AU2015359359A1 - Solid detergents and cleaning agents with amylase - Google Patents

Abstract

The invention relates to solid detergents and cleaning agents containing amylase, the amino acid sequence of which has been modified specifically for use in detergents and cleaning agents. The invention further relates to methods and uses of said detergents and cleaning agents.

Description

Solid detergents and cleaning agents with amylase [0002] The invention relates to a solid detergent and cleaning agent containing an amylase, preferably in combination with a protease, whereby the amino acid sequences have been modified specifically for use in detergents and cleaning agents. The invention further relates to methods and uses of said solid detergents and cleaning agents.

[0003] Proteases are among the most important technical enzymes in existence. They are the most established of all enzymes in detergents and cleaning agents, and are in practically all modern, high-performance detergents and cleaning agents. They serve to degrade protein-containing soils found on items for washing. Further, particularly important among them are the subtilisin-type proteases (subtilases, subtilopeptidases, EC 3.4.21.62), which, owing to catalytically effective amino acids, are termed serine proteases. They act as unspecific endopeptidases, and hydrolyze any acid amide bonds found within peptides or proteins. Their optimal pH usually lies well within the alkaline range. An overview of this family is provided, for example, in the paper “Subtilases: Subtilisin-like Proteases" by R. Siezen, pp. 75-95 in "Subtilisin Enzymes, edited by R. Bott and C. Betzel, New York, 1996. Subtilases are formed naturally by microorganisms. Among these, the most noteworthy group within the subtilases are specifically those produced and excreted by Bacillus species.

[0004] Examples of subtilisin-type proteases preferably used in detergents and cleaners are the BPN' and Carlsberg subtilisins, the PB92 protease, subtilisins 147 and 309, the proteases obtained from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY, as well as the thermitase enzymes, proteinase K and the TW3 and TW7 proteases not strictly classified as subtilisins, in addition to variations of the proteases mentioned having an amino acid sequence modified with respect to the parent protease. Using methods known in the prior art, proteases are modified in controlled or random fashion and are thereby optimized, for example, for use in detergents and cleaning agents. Said methods include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein segments. Correspondingly optimized variants are thus known for the majority of proteases known from the prior art.

[0005] Enzymes usable in detergents and cleaning agents further include amylases. Terms synonymous with amylases may also be used, for example 1,4-alpha-D-glucan-glucanohydrolase or glycogenase. Amylases preferable in terms of the invention are oc-amylases. Decisive in whether an enzyme is an α-amylase in terms of the invention is its ability to hydrolyze a(1-4)-glucosidic linkages in the amylose part of the starch.

[0006] Amylases known in the prior art as well as improved refinements made specifically for use in detergents or cleaning products are described hereinafter. The α-amylase from Bacillus licheniformis (available as Termamyl® from Novozymes or as Purastar®ST from the Danisco/Genencor company) and their derivative products Duramyl® and Temnamyl®ultra (Novozymes), Purastar®OxAm (Danisco/Genencor) and Keistase® (Daiwa Seiko Inc.), and the α-amylases from Bacillus amyloliquefaciens or Bacillus stearothermophilus are suitable amylases. The α-amylase from Bacillus amyloliquefaciens is marketed by the Novozymes company under the name BAN®, as well as variants derived from the a-amylase from Bacillus stearothermophilus under the names BSG® and Novamyl®, likewise from the Novozymes company. Additional known amylases are the a-amylase obtained from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948) as well as refinements of a-amylase obtained from Aspergillus niger and A. oryzae. available under the trade name Fungamyl® from the Novozymes company. Additional commercial products preferable for use in detergents and cleaning products are, for example, Amylase-LT® and Stainzyme® or Stainzyme ultra® as well as Stainzyme PLUS®, the latter also from the Novozymes company. Variants of these enzymes obtainable using point mutation may also be used in detergents and cleaning agents. Particularly preferable amylases are disclosed in the internationally published Patent Applications WO 00/60060, WO 03/002711, WO 03/054177 and WO 07/079938, the disclosure of which is thus hereby expressly referred to, and the disclosed content pertaining thereto is thus expressly included as part of the present patent application.

[0007] Surprisingly, it has now been determined that an α-amylase according to the invention demonstrates outstanding activity in solid detergents and is a significant improvement in comparison with known amylases. Starch stains in particular were removed more efficiently in the washing process using solid detergents. Another surprising finding was that the amylase according to the invention improved the stability and the performance of a protease in a solid detergent and cleaning agent.

[0008] The subject-matter of the present invention is therefore a solid detergent or cleaning agent comprising 5-70% by weight surfactant, 5-55% by weight carbonate, 0-10% by weight phosphate builder and an amylase, wherein the α-amylase is characterized by having sequence identity with the sequence specified in SEQ ID NO. 1 over its entire length of at least 89% and, with increasing preference, at least 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94, 94.5% , 95.5%, 95%, 96%, 96.5%, 97% and 97.5%, 98%, 98.5%, 99%, 99.5% to 100% and, according to SEQ ID NO. 1 numbering, comprises deletions in one or more of the positions 180, 181, 182, 183 and 184.

[0009] Particularly preferable is a deletion in two positions selected from 180 + 181, 181 + 182, 182 + 183 and 183 + 184, most particularly preferable being deletions at 183+184 according to SEQ ID NO. 1 numbering, particularly preferably the deletions H183* + G184*.

[0010] Preferably, the α-amylase according to the invention furthermore comprises amino acid substitutions in one or more of the positions 405, 421,422 and 428 according to SEQ. ID NO. 1 numbering. Particularly preferable are the substitutions I405L; A421H, A422P and A428T.

[0011] In a particularly preferential embodiment of the invention, the α-amylase according to the invention comprises the H183* + G184* deletions in addition to the I405L, A421H, A422P and A428T substitutions according to SEQ ID NO. 1 numbering. In a further embodiment, the solid detergent or cleaning agent comprises 5-55% by weight, preferably 5-35% by weight anionic surfactant, 0-20% by weight, preferably 0-10% by weight alkali metal silicate builder, preferably a sodium silicate builder, and 0-10% by weight, preferably 0-5% by weight zeolite builder.

[0012] In a further embodiment, the solid detergent or cleaning agent comprises 5-55% by weight, preferably 5-35% by weight anionic surfactant, 0-20% by weight, preferably 0-10% by weight sodium silicate builder and 0-10% by weight, preferably 0-5% by weight zeolite builder and/or a protease, specifically protease in a quantity 0.001 to 0.1% by weight, preferably 0.01 to 0.06% by weight.

[0013] The solid detergent or cleaning agent according to the invention most preferably comprises 10 to 30% by weight anionic surfactant, 0 to 5% by weight phosphate builder, 5 to 30% by weight sodium carbonate, 0 to 10% by weight, preferably 1 to 10% by weight sodium silicate builder, 0 to 10% by weight, preferably 1 to 3% by weight polyacrylate, 0 to 5% by weight, preferably from 0 to 1% by weight zeolite builder, 0.005 to 10% by weight, preferably 0.5 to 2% by weight phosphonate, preferably HEDP.

[0014] The protease according to the invention comprises an amino acid sequence having sequence identity with the amino acid sequence specified in SEQ. ID NO. 2 and/or in SEQ ID NO. 3 over its entire length of at least 80% and, with increasing preference, of at least 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90,5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99% or up to 100%.

[0015] Preferable is a protease comprising an amino acid sequence having sequence identity with the amino acid sequence specified in SEQ. ID NO. 2 over its entire length of at least 80% and, with increasing preference, of at least 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%,98%, 98.5% and 99%, and has the amino acid glutamic acid (E) at position 99 according to SEQ ID NO. 2 numbering.

[0016] Even more preferable is a protease comprising an amino acid sequence having sequence identity with the amino acid sequence specified in SEQ. ID NO. 2 over its entire length of at least 80% and, with increasing preference, of at least 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98% 98.5% and 99%, and has the amino acid glutamic acid (T) at position 3, the amino acid isoleucine (I) at position 4 and the amino acid isoleucine (I) at position 199 according to SEQ ID NO. 2 numbering.

[0017] In a further embodiment, the solid detergent or cleaning agent comprises 0-15% by weight, preferably 0-10% by weight nonionic surfactant or 0-25% by weight, preferably 0-15% by weight, of a peroxygen compound and/or a protease according to SEQ ID NO. 4. In a further embodiment, the solid detergent or cleaning agent comprises 0-15% by weight, preferably 0-10% by weight nonionic surfactant.

[0018] In variety of embodiments, the solid detergent or cleaning agent comprises a quantity of amylase 0.001-0.15% by weight, preferably 0.005 to 0.012% by weight, based on the total weight of the detergent or cleaning agent.

[0019] According to a further aspect of the present invention, it concerns the use of an inventive solid detergent or cleaning agent for washing textiles or cleaning hard surfaces.

[0020] According to a further aspect of the present invention, it concerns the use of inventive solid detergents or cleaning agents for removing starch-containing soils from textiles or hard surfaces.

[0021] According to a further aspect of the present invention, it concerns a method for cleaning textiles or hard surfaces, characterized in that at least one method step uses a solid detergent or cleaning agent according to the invention.

[0022] Amino acid positions specified in the context of the present invention by the phrase "according to SEQ ID NO. 1 numbering" are to be understood as follows: The other amino acid positions are to be defined through an alignment of the amino acid sequence of an amylase or protease according to the invention with the amino acid sequence specified in SEQ ID NO. 1. Furthermore, the assignment of the positions is made on the basis of the mature protein. Also, this assignment is to be applied particularly if the amino acid sequence of a protein according to the invention comprises a higher number of amino acid residues than the amylase or protease in SEQ ID NO. 1. Based on the specified positions in the amino acid sequence, the changed positions in an amylase or protease according to the invention are those which are assigned in an alignment to these very positions.

[0023] The combination in terms of the invention of an inventive α-amylase with a protease in a solid detergent or cleaning agent has the effect of improving the cleaning performance of the solid detergent or cleaning agent at least with regard to a protease-sensitive soiling.

[0024] α-amylases according to the invention likewise have a performance-enhancing effect on the protease contained in the detergent and cleaning agent, and the effect they have of stabilizing protease consequently enables the enhanced removal of at least one and preferably multiple protease-sensitive soils from textiles and/or hard surfaces such as dishes. The preferential embodiments of the detergent and cleaning agent according to the invention demonstrate particularly beneficial cleaning performance with soils containing blood, for example the blood/milk/ink soil: Product no. CFT C-05 available from CFT (Center for Test Material) B.V, Vlaardingen, Netherlands.

[0025] Solid detergents and cleaning agents with improved cleaning performance will be produced by way of preferential embodiments of the present invention specifically in relation to protease-sensitive soils.

[0026] The preferential embodiments of combinations of amylase and protease according to the invention achieve such beneficial cleaning performance even at low temperatures, specifically in the temperature ranges between 10°C and 60°C, preferably between 15°C and 50°C, and particularly preferably between 20°C and 40°C. Further preferential embodiments of combinations of amylase and protease according to the invention achieve such beneficial cleaning performance in a wide range of temperatures, for example between 15°C and 90°C, preferably between 20°C and 60°C.

[0027] In the context of the invention, cleaning performance is to be understood as the ability to brighten one or more stains, in particular on washing or dishes. In the context of the invention, cleaning performance is demonstrated by both the detergent or cleaning agent, which includes the combination of amylase and protease, more specifically the wash liquor or cleaning solution formed from said detergent or cleaning agent, as well as the protease and amylase itself. The cleaning performance of the enzymes thus contributes to the cleaning performance of the detergent or cleaning agent, more specifically to that of the wash liquor or cleaning solution formed by the detergent or cleaning agent. The cleaning performance is preferably determined as indicated hereinafter.

[0028] In regard to the present invention, of primary interest will be the cleaning performance of the protease, whereby the synergistic effect of the α-amylase according to the invention will be demonstrated indirectly through the improvement in the protease cleaning performance on protease-containing soils.

[0029] A protease exhibits proteolytic activity, meaning it has the capacity to hydrolyze peptide bonds of a polypeptide or protein, particularly in a detergent or cleaning agent. A protease is therefore an enzyme that catalyzes the hydrolysis of peptide bonds, and is thus able to cleave peptides or proteins. The amylases and proteases according to the invention preferably concern the mature amylase/protease, meaning the catalytically active molecule without signal- and/or pro-peptide(s). Unless otherwise indicated, the sequences indicated each relate to mature enzymes.

[0030] Determining the identity of nucleic acid or amino acid sequences is carried out by sequential comparison. This sequential comparison is based on the BLAST algorithm, which is well-established in the prior art and commonly used (cf. for example Altschul, SF, Gish, W., Miller, W., Myers, E.W. & Lipman, D.J. (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, 5.3389-3402) and occurs principally by similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences being matched with one another. The matching of the particular positions in tabular fashion is known as alignment. An additional algorithm available in the prior art is the FASTA algorithm. Sequence alignments, in particular multiple sequence alignments, are performed using computer programs. For example, the Clustal series of programs or programs based on these programs or algorithms are also frequently used (cf. for example Chenna et al. (2003): Multiple sequence alignment with the Clustal series of programs. Nucleic Acid Research 31, 3497-3500), T-Coffee (cf. for example Notredame et al. (2000): T-Coffee: A novel method for multiple sequence alignments. J. Mol. Biol. 302, 205-217). In the present patent application, all sequence alignments were performed using standard parameters with the Vector NTI® Suite 10.3 computer program (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, CA, USA), whose AlignX sequence comparison module is based on ClustalW.

[0031] An alignment of this kind enables a determination to be made of the similarity between compared sequences. It is normally expressed in terms of percent identity, meaning the proportion of identical nucleotide or amino acid residues at the same or the correspondingly equivalent aligned positions. The broader concept of homology comes into consideration in regard to conservative amino acid substitutions in amino acid sequences, which refers to amino acids having similar chemical activity because they normally carry out similar chemical activities within the protein. As a result, the similarity between aligned sequences can also be specified as percent homology or percent similarity. Specified identity and/or homology information can refer to entire polypeptides or genes or only to specific regions thereof. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by matches between the sequences. Such regions often have identical functions. They may be small and include only a few nucleotides or amino acids. These small regions often carry out functions essential to the overall activity of the protein. Therefore, it may be useful for sequence matches to refer only to single, possibly small regions. Unless otherwise indicated, the identity or homology information specified in the present patent application refers to the entire length of the respective indicated nucleic acid or amino acid sequence.

[0032] The cleaning performance is determined in a washing system with a dose of detergent containing between 3.5 and 6.5 grams per liter of wash liquor as well as the amylase and preferably the protease. The amylases being used for comparison are at equal concentrations (based on active protein). The cleaning performance of the protease is determined in relation to a blood soil 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 with a water hardness (German degree) of between 13.5 and 16.5°.

[0033] The concentration of the protease in the detergent established for this washing system is from 0.001-0.1% by weight, preferably from 0.01 to 0.06% by weight based on active protein. The concentration of the amylase in the detergent established for this washing system is from 0.001-0.15% by weight, preferably from 0.005 to 0.012% by weight based on active protein.

[0034] The solid detergent dose preferably contains between 3.5 and 6.0 grams per liter of wash liquor, for example 4.7, 4.9 or 5.9 grams per liter of wash liquor. Washing preferably takes place at a pH range of between pH 8 and pH 10.5, preferably between pH 8 and pH 9.

[0035] The composition of a preferential detergent in powder form for said washing system is as follows (all amounts in percent by weight): 10% linear alkyl benzene sulfonate (sodium salt), 1.5% C12-C18 fatty alcohol sulfate (sodium salt), 2.0% C12-C18 fatty alcohol with 7 EO, 20% sodium carbonate, 6.5% sodium hydrogen carbonate, 4.0% amorphous sodium disilicate, 17% sodium carbonate peroxyhydrate, 4.0% TAED, 3.0% polyacrylate, 1.0% carboxymethyl cellulose, 1.0% phosphonate, 27% sodium sulfate, remaining ingredients: foam inhibitors, optical brighteners, fragrances. The solid detergent dose in powder form preferably consists of between 4.5 and 7.0 grams per liter of wash liquor, quite preferably 4.7 grams per liter of wash liquor or 5.5, 5.9 or 6.7 grams per liter of wash liquor. Washing preferably takes place at a pH range of between pH 9 and pH 11.

[0036] As a measure of the cleaning performance, the degree of whiteness, meaning the brightening of the stains, is preferably determined using optical measurement methods, preferably photometry. A device suitable for doing so is, for example, the Minolta CM508d spectrometer. Typically, the devices used for the measurement have been previously calibrated with a whiteness standard, preferably a supplied whiteness standard.

[0037] The protein concentration can be determined by using known methods, for example the BCA assay (bicinchoninic acid; 2,2'-Biquinoline-4,4'-dicarboxylic acid) or the biuret test (A.G. Gornall, CS Bardawill and M.M. David, J. Biol. Chem., 177 (1948), pp. 751-766). The active protein concentration can in this case be established by titration of 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).

[0038] In addition to the amino acid modifications described above, amylases and proteases according to the invention may exhibit additional amino acid modifications, specifically amino acid substitutions, insertions or deletions. Refinement of such amylases and proteases are carried out, for example, by means of targeted genetic modification, namely via mutagenesis, and optimized for specific purposes or with regard to special characteristics (for example, with regard to their catalytic activity, stability, etc.). In addition, nucleic acids according to the invention can be incorporated into recombination approaches and thus be used in the production of completely novel amylases and proteases or other polypeptides.

[0039] The aim is to introduce targeted mutations such as substitutions, insertions or deletions into the specified molecules in order to improve, for example, the cleaning performance of enzymes according to the invention. For this purpose, modifications are made in particular to the surface charges and/or the isoelectric point of the molecules, thus resulting in modifications to their interactions with the substrate. For example, the net charge of the enzymes can thus be modified in order to affect the influence of bindings in the substrate specifically for application in detergents and cleaning agents. Alternatively, or additionally, the stability of the amylase or protease can be increased through one or more corresponding mutations, thus improving its cleaning performance. Preferable properties of individual mutations, for example specific substitutions, can complement one another. In terms of the invention, further refinements can be made of amylase or protease already optimized with respect to certain properties, for example, with respect to their stability regarding bleaching agents, surfactants and/or other components.

[0040] The following convention will be used for the description of substitutions concerning exactly one amino acid position: the naturally existing amino acid is first designated in the internationally recognized single-letter code format, followed next by the associated sequence position, and finally the inserted amino acid. Multiple exchanges within the same polypeptide chain will be separated from one another by slashes. For insertions, additional amino acids are specified after the sequence position. For 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 by glycine, A95AG the insertion of glycine after the amino acid phenylalanine at position 95, and A95* the deletion of phenylalanine at position 95. This nomenclature is known to one skilled in the art in the field of enzyme technology.

[0041] An additional object of the present invention is therefore a detergent and cleaning agent containing a combination of an a-amylase and a protease, whereby the α-amylase is characterized in that it is obtainable by way of single or multiple conservative amino acid substitution from an amylase according to the invention acting as a parent molecule. The term "conservative amino acid substitution" means the exchange (substitution) of one amino acid residue for another amino acid residue, whereby this exchange does not lead to a change in the polarity or charge at the position of the exchanged amino acid, for example the exchange of a nonpolar amino acid residue for another nonpolar amino acid residue. Conservative amino acid substitutions in the context of the invention include, for example: G=A=S, l=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.

[0042] An additional object of the present invention is therefore a detergent and cleaning agent containing a combination of an α-amylase and a protease, whereby the α-amylase is characterized in that it is obtainable by way of fragmentation, deletion, insertion or substitution mutagenesis and comprises an amino acid sequence matching the parent molecule over a length of at least 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 475, 480, 482, 484 or 485 associated contiguous amino acids.

[0043] It is thus possible, for example, to delete individual amino acids at the loops or the termini of the enzyme without eliminating or diminishing proteolytic activity. In addition, the allergenicity of relevant enzymes can be reduced and their overall utility improved by using fragmentation, deletion, insertion or substitution mutagenesis of this kind. It is advantageous that the enzymes also maintain their proteolytic activity following mutagenesis, meaning that their proteolytic activity corresponds to at least that of the parent enzyme. Substitutions may exhibit advantageous effects as well. Both individual as well as multiple contiguous amino acids may be replaced with different amino acids.

[0044] An amylase according to the invention may additionally be stabilized, in particular through one or more mutations, for example substitutions, or through linkage to a polymer. Indeed, an increase in stability during storage and/or during use, for example during the washing process, results in enzymatic activity of longer duration, hence an improvement in cleaning performance. In principle, all of the stabilization alternatives that are appropriate and/or are described in the prior art are worthy of consideration. Preferable are stabilization methods achieved through mutations of the enzyme itself, since stabilization in this manner requires no further work steps following the extraction of the enzyme. Sequence modifications suitable for this purpose are well-known in the prior art.

[0045] Additional stabilization alternatives are, for example: [0046] Altering the binding of metal ions, the calcium binding sites in particular, for example by replacing one or more of the amino acid(s) involved in calcium binding with one or more negatively charged amino acids and/or by introducing sequence modifications into at least one of the two arginine/glycine amino acid results; [0047] Protection against the effects of denaturing agents such as surfactants that cause mutations leading to a change in the amino acid sequence or to the surface of the protein; [0048] Replacing amino acids located close to the N-terminal with those presumably coming into contact with the rest of the molecule via noncovalent interactions, thus contributing to maintaining three-dimensional structure.

[0049] Since a plurality of stabilizing mutations work additively or synergistically, preferential embodiments are those in which the enzyme is stabilized in a plurality of ways.

[0050] A further object of the invention is an amylase as described above, characterized in that it comprises at least one chemical modification. An amylase with such a modification is called the derivative, meaning that the amylase has been derivatized.

[0051] In terms of the present application, derivatives are understood as those proteins whose original amino acid chain has been chemically modified. For example, such derivatizations can be carried out in vivo through the host cell that expresses the protein. Particularly worthy of emphasis in this regard are linkages of low molecular weight compounds such as lipids or oligosaccharides. However, derivatizations may also be carried out in vitro, for example by the chemical transformation of an amino acid side chain or by covalent bonding of a different compound onto the protein. As an example, it is possible to modify the isoelectric point by linkage of amines to carboxyl groups of an enzyme. Another such compound can be another protein bound to a protein according to the invention by, for example, bifunctional chemical compounds. Derivatization is likewise to be understood as covalent bonding to a macromolecular carrier, or also as a noncovalent inclusion into suitable macromolecular cages. Derivatizations can influence, for example, the substrate specificity or the strength of bonding to the substrate, or they can bring about the temporary blockage of enzymatic activity if the linked substance is an inhibitor. This can be useful, for example, during the storage period. Such modifications can also have an affect on stability or enzymatic activity. They may also serve to reduce the allergenicity and/or immunogenicity of the protein, thus, for example, increasing its dermatological compatibility. For example, linkages with macromolecular compounds such as polyethylene glycol can improve the protein in terms of stability and/or dermatological compatibility.

[0052] In the broadest sense of the term, "derivatizations" of a protein according to the invention can also be understood to mean preparations of said protein. Depending on how it is obtained, processed or prepared, a protein may be brought into association with a variety of other materials, for example coming from the culture of the producing microorganisms. A protein may also have been admixed with other materials specifically for the purpose of, for example, increasing its stability during storage. As a result, all preparations of said inventive protein are also according to the invention. This is true whether said enzymatic activity in a certain preparation is actually developed or not. Indeed, it might be desirable that little or no activity takes place during storage, and the enzymatic function is not developed until the actual time of use. This can be controlled, for example, by means of appropriate concomitant materials.

[0053] Included in the subject-matter of the invention are all conceivable types of solid detergents or cleaning agents used in either concentrated or undiluted form for use on a commercial scale, in a washing machine or for washing or cleaning by hand. These include, for example, detergents for textiles, carpets or natural fibers with regard to which the term detergent is used. Included, for example, are dishwashing detergents for dishwashers or manual dishwashing detergents or agents for cleaning hard surfaces such as metal, glass, porcelain, ceramics, tile, stone, coated surfaces, plastics, wood or leather, in regard to which the term detergent is used, thus also including both manual and machine dishwashing detergents as well as scouring agents, glass cleaners, scented toilet cleaning products, etc. Additionally included among solid detergents and cleaning agents in the context of the invention are washing aids, doses of which are added to the actual detergent in order to achieve an additional effect during the manual or machine washing of textiles. Detergents and cleaning agents furthermore included in the context of the invention are agents for textile pre- and post-treatment, meaning those brought into contact with the actual items for washing prior to the washing process, for example to dissolve stubborn soils, as well as agents used in a subsequent step for providing the washed textile items with additional desirable properties such as a pleasant feel, resistance to wrinkles or a low static charge. Counted among the latter agents are, for example, fabric softeners.

[0054] The solid detergent or cleaning agent according to the invention may contain other enzymes in addition to the amylase, in particular in addition to the amylase and the protease. Due in specific to their triglyceride splitting activity as well as in order to produce peracids in situ from suitable precursors, lipases or cutinases may for example be used as additional enzymes. Included among them are, for example, lipases obtainable from Humicola lanuginosa (Thermomyces lanuginosus)or further refinements of lipases, in particular those having the D96L amino acid substitution. Included among them are, for example, lipases obtainable from Humicola lanuginosa (Thermomyces lanuginosus)or further refinements of lipases, in particular those having one or more of the following amino acid substitutions based on the specified lipase at positions D96L, T213R and/or N233R, particularly preferably T213R and N233R. As a further example, the cutinases originally isolated from Fusarium solani pisi and Humicola insolens are also usable. Additional usable lipases or cutinases are those whose parent enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

[0055] The detergent or cleaning agent according to the invention may also contain cellulases or hemicellulases such as mannanases, xanthanlyases, pectinylases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases or β-glucanases.

[0056] In order to enhance the bleaching effect, oxidoreductases, for example oxidases, oxygenases and catalases, peroxidases such as haloperoxidases, chloroperoxidases, bromoperoxidases, lignin peroxidases, glucose peroxidases or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) may according to the invention be used. Also advantageous is the addition of further preferential organic, most preferably aromatic compounds interacting with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or, in case of very different redox potentials, to ensure the flow of electrons between the oxidizing enzymes and the soils (mediators).

[0057] Amylases are also usable as additional enzymes, in terms of which all of the previously described amylases are suitable.

[0058] In addition to the previously described ingredients, the solid detergents or cleaning agents may contain active cleaning ingredients, preferable among them substances from the surfactants group, builders, polymers, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. Said preferable ingredients will be described in detail hereinafter.

[0059] Unless otherwise indicated, all of the quantities specified in regard to the detergents or cleaning agents described herein refer to the % by weight based on the total weight of the detergent or cleaning agent. Furthermore, unless otherwise indicated, said quantities specified in relation to at least one component always specify the total quantity of this type of component contained in the detergent or cleaning agent. Which is to say that said quantities, specified for example in relation to "at least one anionic surfactant" refer to the total amount of anionic surfactants contained in the detergent or cleaning agent.

[0060] Information specified in relation to detergents or cleaning agents according to the invention is likewise valid for the methods and applications according to the invention.

[0061] According to a further aspect of the present invention, it concerns the use of inventive solid detergents or cleaning agents as defined herein as detergents or cleaning agents. The present invention concerns in particular the use of the herein defined detergents or cleaning agents as textile detergents, detergents for hand washing, travel detergents, washing detergents, in particular dishwashing detergents, particularly preferably hand dishwashing detergents or toilet cleaners. For example, in a sink containing the composition according to the invention, the wash liquor generates an excellent foaming action if the wash liquor contains dirt.

[0062] As used herein, "at least one" refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to components of the compositions described herein, these are not based on the absolute quantity of molecules but rather on the type of component. For example, "at least one anionic surfactant" therefore means one or more different anionic surfactants, hence one or more different types of anionic surfactants. In connection with specified quantities, the quantities specified refer to the total amount of the component type identified, as defined above.

[0063] The detergents or cleaning agents contain 5-70% by weight surfactant, by which is meant one or more surfactants.

[0064] The detergents or cleaning agents most preferably comprise 5-55% by weight, even more preferably 5-35-¾ by weight surfactant. Anionic tensides. ndnbnic tensides and mixSures thereof specirical'y dome nto quBstion in 1his regard, bur cationic. zwiCenonic andi'or amphoteric surlaGtan-ls may also be contained.

[C-0G5] Used as an ucic surfactants. for example are sultanate and sulfate type surfactants. Sultanate lypa surfactants worthy of cons deration aTB preferably C9-1 3-alkyl Denzyne sulfonates, olerm sulFonates. which refers to matures oF alkenesuitanafes and hydroxyalhanesullonatES as we I as disulF-onates such as those ablainEG For exampE, From C12-iB-monob:efirtES with an interna! nr a terminal double bond by suironatmg witfi gaseous sulfur trioxide end Subsequent alkaline or acidic hydrolysis. Also suitable ere alkapesuilonates obtained tram C12-1&-alkanes. Tor example by suiFocFi deration or sulFcxidabor: and subsequent hydrolysis or neutralization. The Esters o( u-suMo tatty acids jester sulFonaies). such as the cjl-sulFonaled metfiyl esters οΓ hydrogenated coconut, palm kerne! or lallow fatty acids are also suitable.

[ODGC] The detergent or cleaning agant preferably Comprises 5-55% by weight. preFerably 5-35% by weight amaniosurfactant.

[GB&7] Tne detergent or cleaning agent mos1 preferably comprises 5-35% by weight aikylbenzene sulFonate.

[GD&G] Su tab'E alkytbenzene sultanates are praters Ply chosen ircm- linear or branched alkylbenzene sulfonates with the formula

where R' and ff1 are independent H or alkyl groups and bgEther contain S to 1&, preFerably 7 to 15 and in particular B |0 t3 carbon atoms. Sodium dodecybenzanesutronate is a particularly preferred representative. (GB69] PreFarab-e as atkyisuifatas/alkenesuMatas are IhE alkaline and m particular- the sodium salts of the sulfuric acid ha f ester oF C12-C 12—Tatty alcohols, Fo·- example From coconut Tatty alcohol, tallow fatly alcohol, lauryt-, myristyl·, cetyl· or sfearyt alcoFiol or tFiE C1C-C2Q-oxo alcohols arid those half esters oF secondary alcohoiS Fiaving these chain lengths. Further preferable are alkylsuiratesjalkenesulfates of the specified chain length comaining a straight-chain alkyl residue preoared on a petrochemical basis and possessing degradation behavor analogous to Lhe relevant cornoounds based on latty chorncal raw materials. Preferable in the interest oF wash.ng techno logy are the C12-C"i 5-alkyl sulfates and C12-C15-alkylsuHates as weli as ClirClB^alkijipttliateB.

[GD7Q] Also suitable are the sulFuric acid monoeslers of straight-chain or branched C7-21-alcohols elhoxylalad with 1 :o 6 ntolas of Blhylane oxide, such as 2-methyl branched C9-11-alcohols with an average oF 2.5 moles eth-ytene oxide (EO) or C12-1 &-fally alcohols with 1 to 4 EO. SuiLatle alkyl ether sulfates are. Ter example, compounds with the formula R 1-0-( AO }n-503- X+ in this FormuJa, R1 stands for a I near or branched, substituted or unsubsiituted alkyl residue, preferably For a linear, unsuustituied alkyt residue, quiie preferably for a fatty alcohol residue. Preferable residues R1 arF chosen from decyt-. undecvl-, dodecyl-. tridecyl-, tetradecyl-. pentadacyl-. hexadecyt-, heptadecyl- octadecyi-, nonadecyl- and ecasyl residues and mixtures thereof. whereby the representatives haying an even number of carbon atoms are preferable. (0071] Particularly preferable R1 residues are derived From C12-C1S-fady alcohols, for example, coconut tai'y alcohols, fallow Fatty alcohols, lauryl-, myristyl-, cetyl- or slearyl alcohols or C1Q-C20-oxo alcohols. AO stands tor an ethylene oxide FED) nr propylene oxide |POJ grouping, preferably for an ethylene oxide grouping. The index, π s an integer from 1 to 50. preferably from 1 tn 2D. and specifically Trom 2 to ID. IL is quite particularly preferable that n stand for ihe numbers 2. 3, 4, 5, G, 7 or B. X stands Tor a single-valued cation or the nth part οΓ an n-valjed cation, alkali melaJ ions preterably among them including Na+ or K+, whereby Na+ Is most preferable. Chher cations X+ may be Chosen from ΝΗ4τ. %Zn2+ l^Mg2+, ViCa2+, 1ΛΜη2-ι-, and mixtures ttiereof.

[0072] In various embodiments, the alkyl ether sulFale may be selected Trom fatty alcohol Bihar sulfates with the formula

where k = 1 1 to 15Γ n = 2. 3, 4, 5. 6. 7 or S. Especially preferable representatives are Na-C12-14 fatty alcohol ether su;Fatos wifh 2 EO (k = 11-13, n = 2 Fonnula A-1). The specified degree aF ethoxylefion represents a statistical average, which can be a whole or a fractions; number π regard Id a speciFic product. The specified degree οΓ slcoxylaliun represents a slabstical average, 'which can be a whole or a fractional numoer in regard to a specific product. Preferable alcoxyiale&'ethoxylates exhibit a narrow homobg disiribuLkm Inarrowrange elhuxylates. NRE|.

[0073] The term "anionic surfactants" also refers in terms of the present invention to soaps.

[0074] Soaps accordingly come into consideration as additional components of the detergents or cleaning agents. Suitable soaps include saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and, in particular, mixtures of soaps derived from natural fatty acids, for example coconut, palm kernel, or tallow fatty acids.

[0075] The anionic surfactants as well as the soaps may be present in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, the anionic surfactants and soaps are present in the form of their sodium, potassium or magnesium salts, in particular in the form of their sodium salts.

[0076] In regard to the choice of anionic surfactants, there are no basic requirements restricting the degrees of freedom for formulation. Anionic surfactants preferable for use in this regard are the alkyl benzene sulfonates and fatty alcohol sulfates, in particular the alkyl benzene sulfonates.

[0077] The detergent or cleaning agent preferably comprises 0-15% by weight, more preferably 0-10%, more preferably still 5-10% by weight nonionic surfactant.

[0078] The nonionic surfactants used are preferably alkoxylated, preferably ethoxylated, in particular primary alcohols preferably comprising 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue may be linear or preferably 2-methyl-branched, or may contain a mixture of linear and methyl-branched residues, as are typically present in oxo alcohol residues. Particularly preferred, however, are alcohol ethoxylates with linear residues derived from alcohols of native origin comprising 12-18 carbon atoms, [0079] for example coconut, palm, tallow fatty or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol. Included among the preferred alcohol ethoxylates are, for example, C12-14-alcohols with 3 EO or 4 EO, C9-11-alcohol with 7 EO, C13-15-alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18-alcohols with 3 EO, 5 EO or 7 EO, and mixtures thereof, such as mixtures of C12-14-alcohol with 3 EO and C12-18-alcohol with 5 EO. The specified degrees of ethoxylation represent a statistical average, which can be a whole or a fractional number in regard to a specific product. Preferable alcohol ethoxylates exhibit a narrow homolog distribution (narrow range ethoxylates, NRE). Fatty alcohols with more than 12 EO may be used in addition to said nonionic surfactants. Examples thereof are tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO.

[0080] A further class of preferably used nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably comprising 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.

[0081] A further class of nonionic surfactants which may preferably be used are the alkyl polyglycosides (APGs). Usable alkyl polyglycosides correspond to the general formula RO(G)z where R refers to a linear or branched, in particular 2-methyl branched, saturated or unsaturated aliphatic residue comprising 8 to 22 and preferably 12 to 18 carbon atoms, and G stands for a glycose unit comprising 5 or 6 C atoms, preferably glucose. The degree of glycosilation z is between 1.0 and 4.0, preferably between 1.0 and 2.0, and in particular between 1.1 and 1.4. Preferable for use are alkyl polyglycosides, meaning here alkyl polyglycosides in which the polyglycosyl residue is a glucose residue and the alkyl residue is an n-alkyl residue.

[0082] Also possibly suitable are nonionic surfactants based on amine oxides such as n-coco alkyl n,n-dimethylamine oxide and n-tallow alkyl η,η-dihydroxyethyl amine oxide as well as the fatty acid alkanolamides. The quantity of these nonionic surfactants is preferably not greater than that of the ethoxylated fatty alcohols, in particular not more than half of their quantity.

[0083] In regard to the present invention, the term carbonate means alkaline carbonate and alkaline hydrogen carbonate. It preferably refers to sodium carbonate and sodium hydrogen carbonate.

[0084] In various embodiments, the detergent or cleaning agent comprises 5-55% by weight, preferably 5-40% by weight, more preferably 5-35% by weight, even more preferably 5-25% by weight carbonate. In various embodiments, the detergent or cleaning agent comprises 5-55% by weight, preferably 5-40% by weight, more preferably 5-35% by weight, even more preferably 5-25% by weight alkaline carbonate. In preferred embodiments, the detergent or cleaning agent comprises 5-55% by weight, preferably 5-40% by weight, more preferably 5-35% by weight, even more preferably 5-25% by weight sodium carbonate.

[0085] A detergent or cleaning agent preferably contains at least one water-soluble or water-insoluble organic builder. Included among water-soluble organic builder substances are polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid as well as polyaspartic acid, polyphosphonic acids, in particular amino tris- (methylenephosphonic acid), ethylenediamine tetrakis-(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds, such as dextrin, and polymeric (poly)carboxylic acids, in particular the polycarboxylates accessible by oxidation of polysaccharides or dextrins and/or polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain polymerized into them small portions of polymerizable substances having no carboxylic acid functionality. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, each based on free acid. A particularly preferable acrylic acid/maleic acid copolymer has a relative molecular weight from 50,000 to 100,000. Suitable, although 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 proportion of acid is at least 50% by weight. It is also possible to use, as water-soluble builder substances, terpolymers that contain two carboxylic acids and/or salts thereof as monomers, and, as a third monomer, vinyl alcohol and/or an esterified vinyl alcohol or a carbohydrate. The first acidic monomer or salt thereof is derived from a ethylenically monounsaturated C3-C8-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or salt thereof can be a derivative of a C4-C6-dicarboxylic acid, maleic acid being particularly preferred, and/or a derivative of an allyl sulfonic acid that is substituted in the 2-position with an alkyl or aryl residue. Such polymers generally have a relative molecular weight between 1,000 and 200,000. Further preferred copolymers are those preferably having acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers. Specifically for the production of liquid agents in the form of aqueous solutions, said organic builder substances can be preferably used in the form of 30 to 50% by weight aqueous solutions. As a rule, all specified acids are used in the form of their water-soluble salts, in particular their alkaline salts.

[0086] If so desired, organic builder substances of this kind can be contained in quantities of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the aforesaid upper limit are preferably used in pasty or liquid agents, in particular those containing water.

[0087] In a preferential embodiment, the detergent or cleaning agent comprises a water-soluble builder block. The use of the term “builder block” here is intended to express that the compositions comprise no builder substances other than those which are water-soluble, which is to say that all builder substances present in the composition are summarized in the thus characterized “biock," excluding at most the amounts of substances which may be contained in a commercially customary manner as impurities or stabilizing additives in small amounts in the remaining ingredients of the composition. The use of the term "water soluble" should be taken to mean that the building block dissolves without residue at the concentration obtained from the quantity of agent being used under typical conditions. The water-soluble builder block is preferably contained in the detergent or cleaning agent in a quantity at least 15% by weight and up to 55% by weight, in particular from 25% by weight to 50% by weight. This preferably consists of the following components: 5% by weight to 35% by weight citric acid, alkaline citrate and/or alkaline carbonate, which may also be proportionally replaced by alkaline hydrogen carbonate, up to 10% by weight alkali metal silicate with a modulus in the range from 1.8 to 2.5, up to 2% by weight phosphonic acid and/or alkaline phosphonate, up to 10% by weight, preferably 5% by weight phosphate builder, and up to 10% by weight polymeric polycarboxylate, up to 10% by weight zeolite builder, whereby the specified quantities are based on the detergent or cleaning agent in its entirety. Unless expressly indicated otherwise, this also applies to all of the following specified quantities.

[0088] In a preferred embodiment, the water-soluble builder block contains at least 2 of the components b), c), d), e) and f) in quantities greater than 10% by weight.

[0089] In a preferential embodiment regarding component a), it contains: from 15% by weight to 25% by weight alkali metal carbonate, which may also be proportionally replaced by alkali metal hydrogen carbonate, as well as up to 5% by weight, in particular from 0.5% by weight to 2.5% by weight citric acid and/or alkaline citrate. In an alternative embodiment, it contains as component a): from 5% by weight to 25% by weight, in particular from 5% by weight to 15% by weight citric acid and/or alkaline citrate and up to 5% by weight, in particular from 1% by weight to 5% by weight alkali metal carbonate, which may be at least proportionally replaced by alkali metal hydrogen carbonate. In the event that both alkali metal carbonate and alkali metal hydrogen carbonate are present, component a) preferably comprises alkali metal carbonate and alkali metal hydrogen carbonate in a weight ratio of from 10:1 to 1:1.

[0090] In a preferential embodiment regarding component b), it contains from 1% by weight to 5% by weight alkali metal silicate having a modulus in the range from 1.8 to 2.5.

[0091] In a preferential embodiment regarding component c), it contains from 0.05% by weight to 1% by weight phosphonic acid and/or alkaline phosphonate. In this context, phosphonic acids are also understood to mean optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid moieties (known as polyphosphonic acids). They are preferably selected from the hydroxy- and/or aminoalkylphosphonic acids and/or alkali salts thereof, for example dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, aminotris(methylenephosphonic acid), Ν,Ν,Ν',Ν'-ethylenediaminetetrakis(methylenephosphonic acid) and the acylated derivatives of phosphorous acid, which may also be used in any mixtures desired.

[0092] With regard to component d), reference is hereby made to the definition of the phosphate builder.

[0093] With regard to component e), suitable are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight from 500 to 70,000 g/mol. This class of substances was described in detail in the foregoing. The (co)polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The (co)polymeric polycarboxylate content of the compositions is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.

[0094] As it is used herein, the term zeolite builder refers not only to zeolite in the proper sense, but also to both crystalline and amorphous alkali metal aluminosilicate. Zeolite is contained in the detergent or cleaning agent in quantities from 0 to 10% by weight, preferably not more than 5% by weight. Preferable among these for detergent quality are the crystalline sodium aluminosilicates, in particular zeolites A, P and, where appropriate, X. Quantities close to the aforesaid upper limit are preferably used in solid or particulate agents. Suitable aluminosilicates specifically consist of no particles with a size of over 30 pm, and preferably consist of at least 80% by weight particles with a size of smaller than 10 pm. Their calciumbinding capacity, which can be determined in accordance with the instructions in German Patent Specification DE 24 12 837, is usually in the range from 100 to 200 mg of CaO per gram.

[0095] The detergent or cleaning agent preferably comprises 0-10% by weight, preferably 0-5% by weight zeolite builder.

[0096] The term alkali metal silicate refers to crystalline and amorphous alkali metal silicates.

Crystalline alkali metal silicates include layer-shaped sodium silicates with the general formula of NaMSix02x+ryH20 where M means sodium or hydrogen, x 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. They are suitable for the substitution of zeolites or phosphates. Crystalline layer silicates such as these are described, for example, in European Patent Application EP-A-0 164 514. Preferable crystalline layer silicates having the specified formula are those in which M stands for sodium and x assumes the values 2 or 3.

[0097] In particular, both β- and δ-sodium disilicates Na2Si205yH20 are preferred.

[0098] Preferable amorphous alkali metal silicates are amorphous sodium silicates with an Na20:Si02 modulus ranging from 1:2 to 1: 3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which have retarded dissolution and secondary wash properties. The retarded dissolution compared with conventional amorphous sodium silicates may be brought about in a variety of ways, for example by surface treatment, compounding, compaction/compression or by overdrying. For the purposes of this invention, the term “amorphous” is also understood to mean “x-ray-amorphous." This means that, in x-ray diffraction experiments, the silicates do not provide sharp x-ray reflections as are typical of crystalline substances, but rather, at best, one or more maxima of the scattered x-radiation which have a width of several degree units of the diffraction angle. However, it can quite possibly lead even to particularly good builder properties when the silicate particles in electron diffraction experiments provide blurred or even sharp diffraction maxima. This should be interpreted such that the products have microcrystalline regions of from 10 to several hundred nm in size, whereby those up to a maximum of 50 nm and in particular up to maximum of 20 nm are preferred. Such so-called x-ray-amorphous silicates likewise have retarded dissolution compared to the conventional waterglasses, and are described for example in German Patent Application DE-A-44 00 024. Especially preferred are compacted/compressed amorphous silicates, compounded amorphous silicates and overdried x-ray-amorphous silicates, whereby the overdried silicates in particular are also preferable as carriers present in the granulates according to the invention or for use as carriers in the method according to the invention.

[0099] The detergent or cleaning agent preferably comprises 0-15% by weight, more preferably still 0-10% by weight alkali metal silicate builders, preferably sodium silicate builders.

[0100] The detergents or cleaning agents according to the invention comprise 0-10% by weight, preferably 0-5% by weight, more preferably still 0-1% by weight phosphate builders.

[0101] Among the variety of commercially available phosphate builders, the alkali metal phosphates are of great importance to the detergent or cleaning agent according to the invention, with special preference given to pentasodium tripolyphosphate, Na5P3Oi0 (sodium tripolyphosphate) or pentapotassium triphosphate, K5P3O10 (potassiumtripolyphosphate). If phosphates are used as active cleaning substances in the context of the present invention, then the preferred detergent or cleaning agent contains said phosphate(s), preferably pentapotassium triphosphate, whereby the preferable phosphate portion of the total weight of the detergent or cleaning agent is 0 to 10% by weight, preferably 0 to 5% by weight and in particular 0 to 1% by weight.

[0102] The solid detergents or cleaning agents according to the invention may be made available in manufactured forms known to one skilled in the art, for example powders, granules, extruded or compacted products and in particular tablets.

[0103] A material, for example a composition or an agent, is defined as a solid in terms of the invention if it exists in a solid state at 25°C and 1013 mbar.

[0104] A material, for example a composition or an agent, is defined as a liquid in terms of the invention if it exists in a liquid state at 25°C and 1013 mbar. The definition of a liquid thus also applies to a gel.

[0105] In addition to the enzymes according to the invention, the inventive detergents or cleaning agents in solid and specifically in powder form may in principle also contain all well-known and typical ingredients found in detergents and cleaning agents of this kind, whereby at least one additional ingredient is present in the detergent or cleaning agent. The detergents or cleaning agents according to the invention may specifically contain builders, surfactants, bleaches based on organic and/or inorganic peroxygen compounds, bleach activators, bleach catalysts, water-miscible organic solvents, enzymes, sequester agents, electrolytes, pH regulators and other washing aids such as optical brighteners, graying inhibitors, foam regulators as well as dyes and fragrances and combinations thereof.

[0106] In one embodiment, a detergent or cleaning agent further comprises 5% by weight to 70% by weight, in particular 5% by weight to 35% by weight surfactants and/or 0-10% by weight, preferably 0-5% by weight phosphate builders, and 5% by weight to 55% by weight, in particular 5% by weight to 35% by weight carbonate builders and 0.01 to 15% by weight solid inorganic and/or organic acids or acidic salts and/or 0.01 to 5% by weight complexing agents for heavy metals and/or 0.01 to 5% by weight graying inhibitors and/or 0.01 to 5% by weight color transfer inhibitors and/or 0.01 to 5% by weight foam inhibitors.

[0107] Optionally, the detergent or cleaning agent may further comprise optical brighteners, preferably from 0.01 to 5% by weight.

[0108] The production of solid agents presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, whereby enzymes and possible additional thermosensitive ingredients such as bleaching agents may be added later if necessary. In the production of detergents or cleaning agents according to the invention with increased bulk density, in particular in the range from 650 g/L to 950 g/L, a process comprising an extrusion step is preferable.

[0109] In the production of solid detergents or cleaning agents according to the invention in tablet form, which may be for a single phase or multiple phases and consist of one or more colors and in particular of one layer or multiple layers, in particular two layers, the process is preferably such that all of the ingredients - optionally in each layer - are mixed together in a mixer and the mixture is compressed using conventional tablet presses, for example eccentric presses or rotary presses having pressing forces in the range of about 50 to 100 kN, preferably 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is precompressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular 10 to 15 kN. In this way, it is easy to obtain break-proof tablets which nevertheless dissolve with sufficient rapidity under conditions of use and normally exhibit breaking and bending strengths of 100 to 200 N, but preferably about 150 N. Preferably, a tablet thus produced has a weight from 10 gm to 50 gm, in particular from 15 gm to 40 gm. The tablets can assume any three-dimensional form and may be circular, ovular or angular, with intermediate forms also being possible. It is advantageous for corners and edges to be rounded. Round tablets preferably have a diameter from 30 mm to 40 mm. The size in particular of the square- or rectangular-shaped tablets, which are predominantly fed into the washing machine via the metering device, for example that of a washing machine, depends on the geometry and the volume of said metering device. Illustrative preferential embodiments have a surface area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or of 24x38 mm.

[0110] Preferably, the detergent or cleaning agent comprises 0-25% by weight, more preferably 0-15% by weight of a peroxygen compound.

[0111] Peroxygen compounds coming into consideration for use in the detergent or cleaning agent according to the invention are organic peroxides or peroxide salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedoic acids, hydrogen peroxide, as well as inorganic salts yielding hydrogen peroxide under washing conditions, among them perborates, percarbonates, persilicates and/or persulfates such as Caroat. If solid peroxygen compounds are to be introduced, they may be used in the form of powders or granules, which may also be encapsulated in a known manner. In the event a detergent or cleaning agent according to the invention contains peroxygen compounds, they are present in quantities of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. It may be appropriate to add small quantities of known bleach stabilizers such as phosphonates, as well as borates or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate.

[0112] Usable in the solid detergents or cleaning agents are bleach activators, which, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids preferably comprising 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Substances bearing O- and/or N-acyl groups of said number of carbon atoms and/or optionally substituted benzoyl groups are suitable. Preferable are: repeatedly acylated alkyl diamine, in particular tetraacetylethylendiamin (TAED), acylated triazine derivatives, in particular 1.5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetyl glycoluril (TAGU), n-acylimides, in particular n-nonanoylsuccinimide (NOSI), acylated phenol sulfonate, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2.5-diacetoxy 2,5-dihydrofuran and enol esters as well as acetylated sorbitol and mannitol or mixtures described thereof (SORMAN), acetylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactams, for example, N-benzoylcaprolactam. Use of the hydrophilically substituted acyl acetals and the acyl lactams is likewise preferable. Combinations of conventional bleach activators may also be used. Bleaching activators of this kind can, particularly in the presence of the aforementioned hydrogen peroxide-yielding bleaching agents, be contained in the usual quantity range, preferably in quantities of 0.5% by weight to 10% by weight, in particular 1% by weight to 8% by weight based on the agent in total, but are preferably entirely omitted when percarboxylic acids are used as the sole bleaching agent.

[0113] In addition to or instead of the aforementioned conventional bleach activators, sulfonimines and/or bleach-boosting transition metal salts or transition metal complexes may also be present as so-called bleach catalysts.

[0114] Included among the dosing forms according to the invention are extruded products, granules, tablets, or pouches containing the solid agent, which may be packed into bulk containers as well as available in a portion size. Alternatively, the detergent or cleaning agent exists as a granulated powder, in particular having a bulk weight from 300 g/L to 1,200 g/L, in particular 500 g/L to 900 g/L or from 600 g/L to 850 g/L.

[0115] Embodiments of the present invention include all solid, powder, liquid, gel or paste dosing forms of the agent, which may optionally serve for multiple phases and can exist in either a compressed or an uncompressed form. Therefore, in a further embodiment of the invention, the detergent or cleaning agent is characterized in that it consists of a single component system. A detergent or cleaning agent of this kind preferably consists of one phase. Of course, the inventive agent may also consist of multiple phases, for example two liquid phases, two solid phases, or a liquid and a solid phase. Therefore, in a further embodiment of the invention, the detergents or cleaning agents are characterized in that they are divided into several components.

[0116] Based on their total weight, the detergents or cleaning agents according to the invention preferably comprise less than 10% by weight, preferably between 1 and 10% by weight, and in particular between 1 and 5% by weight water.

[0117] A further aspect of the present invention concerns a method for cleaning textiles or hard surfaces, characterized in that at least one method step uses a solid detergent or cleaning agent according to the invention.

[0118] Such methods include manual as well as machine methods, whereby machine methods are preferable. In general, methods for cleaning textiles are distinguished by the fact that various active cleaning substances are applied to the item for washing, and, after the time of action, are washed off, or that the item for washing is treated in some other way with a detergent or a solution for diluting said detergent or cleaning agent. The same applies to methods for the cleaning of all materials other than textiles, hard surfaces in particular. At least one of the steps of any conceivable washing or cleaning method can be enhanced through the application of an detergent or cleaning agent according to the invention, or of an amylase according to the invention, preferably in combination with the protease, therefore constituting embodiments of the present invention. All facts, subject-matter and embodiments that are described in regard to amylase according to the invention, preferably in combination with protease, as well as the agent in which they are contained, are also applicable to this inventive subject-matter. Therefore, reference is expressly made at this juncture to the disclosure made at the appropriate place with the note that said disclosure also applies to the method according to the invention described above.

[0119] Alternative embodiments of this inventive subject-matter also represent methods for the treatment of textile raw materials or for textile care, in which a protease according to the invention is active in at least one method step. Preferable among these are methods for textile raw materials, fibers or textiles containing natural components, most particularly for those containing wool or silk.

[0120] A further object of the invention is the use of a detergent or cleaning agent according to the invention for cleaning textiles or hard surfaces, particularly such that the combination of amylase and protease is used in a quantity from 40 μg to 4 gm, preferably from 50 pg to 3 gm, more preferably from 100 pg to 2 gm and most preferably from 200 pg to 1 gm.

[0121] The following test was carried out in order to examine washing and cleaning performance: [0122] Standard soiled textile materials were used. The following soiling was used: Blood/milk/ink on cotton: Product no. C-05 available from CFT (Center for Test Materials) B.V. Vlaardingen, Netherlands [0123] The solid detergents or cleaning agents according to the invention containing the inventive amylase demonstrated improved cleaning performance compared to corresponding agents containing the Stainzyme® amylase. The advantage was particularly evident when the amylases were combined with protease.

[0124] The synergistic effect of the α-amylase according to the invention and the protease in solid low-phosphate and carbonate-rich detergents was demonstrated by an improvement in cleaning performance of soils containing starch. It was additionally observed that the amylase according to the invention works surprisingly well in so-called soluble builder formulations, which refers to formulations comprising only small quantities of zeolite and phosphate builders.

The improvement in washabilitv was particularly apparent in starch soils and foods with starches such as chocolate cream.

[0125] All facts, subject-matter and embodiments that are described in regard to proteases according to the invention, as well as the agent in which they are contained, are also applicable to this inventive subject-matter. Therefore, reference is expressly made at this juncture to the disclosure made at the appropriate place with note being made that said disclosure also applies to the usage according to the invention described above.

General Definitions [0126] All of the documents cited above are hereby incorporated herein by reference in their entirety. The inventions described herein for clarification may be carried out in a suitable fashion in the absence of any given element or elements, restriction or restrictions which are not specifically disclosed here. Therefore, terms such as "comprising," "including," "containing" and the like can be interpreted broadly and without restriction. In addition, these terms and expressions are merely used for descriptive purposes, not for restrictive purposes, and it is not the intention in using such terms and expressions to exclude anything equivalent to the features shown and described or portions thereof, but it is instead obvious that it is possible to make various modifications within the scope of the claimed invention. It is therefore clear that, although the present invention is disclosed by means of preferential embodiments and optional features, modifications and variations of said inventions are disclosed which a person skilled in the art may refer back to, thus enabling the development of new modifications and variations, which lie within the scope of the present invention. The invention is described in broad and generic terms. Each of the narrower species and subgroups that fall within the general disclosure are likewise a part of the invention. This includes the generic description of the invention with the proviso or negative limitation that excludes items of the genus, regardless of whether the cut material is indicated herein specifically. In cases where features or aspects of the invention in the form of Markush groups are described, a person skilled in the art will recognize that the invention is thus also described in terms of each individual member or subgroup of members of the Markush group. Further embodiments of the invention will become apparent from the claims hereinafter.

Examples [0127] The following examples explain the invention but do not, however, restrict it:

Example 1: [0128] Examination of the solid detergent or cleaning agent according to the invention containing amylase or amylase and protease in the washing machine.

[0129] Standard soiled textile materials were used for this example.

[0130] The same amount of active enzyme was used in each of the comparative examinations. The amylases or the combination of amylases and proteases were added on top of a powdered detergent containing 10% linear alkylbenzene sulfonate (sodium salt), 1.5% C12-C 18-fatty alcohol sulfate (sodium salt), 2.0% C12-C18-fatty alcohol with 7 EO, 20% sodium carbonate, 6.5% sodium hydrogen carbonate, 4.0% amorphous sodium disilicate, 17% sodium carbonate peroxyhydrate, 4.0% TAED, 3.0% polyacrylate, 1.0% carboxymethyl cellulose, 1.0% phosphonate, 27% sodium sulfate, remaining ingredients: foam inhibitors, optical brighteners, fragrances.

[0131] The detergent dose in powder form consisted of between 4.5 and 7.0 grams per liter of wash liquor. Washing took place at a pH value of pH 8.5 and 30°C, water hardness 16°dH, in a Miele 1935 for a total wash time of 70 minutes.

Example 2: [0132] Table 1 shows an inventive powdered detergent B in comparison with non-inventive powdered detergents A and C.

[0133] Protease * (protease comprising an amino acid sequence having the following amino acid substitutions according to SEQ ID NO. 2 numbering: S3T, V4I, V199I, otherwise comprising the amino acid sequence specified in SEQ ID NO. 2) Amylase *: amylase according to the invention

Example 3: Wash test to demonstrate improved stain removal [0134] Substances used: [0135] For the wash tests, household washing machines (Miele W 1935, 53 min. wash cycle, 16°d water hardness) were loaded with 3.5 kg of additional laundry as well as the soiled cloth rags.

[0136] In addition, 65g/115 ml_ dose of the test detergent was added and washed at 30°C. Detergent A from Table 1 was used for reference and compared with inventive detergent B. After hanging the cloth rags to dry and pressing them, their whiteness degree (tristimulus value Y without UV) was determined using spectrophotometry (Minolta CR200-1).

[0137] The specified values (Table 2) are averages of 6 determinations. The soiled textiles had been purchased. The mean reflectance values are shown in column A (for composition A) and column B (for composition B). Table 3 shows the differences in reflectance values in regard to standard detergent as well as the errors in the 6-fold determination (HSD) in Table 3. Use of the amylase according to the invention in detergent formulation B showed soil removability improvements in comparison to detergent formulation A, which contained the amylase Thermamyl®, particularly for starch stains.

Table 3: Washing results using statistical analysis in a 6-fold determination (HSD) as per Tukey

It is thus shown that inventive composition B is significantly better at removing soils containing starch.

Example 4: Wash test to demonstrate improved stain removal [0138] An inventive powdered detergent B in comparison with a non-inventive, low-carbonate powdered detergent C containing phosphate.

[0139] Substances used:

For the wash tests, household washing machines (Miele W 1935, 53 min. wash cycle, 16°d water hardness) were loaded with 3.5 kg of additional laundry as well as the soiled cloth rags. In addition, 65g/115 ml dose of the test detergent was added and washed at 30°C. Detergent C from Table 1 was used for reference and compared with inventive detergent B. After hanging the cloth rags to dry and pressing them, their whiteness degree (tristimulus value Y without UV) was determined using spectrophotometry (Minolta CR200-1).

[0140] The soiled textiles had been purchased. The averages of 6 determinations were established and the differences between the average reflectance values for detergents B and C as well as errors in the 6-fold determination (HSD) were calculated (Table 4). Use of the amylase according to the invention in detergent formulation B showed soil removability improvements in comparison to detergent formulation C, which contained the same amylase, particularly for starch stains.

Table 4: Washing results using statistical analysis in a 6-fold determination (HSD) as per Tukey

[0141] It is thus shown that inventive composition B is significantly better at removing soils containing starch.

Claims (13)

1. Claims

   1. Solid detergent or cleaning agent containing 5-70% by weight surfactant, 5-55% by weight carbonate, 0-10% by weight phosphate builder and an α-amylase, wherein the α-amylase is characterized by having sequence identity with the sequence specified in SEQ ID NO. 1 over its entire length of at least 89% and, with increasing preference, of at least 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94, 94.5% , 95.5%, 95%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5% and up to 100%, and, according to SEQ ID NO. 1 numbering, comprises deletions in one or more of the positions 180, 181, 182, 183 and 184.
2. 2. Solid detergent or cleaning agent according to claim 1, wherein the amylase comprises deletions in at least two positions selected from the positions 180 + 181, 181 + 182, 182 + 183 and 183 + 184 according to SEQ ID NO. 1 numbering, most particularly preferable being deletions in positions 183 + 184 according to SEQ ID NO. 1 numbering.
3. 3. Solid detergent or cleaning agent according to claims 1 and 2, wherein the amylase comprises the H183* + G184* deletions according to SEQ ID NO. 1 numbering.
4. 4. Solid detergent or cleaning agent according to claims 1 to 3, wherein the amylase furthermore comprises amino acid substitutions at one or more of the positions 405, 421, 422 and 428 according to SEQ. ID NO. 1 numbering.
5. 5. Solid detergent or cleaning agent according to claims 1 to 4, wherein the amylase comprises the I405L, A421H, A422P and A428T substitutions according to SEQ ID NO. 1 numbering.
6. 6. Solid detergent or cleaning agent according to claims 1 to 5, wherein a) said detergent or cleaning agent comprises 5-55% by weight, preferably 5-35% by weight anionic surfactant, 0-20% by weight, preferably 0-10% by weight sodium silicate builder and 0-10% by weight, preferably 0-5% by weight zeolite builder and/or b) said agent comprises a protease, specifically protease in a quantity 0.001-0.1% by weight, preferably 0.01 to 0.06% by weight.
7. 7. Solid detergent or cleaning agent according to claim 6, wherein the protease comprises an amino acid sequence having sequence identity with the amino acid sequence specified in SEQ ID NO. 2 and/or in SEQ ID NO. 3 over its entire length of at least 80% and, with increasing preference, of at least 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99%, or b) the protease comprises an amino acid sequence having sequence identity with the amino acid sequence specified in SEQ ID NO. 2 over its entire length of at least 80% and, with increasing preference, of at least 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99%, and has the amino acid glutamic acid (E) at position 99 according to SEQ ID NO. 2 numbering, or c) the protease comprises an amino acid sequence having sequence identity with the amino acid sequence specified in SEQ. ID NO. 2 over its entire length of at least 80% and, with increasing preference, of at least 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% and 99%, and has the amino acid glutamic acid (T) at position 3, the amino acid isoleucine (I) at position 4 and the amino acid isoleucine (I) at position 199 according to SEQ ID NO. 2 numbering.
8. 8. Solid detergent or cleaning agent according to claims 1 to 7, wherein the protease is a protease according to SEQ ID NO. 4 and/or said detergent or cleaning agent comprises ΟΙ 5% by weight, preferably 0-10% by weight nonionic surfactant and/or 0-25% by weight, preferably 0-15% by weight of a peroxygen compound.
9. 9. Solid detergent or cleaning agent according to claims 1 to 8, characterized in that contained therein is a quantity of amylase 0.001-0.15% by weight, preferably from 0.005 to 0.012% by weight based on the total weight of said detergent or cleaning agent.
10. 10. Solid detergent or cleaning agent according to claims 1 to 9, characterized in that the solid detergent or cleaning agent according to the invention preferably comprises 10 to 30% by weight anionic surfactant, 0 to 5% by weight phosphate builder, 5 to 30% by weight sodium carbonate, 0 to 10% by weight, preferably 1 to 10% by weight sodium silicate builder, 0 to 10% by weight, preferably 1 to 3% by weight polyacrylate, 0 to 5% by weight, preferably from 0 to 1% by weight zeolite builder and 0.005 to 10% by weight, preferably 0.5 to 2% by weight phosphonate, preferably HEDP.
11. 11. The use of a solid detergent or cleaning agent according to any of the claims 1-10 for the washing of textiles or the cleaning of hard surfaces.
12. 12. The use of solid detergents or cleaning agents according to any of the claims 1-10 for the removal of starch-containing soils from textiles or hard surfaces.
13. 13. A method for cleaning textiles or hard surfaces, characterized in that a solid detergent or cleaning agent according to any of the claims 1-10 is used in at least one method step.