0 or 1, in particular 1, and M' is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine, alkyl-substituted imino acids according to formula (VII), R 15 -N-[(CH 2 ) v -COOM"] 2 (VII) in the R 15 a saturated or unsaturated C 6-22 -alkyl radical, preferably C 8-18 -alkyl radical, in particular a saturated C 10-16 -alkyl radical, for example a saturated C 12-14 -alkyl radical, a number from 1 to 5, preferably 2 or 3, in particular 2, and M"is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine, where M" in the two carboxy groups can have the same or two different meanings, e.g. hydrogen and sodium or twice sodium, and mono- or dialkyl-substituted natural amino acids according to formula (VIII), R 16 -N(R 17 )-CH(R 16 )-COOM‴ (VIII) in the R 16 a saturated or unsaturated C 6-22 -alkyl radical, preferably C 8-18 -alkyl radical, in particular a saturated C 10-16 -alkyl radical, for example a saturated C 12-14 -alkyl radical, R 17< is a hydrogen atom or a C 1-4 alkyl radical, optionally hydroxy- or amine-substituted, e.g. a methyl, ethyl, hydroxyethyl or aminopropyl radical, R 18< is the radical of one of the 20 natural α-amino acids H 2 NCH(R 18< )COOH, and M"' is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine.

[0079] Particularly preferred alkyl-substituted amino acids are the aminopropionates according to formula (VIa), R 13< -NH-CH 2 CH 2 COOM' (VIa) in which R 13< and M' have the same meaning as in formula (VI).

[0080] Acylated amino acids are amino acids, in particular the 20 natural α-amino acids, which carry the acyl radical R 19< CO of a saturated or unsaturated fatty acid R 19< COOH on the amino nitrogen atom, where R 19< is a saturated or unsaturated C 6-22 alkyl radical, preferably C 8-18 alkyl radical, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical. The acylated amino acids can also be used as alkali metal salt, alkaline earth metal salt or alkanolammonium salt, e.g. mono-, di- or triethanolammonium salt. Examples of acylated amino acids are the acyl derivatives summarized under Amino Acids according to the INCI, e.g. Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine or Myristoyl Methylalanine.

[0081] In a particular embodiment of the invention, a combination of two or more different amphoteric surfactants, in particular a binary amphoteric surfactant combination, is used.

[0082] The amphoteric surfactant combination preferably contains at least one betaine, in particular at least one alkylamidobetaine, particularly preferably cocoamidopropylbetaine.

[0083] In a further particular embodiment, the agent according to the invention contains one or more amphoteric surfactants in an amount of more than 8% by weight. In yet another particular embodiment, the agent according to the invention contains one or more amphoteric surfactants in an amount of less than 2% by weight.

[0084] Nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol. The alcohol radical can be linear or, preferably, methyl-branched in the 2-position, or can contain linear and methyl-branched radicals in a mixture, as is usually the case in oxo alcohol radicals. However, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, for example, from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO, or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO, or 8 EO, C 12-18 alcohols with 3 EO, 5 EO, or 7 EO, and mixtures thereof, such as mixtures of C 12-14 alcohols with 3 EO and C 12-18 alcohols with 7 EO. The stated degrees of ethoxylation represent statistical averages, which can be a whole or fractional number 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 alcohol with 14 EO, 25 EO, 30 EO, or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.More preferably, the cleaning agent for hard surfaces contains a C 12-18 fatty alcohol with 7 EO or a C 13-15 oxo alcohol with 7 EO as non-ionic surfactant.

[0085] The content of non-ionic surfactants in the cleaning agent is preferably 1 to 30 wt.% and preferably 2 to 25 wt.%, in each case based on the total cleaning agent.

[0086] These non-ionic surfactants, in combination with an amine oxide, have good cleaning performance on grease-soiled hard surfaces, such as dishes.

[0087] Nonionic surfactants within the scope of the invention include alkoxylates, but also alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers, and fatty acid polyglycol esters. Block polymers of ethylene oxide and propylene oxide, as well as fatty acid alkanolamides and fatty acid polyglycol ethers, are also suitable. Other important classes of nonionic surfactants according to the invention are amine oxides and sugar surfactants, especially alkyl polyglucosides.

[0088] The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy formula IX, R 6< R 7< R 8< N +< -O -< (IX) R 6< -[CO-NH-(CH 2 ) w ] z -N +< (R 7< )(R 8< )-O -< (IX) in which R 6< is a saturated or unsaturated C 6-22 alkyl radical, preferably C 8-18 alkyl radical, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical, which in the alkylamidoamine oxides is bonded to the nitrogen atom N via a carbonylamidoalkylene group -CO-NH-(CH 2 ) z - and in the alkoxyalkylamine oxides via an oxaalkylene group -O-(CH 2 ) z -, where z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3, R 7< , R 8< are independently a C 1-4 alkyl radical, optionally hydroxy-substituted such as a hydroxyethyl radical, in particular a methyl radical.

[0089] The content of amine oxide in the cleaning agent is preferably 1 to 15 wt.% and preferably 2 to 10 wt.%, in each case based on the total cleaning agent.

[0090] Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerol amides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides), and alkyl polyglycosides. Preferred sugar surfactants within the scope of the invention are the alkyl polyglycosides and the sugar amides, as well as their derivatives, in particular their ethers and esters. The ethers are the products of the reaction of one or more, preferably one, sugar hydroxyl group with a compound containing one or more hydroxyl groups, for example C 1-22 alcohols or glycols such as ethylene and / or propylene glycol, where the sugar hydroxyl group can also carry polyethylene glycol and / or polypropylene glycol residues. The esters are the reaction products of one or more, preferably one, sugar hydroxyl group with a carboxylic acid, in particular a C 6-22 fatty acid.

[0091] Particularly preferred sugar amides satisfy the formula R'C(O)N(R")[Z], in which R' represents a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, having 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R" represents a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, a C 1-5 alkyl radical, in particular a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or n-pentyl radical, or hydrogen and Z represents a sugar radical, ie a monosaccharide radical, Particularly preferred sugar amides are the amides of glucose, the glucamides, for example lauroylmethylglucamide.

[0092] The alkyl polyglycosides (APG) are particularly preferred sugar surfactants within the scope of the invention. They are known substances that can be obtained by the relevant processes of preparative organic chemistry. They preferably conform to the general formula R i< O(AO) a [G] x , in which R i< represents a linear or branched, saturated or unsaturated alkyl radical having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] represents a glycosidically linked sugar radical, preferably xylose, but in particular glucose, and AO represents an alkyleneoxy group, e.g., an ethyleneoxy or propyleneoxy group, and a represents the average degree of alkoxylation from 0 to 20. Here, the group (AO) a can also contain various alkyleneoxy units, e.g. ethyleneoxy or propyleneoxy units, where a is then the average total degree of alkoxylation, iethe sum of the degree of ethoxylation and propoxylation. The index number x indicates the degree of oligomerization (DP degree), i.e. the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x in a given compound must always be an integer and can primarily assume the values ​​x = 1 to 6, the value x for a specific alkyl glycoside is an analytically determined calculated value that is usually a fractional number. Preference is given to using alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0. From an application point of view, preference is given to alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6. Unless otherwise stated below, the alkyl radicals R i< of the APG are linear unsaturated radicals with the specified number of carbon atoms.

[0093] The alkyl or alkenyl radical R i< can be derived from primary alcohols having 8 to 18, preferably 8 to 14, carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol, and undecyl alcohol, as well as their technical mixtures, such as those obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from the Roelen oxo synthesis.

[0094] Preferably, the alkyl or alkenyl radical R i< is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, or oleyl alcohol. Other suitable alcohols include elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and technical mixtures thereof.

[0095] Particularly preferred APGs are not alkoxylated (a = 0) and satisfy the formula RO[G] x , in which R, as before, represents a linear or branched, saturated or unsaturated alkyl radical having 4 to 22 carbon atoms, [G] represents a glycosidically linked sugar radical, preferably glucose radical, and x represents a number from 1 to 10, preferably 1.1 to 3, in particular 1.2 to 1.6. Accordingly, preferred alkyl polyglycosides are, for example, C 8-10 and a C 12-14 alkyl polyglucoside with a DP degree of 1.4 or 1.5, in particular C 8-10 alkyl 1,5-glucoside and C 12-14 alkyl 1,4-glucoside.

[0096] The agent according to the invention may additionally contain one or more cationic surfactants (cationic surfactants; INCI Quaternary Ammonium Compounds), usually in an amount of 0.001 to 5 wt.%, preferably 0.01 to 4 wt.%, in particular 0.1 to 3 wt.%, particularly preferably 0.2 to 2 wt.%, extremely preferably 0.5 to 1.5 wt.%, for example 1 wt.%.

[0097] Preferred cationic surfactants are quaternary surface-active compounds, especially those with an ammonium, sulfonium, phosphonium, iodonium, or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with antimicrobial activity, the agent can be given an antimicrobial effect or its existing antimicrobial effect, possibly due to other ingredients, can be improved.

[0098] Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV; INCI Quaternary Ammonium Compounds) according to the general formula (RI< )(R II< )(R II< )(R IV< )N +< X -< , in which RI< to R IV< are identical or different C 1-22 alkyl radicals, C 7-28 aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic bond such as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, e.g. a pyridinium or imidazolinium compound, and X -< are halide ions, sulfate ions, hydroxide ions or similar anions. For optimal antimicrobial action, at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, C atoms.

[0099] QACs can be prepared by reacting tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, and even ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out under mild conditions using methyl chloride. Amines with three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferentially quaternized with dimethyl sulfate.

[0100] To avoid possible incompatibilities between the cationic surfactants and the anionic surfactants contained according to the invention, surfactants that are as compatible with anionic surfactants and / or contain as little cationic surfactants as possible are used or, in a particular embodiment of the invention, cationic surfactants are omitted entirely.

[0101] An agent according to the invention, in particular a washing or cleaning agent, may contain at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.

[0102] Generally applicable builders include aminocarboxylic acids and their salts, zeolites, silicates, carbonates, and organic (co)builders. These agents are preferably phosphate-free.

[0103] Water-soluble organic builder substances include polycarboxylic acids, especially citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, especially methylglycinediacetic acid, glutaminediacetic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, as well as polyaspartic acid, polymeric hydroxy compounds such as dextrin, as well as polymeric (poly)carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids, and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the acid content is at least 50% by weight.The organic builders can be used, particularly 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, especially their alkali metal salts.

[0104] Organic builder substances may, if desired, be present in amounts up to 40% by weight, in particular up to 25% by weight and preferably from 1% to 8% by weight.

[0105] Alkali silicates are particularly suitable as water-soluble inorganic builder materials. Crystalline or amorphous alkali aluminosilicates, if desired, can be used as water-insoluble, water-dispersible inorganic builder materials, in particular in amounts of up to 50 wt.%, preferably not more than 40 wt.%, and in liquid compositions in particular from 1 wt.% to 5 wt.%. Among these, crystalline sodium aluminosilicates of detergent quality, in particular zeolite A, P, and optionally X, are preferred. Amounts close to the stated upper limit are preferably used in solid, particulate compositions. Suitable aluminosilicates, in particular, have no particles with a grain size exceeding 30 µm and preferably consist of at least 80 wt.% particles with a size below 10 µm.

[0106] 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 usable as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 of less than 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are sodium silicates, in particular amorphous sodium silicates, with a molar Na 2 O:SiO 2 ratio of 1:2 to 1:2.8. As crystalline silicates, which can be present alone or in a mixture with amorphous silicates, crystalline layered silicates of the general formula Na 2 Si x O 2x+1 · y H 2 O are preferably used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values ​​for x are 2, 3 or 4.Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values ​​2 or 3. In particular, both beta- and delta-sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred. Virtually anhydrous crystalline alkali silicates produced from amorphous alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, can also be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline sodium layered silicate with a modulus of 2 to 3 is used, such as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention.If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based on anhydrous active substances, is preferably 1:10 to 10:1. In agents containing both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.

[0107] Inorganic builder substances are, if desired, contained in the compositions according to the invention preferably in amounts of up to 60% by weight, in particular from 1% by weight to 10% by weight.

[0108] Detergents or cleaning agents according to the invention can contain other enzymes in addition to amylase. These can be hydrolytic enzymes or other enzymes in a concentration appropriate for the effectiveness of the agent. One embodiment of the invention thus represents agents that comprise one or more enzymes. Preferred enzymes that can be used are all enzymes that can exhibit catalytic activity in the agent according to the invention, in particular a protease, amylases distinguishable from the amylase according to SEQ ID NO:1, a cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, β-glucosidase, pectinase, carrageenase, perhydrolase, oxidase, oxidoreductase or a lipase, as well as mixtures thereof. The additional enzyme is, as described above, preferably a protease. Enzymes are advantageously contained in the agent in an amount of 1 x 10 -8< to 5 wt.% based on active protein.With increasing preference, each enzyme is present in agents according to the invention in an amount of 1 x 10 -7 < -3 wt.%, of 0.00001-1 wt.%, of 0.00005-0.5 wt.%, of 0.0001 to 0.1 wt.% and particularly preferably of 0.0001 to 0.05 wt.%, based on active protein. The enzymes particularly preferably exhibit synergistic cleaning performance against specific soils or stains, i.e., the enzymes contained in the agent 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 agent according to the invention.

[0109] The other amylase(s) is / are preferably an α-amylase. The hemicellulase is preferably a β-glucanase, a pectinase, a pullulanase, and / or a mannanase. The cellulase is preferably a cellulase mixture or a single-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase. The oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.

[0110] The proteases used are primarily alkaline serine proteases. They act as nonspecific endopeptidases, meaning they hydrolyze any acid amide bonds found within peptides or proteins, thereby breaking down protein-containing soils on the items being cleaned. Their pH optimum is usually in the significantly alkaline range.

[0111] The protein concentration can be determined using known methods, for example, the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method. The active protein concentration is determined by titrating the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913).

[0112] In the products described herein, the enzymes to be used can also be formulated together with accompanying substances, such as those from fermentation. In liquid formulations, the enzymes are preferably used as liquid enzyme formulation(s).

[0113] The enzymes are generally not provided in the form of pure protein, but rather in the form of stabilized, storable, and transportable preparations. These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably as concentrated as possible, with little water content, and / or containing stabilizers or other additives.

[0114] Alternatively, the enzymes can be encapsulated for both solid and liquid dosage forms, for example by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a water-, air-, and / or chemical-impermeable protective layer. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shake or roll granulation or in fluid-bed processes. Such granules, for example by applying polymeric film formers, are advantageously low in dust and, due to the coating, are stable during storage.

[0115] Furthermore, it is possible to package two or more enzymes together so that a single granulate has multiple enzyme activities.

[0116] In various embodiments, the agent according to the invention can comprise one or more enzyme stabilizers. Therefore, the agent according to the invention can further contain an enzyme stabilizer, for example, selected from the group consisting of sodium formate, sodium sulfate, lower aliphatic alcohols, and boric acid, as well as their esters and salts. Of course, two or more of these compounds can also be used in combination. The salts of the aforementioned compounds can also be used in the form of hydrates, such as sodium sulfate decahydrate.

[0117] The term "lower aliphatic alcohols," as used herein, includes monoalcohols, diols, and higher-hydric alcohols with up to 6 carbon atoms. Polyols belonging to the group of lower aliphatic alcohols include, in particular, polyols, for example, glycerol, (mono)ethylene glycol, (mono)propylene glycol, or sorbitol, without the invention being limited to these.

[0118] In addition to the at least one enzyme stabilizer selected from the above group, a composition according to the invention may also contain at least one further stabilizer. Such stabilizers are known in the art.

[0119] Reversible protease inhibitors protect the enzymes contained in a detergent or cleaning agent from proteolytic degradation by reversibly inhibiting the enzymatic activity of the proteases contained in the agent. Benzamidine hydrochloride, boronic acids, or their salts or esters are frequently used as reversible protease inhibitors, especially derivatives with aromatic groups, such as ortho-, meta-, or para-substituted phenylboronic acids, especially 4-formylphenylboronic acid, or the salts or esters of the aforementioned compounds. Peptide aldehydes, i.e., oligopeptides with a reduced C-terminus, especially those consisting of 2 to 50 monomers, are also used for this purpose. Peptide reversible protease inhibitors include, among others, ovomucoid and leupeptin.

[0120] Other enzyme stabilizers include amino alcohols such as mono-, di-, triethanolamine, and propanolamine and their mixtures; aliphatic carboxylic acids up to C12, such as succinic acid; other dicarboxylic acids; or salts of these acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Some organic acids used as builders can also stabilize an enzyme. Calcium and / or magnesium salts, such as calcium acetate, are also used for this purpose.

[0121] Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers, and / or polyamides stabilize the enzyme preparation against, among other things, physical influences or pH fluctuations. Polyamine N-oxide-containing polymers act simultaneously as enzyme stabilizers and dye transfer inhibitors. Other polymeric stabilizers are linear C 8 -C 18 polyoxyalkylenes. Alkyl polyglycosides can also stabilize the enzymatic components of the inventive agent and, preferably, can additionally enhance their performance. Crosslinked N-containing compounds preferably fulfill a dual function as soil-release agents and enzyme stabilizers. Hydrophobic, nonionic polymers particularly stabilize any cellulase present.

[0122] Reducing agents and antioxidants increase the stability of enzymes against oxidative degradation; for example, sulfur-containing reducing agents, such as sodium sulfite and reducing sugars, are common for this purpose.

[0123] In one embodiment, the agents according to the present invention are liquid and contain water as the main solvent, i.e., they are aqueous agents. The water content of the aqueous agent according to the invention is typically 15 to 70 wt.%, preferably 20 to 60 wt.%. In various embodiments, the water content is more than 5 wt.%, preferably more than 15 wt.%, and particularly preferably more than 50 wt.%, in each case based on the total amount of agent.

[0124] Non-aqueous solvents may also be added to the product. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines, or glycol ethers, provided they are miscible with water within the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these solvents.

[0125] The one or more non-aqueous solvents are usually present in an amount of 0.1 to 10 wt.%, preferably 1 to 8 wt.%, based on the total composition.

[0126] In addition to the components mentioned above, the agents according to the invention can contain other ingredients that further improve the application and / or aesthetic properties of the cleaning agent. These include, for example, additives to improve drainage and drying behavior, to adjust viscosity, and / or for stabilization, as well as other auxiliaries and additives commonly found in cleaning agents, such as UV stabilizers, perfume, pearlescent agents, dyes, corrosion inhibitors, preservatives, bittering agents, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients (e.g., encapsulated perfume), pH adjusters, and skin-feel-improving or conditioning additives.

[0127] Polymeric thickeners within the meaning of the present invention are the polycarboxylates which act as polyelectrolytes to thicken, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, as well as other customary thickening polymers.

[0128] Suitable polysaccharides or heteropolysaccharides are polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan gum, ramsan gum, dextran or xanthan gum and their derivatives, e.g., propoxylated guar gum, as well as their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably in addition, to a polysaccharide gum. These include starches of various origins and starch derivatives, e.g., hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropylmethyl or hydroxyethylmethylcellulose, or cellulose acetate.

[0129] Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI Carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.

[0130] Particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C 1-4 alkanols (INCI Acrylates Copolymer), which include, for example, the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3); (ii) cross-linked high molecular weight acrylic acid copolymers, which include, for example, copolymers of C 10-30 alkyl acrylates cross-linked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C 1-4 alkanols (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer).

[0131] The content of polymeric thickener is usually not more than 8 wt.%, preferably between 0.1 and 7 wt.%, particularly preferably between 0.5 and 6 wt.%, in particular between 1 and 5 wt.% and most preferably between 1.5 and 4 wt.%, for example between 2 and 2.5 wt.%, based on the total weight of the cleaning agent.

[0132] To stabilize the agent according to the invention, particularly with a high surfactant content, one or more dicarboxylic acids and / or their salts can be added, in particular a composition of sodium salts of adipic, succinic, and glutaric acid, such as is available under the trade name Sokalan®< DSC. They are advantageously used in amounts of 0.1 to 8 wt.%, preferably 0.5 to 7 wt.%, in particular 1.3 to 6 wt.%, and particularly preferably 2 to 4 wt.%, based on the total weight of the cleaning agent.

[0133] However, if their use can be dispensed with, the agent according to the invention is preferably free of dicarboxylic acid (salts).

[0134] The detergents according to the invention can be compared with reference detergents to determine the increased washing performance of the detergents according to the invention. Such a washing system can be composed as follows (all data in percent by weight): Reference detergent: 4-7% by weight LAS, 5-9% by weight anionic surfactants, 2-4% by weight C12-C18 fatty acid sodium salts, 4-7% by weight nonionic surfactants, 0.1-1% by weight phosphonates, 1-4% by weight citric acid, 1-3% by weight NaOH, 1-3% by weight defoamer, 1-3% by weight glycerin, 0.05-1% by weight preservative, 0.5-2% by weight ethanol, and the remainder water (demin.). Agent according to the invention: 4-7 wt% LAS, 5-9 wt% anionic surfactants, 2-4 wt% C12-C18 fatty acid Na salts, 4-7 wt% non-ionic surfactants, 0.1-1 wt% phosphonates, 1-4 wt% citric acid, 1-3 wt% NaOH, 1-3 wt% defoamer, 1-3 wt% glycerin, 0.05-1 wt% preservative, 0.5-2 wt% ethanol, 0.001-1 wt% amylase (SEQ ID NO:1) and the remainder water (demin.).The dosage of the solid detergent is preferably between 45 and 85 grams per wash liquor, for example 50, 65, or 70 grams per wash liquor. Washing is preferably carried out in a pH range between pH 7.5 and pH 9.5, preferably between pH 8 and pH 9.

[0135] The aforementioned embodiments of the present invention encompass all solid, powdered, liquid, gel-like, or pasty dosage forms of agents according to the invention, which may optionally also consist of multiple phases and may be present in compressed or uncompressed form. The agent may be in the form of 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. Solid dosage forms of the agent also include extrudates, granules, tablets, or pouches. Alternatively, the agent may also be liquid, gel-like, or pasty, for example in the form of a non-aqueous liquid detergent or a non-aqueous paste, or in the form of an aqueous liquid detergent or a water-containing paste. Furthermore, the agent may be in the form of a one-component system. Such agents consist of one phase.Alternatively, a remedy can also consist of multiple phases. Such a remedy is therefore divided into several components.

[0136] A further subject matter of the invention is a washing process comprising the process steps a) providing a washing or cleaning solution comprising an agent according to the invention, and b) bringing a textile or a hard surface into contact with the washing or cleaning solution according to (a).

[0137] In various embodiments, the method described above is characterized in that the agent according to the invention is used at a temperature of 0-100°C, preferably 0-80°C, more preferably 20-55°C and most preferably at 25-45°C.

[0138] This includes both manual and mechanical processes, with mechanical processes being preferred. Processes for cleaning textiles are generally characterized by the fact that various cleaning-active substances are applied to the items to be cleaned in several process steps and are washed off after the contact time, or by the items to be cleaned being treated in some other way with a detergent or a solution or dilution of this detergent. All conceivable washing or cleaning processes can be enhanced in at least one of the process steps by the use of a washing or cleaning agent according to the invention and then represent embodiments of the present invention. All facts, objects, and embodiments described for agents according to the invention are also applicable to this subject matter of the invention.Therefore, at this point, express reference is made to the disclosure at the corresponding point with the note that this disclosure also applies to the above methods according to the invention.

[0139] A third subject of the invention is the use of the agent according to the invention for removing starch-containing soils.

[0140] All facts, objects, and embodiments described for the agents according to the invention and the amylase are also applicable to the other subject matters of the invention. Therefore, express reference is made here to the disclosure at the appropriate point, with the note that this disclosure also applies to the above-mentioned method according to the invention and the uses according to the invention. Beispiele Beispiel 1: Stabilitätstest

[0141] Hand dishwashing matrix used (Table 1) Trade or chemical name % AM (raw material) % active material in the formula LABS 96 10-14 caustic soda 50 2-5 Galaxy SLES 70 6-8 Galaxy CAPB Plus 37 1-4 Parmetol A 28 S 100 0-1 Perfume 04-8862 100 0-1 Tartrazine Yellow 85 E 102 1 0-1 Potassium acetate 70 0-1 Ethanol 100 1-4 demineralized water 100 rest Detergent matrix used (Table 2) Trade or chemical name % AM (raw material) % active material in the formula demineralized water 100 rest Alkylbenzenesulfonic acid 96 4-7 Anionic surfactants 70 5-9 C12-C18 fatty acids sodium salt 30 2-4 Non-ionic surfactants 100 4-7 Phosphonate 40 0,1-1 Citric acid 100 1-4 NaOH 50 1-3 Antifoam tq 0,01-1 Glycerin 100 1-3 Preservatives 100 0,05-1 Ethanol 93 0,5-2 Without optical brighteners, perfume, dyes, or enzymes; dosage: 4.7 g / L Determination of amylase activity

[0142] The enzyme-containing solution is incubated with soluble starch under standardized conditions. Dextrins are formed, which contain terminal glucose residues with reducing groups. These form a stable, yellow color complex with p-hydroxybenzoic acid hydrazide (PAHBAH). Detection occurs in the flow-through at 410 nm.

[0143] The method is used to determine amylase activity in raw materials and finished products using a continuous flow system in the concentration range of 30 to 450 CAE / liter. Storage stability of amylase

[0144] To determine the storage stability of the amylase according to the invention, 0.1% of the amylase according to the invention and 0.1% of the reference amylase were formulated into the matrices listed in Tables 1 and 2.

[0145] The samples were then stored in climate-controlled cabinets at 30°C and 40°C for 2, 4, and 8 weeks. After the respective storage periods, a sample was taken and tested for residual amylase activity using the activity measurement described above. Results of storage tests in different matrices

[0146] Storage stability after storage in hand dishwashing matrix (Table 3) 0.1% reference amylase 0.1% amylase according to the invention (SEQ ID NO:1) Initial value 100% 100% 30°C 2 weeks 74% 73% 4 weeks 61% 65% 40°C 2 weeks 45% 62% 4 weeks 26% 56% Storage stability after storage in detergent matrix (Table 4) 0.1% reference amylase 0.1% amylase according to the invention (SEQ ID NO:1) Initial value 100% 100% 30°C 8 weeks 83% 89% 40°C 8 weeks 51% 79%

[0147] As can be seen from the data in Tables 3 and 4, the amylase according to the invention exhibits significantly increased storage stability in both hand dishwashing detergents and laundry detergents. This improved storage stability was determined after storage at both 30°C and 40°C.

Claims

1. Agent, preferably washing or cleaning agent, particularly preferably liquid washing or liquid cleaning agent, characterized in that it contains at least one amylase which comprises an amino acid sequence which over its entire length has at least 98% sequence identity with the amino acid sequence given in SEQ ID NO:1, wherein the composition contains 0.0001 to 1% by weight, preferably 0.006 to 0.6% by weight, of the amylase based on the total weight and wherein the following compositions are excluded if they contain the amylase in a concentration of 0.2 mg / l active protein content or 0.05 mg / l active protein content: CompoundContent of compound (% w / w)% active component (% w / w)LAS (linear alkylbenzene sulfonates)5,155,00AS (alkylbenzene sulfonates)5,004,50AEOS (alkyl ethoxy sulfate)14,1810,00Coco fatty acid1,001,00AEO (alkyl ethoxylate)5,005,00MEA (monoethanolamine)0,300,30MPG (monopropylene glycol)3,003,00Ethanol1,501,35DTPA (as Na5 salt) pentasodium diethylenetriaminepentaacetic acid0,250,10Sodium citrate4,004,00Sodium formats1,001,00Sodium hydroxide0,660,66H2O, ion exchanged58,9558,95 and CompoundContent of compound (% w / w)% active component (% w / w)LAS (linear alkylbenzene sulfonates)12,0011,60AEOS (alkyl ethoxy sulfate), SLES (sodium lauryl ether sulfate)17,634,90Soy fatty acid2,752,48Coco fatty acid2,752,80Sodium hydroxide1,751,80Ethanol / propan-2-ol3,002,70 / 0,30MPG (monopropylene glycol)6,006,00Glycerol1,711,70TEA (triethanolamine)3,333,30Sodium formats1,001,00Sodium citrate2,002,00DTMPA (diethylenetriaminepentaacetic acid)0,480,20PCA (polycarboxylic acid type polymer)0,460,18Phenoxy ethanol0,500,50H2O, ion exchanged33,6433,642. The agent, preferably washing or cleaning agent, particularly preferably liquid washing or liquid cleaning agent according to claim 1, characterized in that (a) the amylase is obtainable from an amylase according to claim 1 as starting molecule by single or multiple conservative amino acid substitution; and / or (b) the amylase is obtainable from an amylase according to claim 1 as starting molecule by fragmentation, deletion, insertion or substitution mutagenesis and comprises an amino acid sequence which corresponds to the starting molecule over a length of at least 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480 or 482 contiguous amino acids.

3. The agent, preferably a detergent or cleaning composition, particularly preferably a liquid detergent or liquid cleaning composition, according to one of claims 1 to 2, characterized in that the amylase comprises an amino acid sequence which is at least 98.5%, 98.8%, 99.0%, 99.2%, 99.4%, 99.6%, 99.8% or 100.0% identical to the amino acid sequence given in SEQ ID NO:1 over its entire length.

4. The agent, preferably washing or cleaning agent, particularly preferably liquid washing or liquid cleaning agent, according to one of claims 1 to 3, characterized in that the agent further comprises at least one further constituent selected from the group consisting of surfactants, other enzymes, enzyme stabilizers, complexing agents for heavy metals, builders, bleaching agents, builders, electrolytes, non-aqueous solvents, pH adjusters, odour absorbers, deodorizing substances, fragrances, fragrance carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antideposition agents, greying inhibitors, shrinkage inhibitors, other crease inhibitors, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobizing and impregnating agents, swelling and lubricating agents, softeners and UV absorbers.

5. The agent, preferably washing or cleaning agent, particularly preferably liquid washing or liquid cleaning agent, according to claim 4, characterized in that the agent contains at least one surfactant, wherein the at least one surfactant is preferably selected from linear alkyl benzene sulphonates, alkyl ether sulphates, alkyl sulphonates, alkyl sulphates, monoglyceride sulphates, ester sulphonates (sulphofatty acid esters), lignin sulphonates, fatty acid cyanamides, anionic sulphosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid arcosinates, ether carboxylic acids, alkyl(ether) phosphates, alkylamidoal-kylamines, alkyl-substituted amino acids, acylated amino acids, betaines, fatty alcohol alkoxylates, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers, fatty acid polyglycol esters, fatty acid alkanolamides, fatty acid polyglycol ethers, amine oxides, alkyl polyglucosides and combinations of the foregoing.

6. The agent, preferably washing or cleaning agent, particularly preferably liquid washing or liquid cleaning agent, according to claim 5, characterized in that the agent contains at least one surfactant, the at least one surfactant being selected from linear alkyl benzene sulphonates, alkyl ether sulphates, betaines, fatty alcohol alkoxylates, amine oxides, alkyl polyglucosides and combinations of the aforementioned, in particular linear alkyl benzene sulphonates and amine oxides.

7. The agent, preferably washing or cleaning agent, particularly preferably liquid washing or liquid cleaning agent, according to one of claims 1 to 6, characterized in that the agent is a liquid textile washing agent or dishwashing agent, in particular hand dishwashing agent.

8. Use of an agent according to any one of claims 1-7 for removing starch-containing soiling.

9. Washing or cleaning process comprising the process steps a) Providing a washing or cleaning solution comprising an agent according to any one of claims 1 to 8, and b) Bringing a textile or hard surface into contact with the washing or cleaning solution according to (a).