Cleaning agent containing protease and amylase

Description

[0001] The present application relates to a hand dishwashing liquid containing at least one protease and at least one amylase, as defined herein, as well as the use of such a liquid for cleaning solid surfaces and a method for cleaning hard surfaces using the described liquid. Finally, the invention also relates to the use of a specific enzyme combination, as defined herein, to improve the cleaning performance of a hand dishwashing liquid.

[0002] The most important criterion when cleaning hard surfaces, especially when washing dishes, is the cleaning performance against various types of soiling, particularly food residue. While the cleaning performance of modern dishwashing detergents is generally high, the increasing trend towards lower washing temperatures has led to a problem: many common detergents are insufficient for stubborn stains. This inadequate cleaning performance, and the resulting poor cleanliness, leads to consumer dissatisfaction and the tendency to pre-treat such stains, which in turn increases water and energy consumption.Therefore, there is a general need for dishwashing detergents that still provide good cleaning performance even on stubborn soiling without reducing the existing good cleaning performance on other types of soiling.

[0003] Amylase- and protease-containing washing and cleaning agents are known from, for example, WO 2013 / 087545, WO 2014 / 183920 and WO 2015 / 149641.

[0004] The object of the present invention was therefore to provide a hand dishwashing detergent which has an increased cleaning performance with regard to such soiling, without reducing the cleaning performance with regard to other soiling.

[0005] Surprisingly, it has now been found that the use of a combination of a specific protease with a specific amylase synergistically improves the cleaning performance of corresponding hand dishwashing detergents on enzyme-sensitive soils.

[0006] In a first aspect, the present invention therefore relates to a hand dishwashing detergent comprising at least one protease and at least one amylase, wherein a) the amylase has an amino acid sequence that is 100% identical over its entire length to the amino acid sequence specified in SEQ ID NO:1; and b) the at least one protease has the amino acid sequence according to SEQ ID NO:3.

[0007] When this combination is used, it results in a significantly increased cleaning performance on stubborn dirt, especially starch-based dirt.

[0008] A further object of the present invention is the use of a hand dishwashing detergent described herein in a cleaning process, preferably a dishwashing process, preferably the use to improve the cleaning performance, in particular the cleaning performance on enzyme-sensitive soiling, on hard surfaces, in particular dishes during their cleaning, especially stubborn soiling, among other things also at temperatures that are lower than the temperatures usually used.

[0009] Another aspect of the present invention is a dishwashing method in which a dishwashing detergent described herein is used, particularly for the purpose of improving the cleaning performance on enzyme-sensitive soiling. In various embodiments of the invention, temperatures lower than those commonly used are employed in the dishwashing method.

[0010] Another aspect of the invention is the use of the enzyme combinations described herein to improve the cleaning performance of a dishwashing detergent.

[0011] "Low temperatures" or "temperatures lower than the temperatures normally used", as used herein in connection with dishwashing processes, preferably refers to temperatures below 60°C, particularly below 55°C, more preferably 50°C or lower, particularly preferably 45°C or lower and most preferably 40°C or lower.

[0012] These and other aspects, features, and advantages of the invention will become apparent to the person skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be incorporated into any other aspect of the invention. Furthermore, it is understood that the examples contained herein are intended to describe and illustrate the invention, but do not limit it, and in particular, the invention is not limited to these examples. All percentages are weight percentages unless otherwise stated. Numerical ranges specified in the format "from x to y" include the stated values. If several preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the different endpoints are also included.

[0013] "Variant," as used herein in connection with enzymes, refers to natural or artificially generated variations of an enzyme that have a modified amino acid sequence compared to the reference form. Such a variant may have one or more point mutations, i.e., substitutions of one naturally occurring amino acid at the corresponding position by another, insertions (insertion of one or more amino acids), and / or deletions (removal of one or more amino acids), in particular one or more point mutations. Such variants preferably have at least 50%, preferably 60% or more, and more preferably 70%, 80%, 90%, 100% or more of the enzyme activity of the reference form. In various embodiments, such a variant has an amino acid sequence that is identical to the reference sequence over its entire length to at least 70%, preferably 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, or 99%.The variants preferably have the same length as the reference sequence. Variants may exhibit improved properties compared to the reference form, such as higher enzyme activity, higher stability, altered substrate specificity, etc. Only variants exhibiting enzymatic activity are used. "Enzymatic activity," as used in this context, means in particular that the corresponding enzymes exhibit at least 50%, preferably at least 90%, of the catalytic activity of their reference enzyme.

[0014] "Fragment," as used herein in connection with enzymes, refers to polypeptides shortened by one or more amino acids at the N-terminus and / or C-terminus compared to the reference enzyme. Only fragments exhibiting enzymatic activity are used. "Enzymatic activity," as used in this context, means in particular that the corresponding enzymes exhibit at least 50%, preferably at least 90%, of the catalytic activity of their reference enzyme.

[0015] The identity of nucleic acid or amino acid sequences is determined by sequence comparison. This sequence comparison is based on the established 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 achieved 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 prior art is the FASTA algorithm.

[0016] Such a comparison also allows for a statement about the similarity of the compared sequences to one another. This is usually expressed as percent identity, meaning the proportion of identical nucleotides or amino acid residues at the same positions or positions corresponding to each other in an alignment. The broader concept of homology, in the case of amino acid sequences, includes conserved amino acid substitutions in the analysis, 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 only for individual regions. Homologous or identical regions of different nucleic acid or amino acid sequences are thus 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. Often, such small regions perform essential functions for the overall activity of the protein. It can therefore be useful to refer to sequence similarities only for individual, possibly small, regions. Unless otherwise stated, however, statements of identity or homology in this application refer to the total length of the respective nucleic acid or amino acid sequence.

[0017] The amylases used are alkaline α-amylases. They act as hydrolases, cleaving the α(1-4) glycosidic bonds of polysaccharides, especially starches like amylose, thereby breaking down starch-based soils on the items being cleaned. The breakdown products are dextrins, which are then further broken down into maltose, glucose, and branched oligosaccharides. Their optimum pH is usually in the strongly alkaline range.

[0018] The amylase used in the sense of the present invention is an amylase comprising an amino acid sequence that is 100% identical over its entire length to the amino acid sequence specified in SEQ ID NO:1.

[0019] The agents described herein also contain at least one protease. These proteases are primarily alkaline serine proteases. They act as non-specific endopeptidases, meaning they hydrolyze any amide bonds located within peptides or proteins, thereby breaking down protein-containing soils on the items being cleaned. Their optimum pH is usually in the strongly alkaline range.

[0020] The at least one protease comprises an alkaline protease made of Bacillus lentus DSM 5483 or a functional fragment or variant thereof. The sequence of mature alkaline protease from Bacillus lentusDSM 5483 is listed under SEQ ID NO:2. Such a protease has an amino acid sequence that, according to SEQ ID NO:2, contains the amino acid substitutions R99E, S3T, V4I, and V199I. Such a protease is listed under SEQ ID NO:3.

[0021] In various embodiments, these combinations of amylase and protease are used in a mass ratio based on active protein of 10:1 to 1:10, preferably 5:1 to 1:5, particularly preferably 3:1 to 1:3, even more preferably 1:1 to 1:3, most preferably 1:2.

[0022] In various embodiments, the at least one amylase is contained in the composition according to the invention in amounts of 0.01 to 2.0 wt.%, preferably 0.05 to 1.5 wt.%, more preferably 0.1 to 1.0 wt.% based on the active protein and the total weight of the composition.

[0023] In various embodiments, the at least one protease is contained in the composition according to the invention in amounts of 0.01 to 2.0 wt.%, preferably 0.05 to 1.5 wt.%, most preferably 0.1 to 1.0 wt.% based on active protein and the total weight of the composition.

[0024] Surprisingly, the combinations of certain amylases and proteases described herein exhibit the property of improving the performance of the hand dishwashing detergent by leading to a synergistically improved cleaning performance on stubborn soils.

[0025] The improvement in cleaning performance generally means that, when using the agents described herein, the removal of soiling on hard surfaces, especially dishes, is noticeably improved when cleaning them, compared to using agents that do not contain the enzyme combinations described herein.

[0026] The enzymes used can also be formulated together with accompanying substances, such as those from fermentation, or with stabilizers. In liquid formulations, the enzymes are preferably used as liquid enzyme formulation(s).

[0027] Protein concentration can be determined using established methods, such as the BCA method (bicinchoninic acid; 2,2'-bicinolyl-4,4'-dicarboxylic acid) or the biuret method. The determination of the active protein concentration is carried out by titration of the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonylfluoride (PMSF)) and determination of the residual activity (see M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913).

[0028] Enzymes, especially the amylases and proteases described herein, can be protected against damage such as inactivation, denaturation or degradation, for example by physical influences, oxidation or proteolytic cleavage, particularly during storage.

[0029] For microbial production, inhibition of proteolysis is particularly advantageous. The described agents may contain stabilizers for this purpose.

[0030] Cleaning-active enzymes are generally not supplied in the form of pure protein, but rather in the form of stabilized preparations that are suitable for storage and transport. These pre-prepared formulations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization, or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with low water content, and / or containing stabilizers or other additives.

[0031] 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, such as those in which the enzymes are enclosed as if in a solidified gel, or in core-shell type capsules in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are produced using methods known per se, for example, by shake or roll granulation or in fluid-bed processes. Advantageously, such granules are low in dust, for example, by applying polymeric film formers, and are stable during storage due to the coating.

[0032] Furthermore, it is possible to combine two or more enzymes so that a single granule has multiple enzyme activities.

[0033] As can be seen from the preceding explanations, the enzyme protein constitutes only a fraction of the total weight of conventional enzyme preparations. Preferably used enzyme preparations contain between 0.1 and 40 wt%, preferably between 0.2 and 30 wt%, particularly preferably between 0.4 and 20 wt%, and especially between 0.8 and 15 wt% of the enzyme protein. The described agents therefore preferably contain such enzyme preparations in an amount that achieves the active protein concentrations specified above.

[0034] The agents described herein may be of a solid or liquid nature and may, in particular, be in the form of homogeneous solutions or suspensions.

[0035] The agents described herein may contain surfactants, the group of which includes non-ionic, anionic, cationic and amphoteric surfactants.

[0036] All nonionic surfactants known to those skilled in the art can be used. Suitable nonionic surfactants include, for example, alkyl glycosides of the general formula RO(G) x, where R corresponds to a primary straight-chain or methyl-branched, particularly 2-position methyl-branched, aliphatic residue with 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol representing a glucose unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably, x is between 1.2 and 1.4.

[0037] Another class of preferably applicable non-ionic surfactants, which can be used either as a sole non-ionic surfactant or in combination with other non-ionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

[0038] Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

[0039] Weakly foaming nonionic surfactants can be used as preferred surfactants. The compositions particularly favorably contain nonionic surfactants from the group of alkoxylated alcohols. Preferably, alkoxylated, advantageously ethoxylated, and 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 are used as nonionic surfactants. The alcohol residue in these alcohols may be linear or, preferably, methyl-branched at the 2-position, or may contain both linear and methyl-branched residues in the mixture, as is commonly found in oxo alcohol residues. However, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, e.g., from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol, are particularly preferred.Preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 or 4 EO, C9-11 alcohols with 7 EO, C13-15 alcohols with 3, 5, 7, or 8 EO, C12-18 alcohols with 3, 5, or 7 EO, and mixtures thereof, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a whole number or a fraction for a specific product. Preferred alcohol ethoxylates exhibit a narrow range of homologs (NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

[0040] In various preferred embodiments, the composition of the invention contains at least one amine oxide as a nonionic surfactant. In principle, all amine oxides established in the prior art for this purpose, i.e., compounds having the formula R<1<R<2<R<3<NO), wherein each R<1<, R<2<, and R<3< is, independently of the others, an optionally substituted, for example, hydroxy-substituted, C<1-C<30 hydrocarbon chain, can be used. Particularly preferred amine oxides are those in which R<1< is C<12-C<18 alkyl and R<2< and R<3< are each independently C<1-C<4 alkyl, especially C<12-C<18 alkyldimethylamine oxides. Exemplary representatives of suitable amine oxides are N-cocosalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide. C 12 -C 18 alkyldimethylamine oxides or mixtures which also contain C 16 and C 18 alkyldimethylamine oxides are preferred over C 12 -C 14 alkyldimethylamine oxides.Similarly, amine oxides in which R< 1< also includes C<16 and C<18 residues are generally preferred over those in which R< 1< includes only C<12-14 residues. In various embodiments, the amine oxides used therefore contain at least 20 wt.%, preferably at least 30 wt.%, more preferably at least 40 wt.%, and most preferably at least 50 wt.%, 60 wt.%, 70 wt.%, or 80 wt.% C16-18 amine oxides based on the total weight of the amine oxides. In such embodiments, the remainder of the amine oxides may consist of C12-14 amine oxides. The at least one amine oxide is preferably used in an amount of 0.5 to 10.0 wt.%, more preferably 0.8 to 8.0 wt.%, based on the total weight of the composition.

[0041] In various preferred embodiments, at least one anionic surfactant is also used. These include, in particular, alkylbenzenesulfonates, (fatty) alkyl sulfates, (fatty) alkyl ether sulfates, and alkanesulfonates. The composition of the invention preferably contains at least one anionic surfactant from the group of alkyl ether sulfates. Preferred alkyl ether sulfates are those of formula (I) R 1< -O-(AO) n -SO 3 -< X +< (I).

[0042] In this formula (I), R< represents a linear or branched, substituted or unsubstituted alkyl group, preferably a linear, unsubstituted alkyl group, and particularly preferably a fatty alcohol group. Preferred groups R< are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups and mixtures thereof, with those having an even number of carbon atoms being preferred. Particularly preferred groups R< are derived from C<12-C<18 fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from C10-C20 oxo alcohols. X represents a monovalent cation or the nth part of an n-valent cation, preferably the alkali metal ions and among them Na+ or K+, with Na+ being most preferred.Other cations X +< can be selected from NH 4 +< , ½ Zn 2+< ,½ Mg 2+< ,½ Ca 2+< ,½ Mn 2+< , and their mixtures.

[0043] AO stands for an ethylene oxide (EO) or propylene oxide (PO) grouping, preferably for an ethylene oxide grouping. The index n stands for an integer from 1 to 50, preferably from 1 to 20, and particularly from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7, or 8.

[0044] Fatty alcohol ether sulfates of formula I-1 are preferred. with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Particularly preferred representatives are Na-C 12-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2 in formula II-1).

[0045] The alkyl ether sulfates are preferably used in an amount of 3.0 to 30.0 wt.%, more preferably 4.0 to 25.0 wt.%, most preferably 4.0 to 18.0 wt.% based on the total weight of the agent.

[0046] Finally, in various preferred embodiments, the means of the invention further comprise at least one betaine. Suitable betaines are those of the formula (R iii< )(R iv< )(R v< )N +< CH 2 COO -< , in which R iii< represents an alkyl group, optionally interrupted by heteroatoms or heteroatom groups such as O, S, NH, C(O), C(O)NH or C(O)O, with 8 to 25, preferably 10 to 21, carbon atoms, and R iv< and R v< represent similar or different alkyl groups with 1 to 3 carbon atoms. C 10-C 18 alkyl-dimethylcarboxymethyl betaine and C 11-C 17 alkylamidopropyl-dimethylcarboxymethyl betaine are particularly preferred. The at least one betaine is preferably used in an amount of 0.9 to 15.0 wt.%, more preferably 1.0 to 12.0 wt.%, most preferably 1.5 to 8.0 wt.% based on the total weight of the agent.

[0047] Furthermore, in addition to those mentioned above, other surfactants can be used in the invention. Suitable examples include surfactants from the groups of alkylbenzenesulfonates, alkyl sulfates, alkyl ester sulfonates, secondary alkanesulfonates, fatty alcohol alkoxylates, alkyl glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides, and alkoxylated alcohols. Such surfactants are known in the prior art.

[0048] In various embodiments, the total amount of surfactants based on the weight of the agent is 4 to 45 wt.%, preferably 6 to 40 wt.%, more preferably 10 to 32 wt.%.

[0049] In one embodiment, the agents according to the present invention are liquid and contain water as the main solvent; that is, they are aqueous agents. The water content of the aqueous agent according to the invention is typically 15 to 95 wt.%, preferably 20 to 90 wt.%. In various embodiments, the water content is more than 5 wt.%, preferably more than 15 wt.%, and particularly preferably more than 25 wt.%, in each case based on the total amount of agent.

[0050] In addition, non-aqueous solvents may 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. Preferably, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycyl, propyldiglycol, butyldiglycyl, 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.

[0051] The one or more non-aqueous solvents are / are usually present in an amount of 0.1 to 10 wt.%, preferably 1 to 8 wt.%, based on the total composition.

[0052] In addition to the components mentioned above, the compositions according to the invention may contain further ingredients that further improve the application-related and / or aesthetic properties of the composition. These include, for example, additives for improving flow and drying behavior, for adjusting viscosity and / or for stabilization, as well as other auxiliary and additive substances commonly found in compositions, 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-enhancing or conditioning additives.

[0053] To further improve the flow and / or drying behavior, the agent according to the invention can contain one or more additives from the group of polymers and builder substances (builders), typically in an amount of 0.001 to 5 wt.%, preferably 0.01 to 4 wt.%, in particular 0.1 to 3 wt.%, especially preferably 0.2 to 2 wt.%, most preferably 0.5 to 1.5 wt.%, for example 1 wt.%.

[0054] Polymeric thickening agents within the meaning of the present invention are the polycarboxylates acting as polyelectrolytes, 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 conventional thickening polymers.

[0055] Suitable polysaccharides or heteropolysaccharides include polysaccharide gums, such as gum arabic, agar, alginates, carrageenan and its salts, guar, guaranine, tragacanth, gellan gum, ramsan, 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. Examples include starches of various origins and starch derivatives, e.g., hydroxyethyl starch, starch phosphate esters, or starch acetates, or carboxymethylcellulose or its sodium salt, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, or hydroxyethylmethylcellulose, or cellulose acetate.

[0056] Acrylic acid polymers suitable as polymeric thickening agents include, for example, high molecular weight homopolymers of acrylic acid (INCI Carbomer) cross-linked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.

[0057] Particularly suitable polymeric thickening agents are the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group consisting 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) crosslinked high molecular weight acrylic acid copolymers, which include, for example, copolymers of C 10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters formed preferably with C 1-4 alkanols (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer).

[0058] The content of polymeric thickening agent is usually no more than 8 wt.%, preferably between 0.1 and 7 wt.%, particularly preferably between 0.5 and 6 wt.%, especially 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 agent.

[0059] To stabilize the composition according to the invention, particularly at high surfactant content, one or more dicarboxylic acids and / or their salts can be added, especially a composition of sodium salts of adipic, succinic, and glutaric acid, such as that available under the trade name Sokalan® DSC. Advantageously, these are used in amounts of 0.1 to 8 wt.%, preferably 0.5 to 7 wt.%, particularly 1.3 to 6 wt.%, and most preferably 2 to 4 wt.%, based on the total weight of the composition.

[0060] However, if their use can be dispensed with, the agent according to the invention is preferably free of dicarboxylic acid (salts).

[0061] In addition, one or more other auxiliary and additive substances – particularly common in hand dishwashing detergents – may be present, especially UV stabilizers, perfume, opacifying agents (INCI: Opacifying Agents; for example, glycol distearate, e.g., Cutina® AGS from Cognis, or mixtures containing it, e.g., Euperlane® from Cognis), dyes, corrosion inhibitors, preservatives (e.g., the technical compound 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), also known as Bronopol, which is commercially available from Boots as Myacide® BT or Boots Bronopol BT), organic salts, disinfectants, enzymes, pH adjusters, and skin-feeling or skin-conditioning additives (e.g.,dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolysate, various vegetable protein partial hydrolysates, protein hydrolysate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes, glycerin, urea, quaternized hydroxyethylcellulose), in amounts of usually not more than 5% by weight, based on the total weight of the product.

[0062] The pH value of the agent according to the invention can be adjusted using conventional pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, wherein - particularly if hand compatibility is desired - a range of 4 to 9, preferably 5 to 8, particularly 5.5 to 7.5, is preferred.

[0063] To adjust and / or stabilize the pH value, the composition according to the invention can contain one or more buffering agents (INCI buffering agents), typically in amounts of 0.001 to 5 wt.%, preferably 0.005 to 3 wt.%, particularly 0.01 to 2 wt.%, especially preferably 0.05 to 1 wt.%, most preferably 0.1 to 0.5 wt.%, for example 0.2 wt.%. Buffering agents that are also complexing agents or even chelating agents (INCI chelating agents) are preferred. Particularly preferred buffering agents are citric acid or citrates, especially sodium and potassium citrates, for example trisodium citrate dihydrate and tripotassium citrate dihydrate.

[0064] The agent according to the invention can be used for the manual cleaning of dishes.

[0065] The product is manufactured using standard and well-known methods and procedures.

[0066] Finally, the present invention also relates to a method for cleaning hard surfaces, characterized in that an agent described herein is used in at least one process step.

[0067] Another aspect of the invention is the use of a means described herein for cleaning hard surfaces.

[0068] Another aspect of the invention is the use of the enzyme combinations described herein to improve the washing performance of a hand dishwashing detergent.

[0069] All facts, objects, and embodiments described herein for the means described herein are also applicable to the aforementioned processes and uses. Therefore, explicit reference is made here to the disclosure at the relevant point, with the note that this disclosure also applies to the aforementioned processes and uses. Examples Example 1: Formulations

[0070] Inventive formulation (E1) 4.5% FAEOS, 1.5% Betaine, 1.0% Amine Oxide, 0.1% Amylase (SEQ ID NO:1), 0.4% Protease (SEQ ID NO:3) to 100% Perfume, Color, Preservative, Water

[0071] Reference Formula 1 (V1) 4.5% FAEOS, 1.5% Betaine, 1.0% Amine Oxide, 0.21% Amylase (Termamyl 300L (Novozymes, DK)), 0.39% Protease (Alcalase® (Novozymes, DK)) to 100% Perfume, Colour, Preservative, Water

[0072] Reference Formula 2 (V2) 4.5% FAEOS, 1.5% Betaine, 1.0% Amine Oxide, 0.21% Amylase (Thermamyl 300L), 0.43% Protease (Biotouch® < ROC 250 L (AB Enzymes, DE)) to 100% Perfume, Color, Preservative, Water

[0073] Reference Formula 3 (V3) 4.5% FAEOS, 1.5% Betaine, 1.0% Amine Oxide, 0.21% Amylase (Thermamyl 300L), 0.34% Protease (Purafect® < Prime 4000 L (DuPont, US)) to 100% Perfume, Color, Preservative, Water

[0074] Reference Formula 4 (V4) 4.5% FAEOS, 1.5% Betaine, 1.0% Amine Oxide, 0.1% Amylase (SEQ ID NO:1), 0.43% Protease (Biotouch® < ROC 250 L (AB Enzymes, DE)) to 100% Perfume, Color, Preservative, Water

[0075] Reference Formula 5 (V5) 4.5% FAEOS, 1.5% Betaine, 1.0% Amine Oxide, 0.21% Amylase (Termamyl 300L), 0.4% Protease (SEQ ID NO:3) to 100% Perfume, Color, Preservative, Water

[0076] Reference Formula 5 (V5) 4.5% FAEOS, 1.5% Betaine, 1.0% Amine Oxide, 0.21% Amylase (Termamyl 300L), 0.4% Protease (SEQ ID NO:3) to 100% Perfume, Color, Preservative, Water

[0077] Reference Formula 6 (V6) 19.1% FAEOS, 7.2% Betaine, 4.8% Amine Oxide, 0.3% Amylase (SEQ ID NO:1) to 100% Perfume, Colour, Preservative, Water

[0078] Reference Formula 7 (V7) 19.1% FAEOS, 7.2% Betaine, 4.8% Amine Oxide, 0.6% Amylase (SEQ ID NO:1) to 100% Perfume, Colour, Preservative, Water

[0079] Reference Formula 8 (V8) 19.1% FAEOS, 7.2% Betaine, 4.8% Amine Oxide, 0.3% Protease (SEQ ID NO:3) to 100% Perfume, Color, Preservative, Water

[0080] Reference Formula 9 (V9) 19.1% FAEOS, 7.2% Betaine, 4.8% Amine Oxide, 0.6% Protease (SEQ ID NO:3) to 100% Perfume, Color, Preservative, Water

[0081] Inventive formulation 2 (E2) 19.1% FAEOS, 7.2% Betaine, 4.8% Amine Oxide, 0.3% Amylase (SEQ ID NO:1), 0.3% Protease (SEQ ID NO:3) to 100% Perfume, Color, Preservative, Water

[0082] All figures are % by weight of active substance based on total weight. Example 2: Cleaning performance

[0083] Average starch removal in % (starch contamination) Average protein removal in % (cheese contamination*) E1 92 92 V1 20 85 V2 16 76 V3 22 75 V4 70 86 V5 21 64 V6 57 V7 61 V8 37 V9 40 E2 77 *The cheese smearing is a commercially available "4 cheese sauce", as offered by various suppliers, which is applied to plates or steel sheets and baked on.

[0084] It is evident that the enzyme combination according to the invention is more effective on starch- and protein-containing soiling than the respective enzymes alone or combinations of other enzymes known in the prior art.

Claims

1. Hand dishwashing detergent, characterized in that the detergent comprises at least one protease and at least one amylase, wherein a) the amylase has an amino acid sequence that is 100% identical to the amino acid sequence specified in SEQ ID NO:1 over its entire length; and b) the at least one protease has the amino acid sequence according to SEQ ID NO:3.

2. The detergent according to claim 1, characterized in that (i) the at least one amylase and the at least one protease are used in a mass ratio based on active protein of 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3, even more preferably 1:1 to 1:3, most preferably 1:2; and / or (ii) the at least one amylase is used in amounts of 0.01 to 2.0 wt.%, preferably 0.05 to 1.5 wt.%, based on active protein and the total weight of the agent; and / or (iii) the at least one protease is used in amounts of 0.01 to 2.0% by weight, preferably 0.05 to 1.5% by weight, based on active protein and the total weight of the agent.

3. The agent according to one of the preceding claims, characterized in that the agent further contains surfactants, wherein the total amount of surfactants, based on the weight of the agent, is 4 to 45 wt.%, preferably 6 to 40 wt.%, more preferably 10 to 32 wt.%.

4. The agent according to one of the preceding claims, characterized in that the agent contains (i) at least one amine oxide, preferably a C12-C18 alkyldimethylamine oxide, preferably in an amount of 0.5 to 10.0 wt.%, more preferably 0.8 to 8.0 wt.% based on the total weight of the agent; (ii) at least one ether sulphate, preferably in an amount of 3.0 to 30.0% by weight, more preferably 4.0 to 25.0% by weight, based on the total weight of the agent; and (iii) at least one betaine, preferably in an amount of 0.9 to 15.0% by weight, more preferably 1.0 to 12.0% by weight, based on the total weight of the agent.

5. The agent according to one of the preceding claims, characterized in that the agent contains at least one additional ingredient selected from the group consisting of additives for improving the draining and drying behaviour, for adjusting the viscosity and / or for stabilisation, UV stabilisers, perfume, pearlescent agents, dyes, corrosion inhibitors, preservatives, bittering agents, organic salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients, pH adjusters and skin feel-improving or skin care additives.

6. Use of a hand dishwashing detergent according to any of claims 1 to 5 for cleaning solid surfaces.

7. Method for cleaning hard surfaces, characterized in that a hand dishwashing detergent according to one of claims 1 to 5 is used in at least one step of the method.

8. Use of an enzyme combination comprising at least one protease and at least one amylase, wherein a) the amylase has an amino acid sequence that is 100% identical to the amino acid sequence specified in SEQ ID NO:1 over its entire length; and b) the at least one protease has the amino acid sequence according to SEQ ID NO:3, for improving the rinsing performance of a hand dishwashing detergent.