Cleaners containing enzymes

Abstract

The invention relates to cleaning agents, preferably dishwasher detergents, in particular dishwashing machine detergents, comprising at least one gel-like phase with a low water content, preferably a substantially water-free gel-like phase, which contains at least one enzyme, preferably at least one enzyme granulate.

Description

[0001] The present invention relates to cleaning agents, preferably dishwasher detergents, in particular automatic dishwasher detergents, comprising at least one low-water, preferably substantially water-free gel phase, said gel phase containing at least one enzyme, preferably at least one enzyme granulate.

[0002] Detergents or cleaning agents are usually presented in solid form (e.g., as tablets) or in liquid form (or as flowing gels). In particular, liquid detergents or cleaning agents are becoming more and more popular with consumers. Pre-dispensed forms are popular with consumers because they are easier to meter. Pre-dispensed flowing gels are often problematic because, for example, they tend to leak when packaged in single-chamber bags or multi-chamber bags.

[0003] The problem addressed by the present invention is to provide cleaning agents, in particular dishwasher detergents, preferably automatic dishwasher detergents, which can be produced easily and cost-effectively while improving the cleaning performance, in particular on enzyme-sensitive stains.

[0004] The present invention therefore firstly relates to cleaning agents comprising at least one low-water, preferably substantially water-free gel phase which contains at least one enzyme.

[0005] One advantage of the present invention is that the resulting cleaning agents have good stability, particularly during storage, and improved cleaning performance, particularly with respect to stains such as crème brûlée, egg yolk and pasta.

[0006] Surprisingly, it has been found that the cleaning agents according to the invention have particularly good cleaning performance on enzyme-sensitive stains. It is particularly worth mentioning that the cleaning agents also have improved cleaning performance on non-protease-specific stains.

[0007] In a preferred embodiment, the cleaning agent, preferably a dishwasher detergent, in particular an automatic dishwasher detergent, comprises at least one low-water, preferably substantially anhydrous gel phase, which contains at least one enzyme granule. Thus, at least one enzyme is preferably in the form of granules. Particularly preferably, all enzymes in the gel phase are in the form of granules.

[0008] This has the advantage that the stability of the enzyme or enzymes is very well ensured.In addition, visible particles in a transparent detergent phase, for example from enzyme particles, are very popular with consumers due to their attractive appearance.

[0009] The enzymes contained in the gel phase include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are of natural origin in principle; starting from natural molecules, variants which have been improved for use in cleaning agents are available, which are preferably used accordingly. The cleaning agents according to the invention preferably contain a total amount of 1×10 -6 % to 5% by weight of enzyme. The protein concentration can be determined using known methods such as the BCA method or the biuret method.

[0010] According to a preferred embodiment, the proportion by weight of all enzymes in the at least one gel phase (based on the amount of active enzyme protein), based on the total weight of the gel phase, is from 0.001 to 10.0 wt.-%, preferably from 0.01 to 7.5 wt.-%, more preferably from 0.05 to 6.0 wt.-%, and even more preferably from 0.1 to 5.0 wt.-%.

[0011] Among the proteases, subtilisin-type proteases are preferred. Examples of these are subtilisin BPN' and Carlsberg and their development forms, protease PB92, subtilisin 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and also thermitase, proteinase K and proteases TW3 and TW7, which belong to the subtilase, but no longer to the more narrow subtilisin.

[0012] According to a particularly preferred embodiment, at least one gel phase comprises at least one enzyme, preferably at least one enzyme particle, selected from proteases, preferably from subtilisin (or a subtilisin-containing enzyme), wherein the preferred protease is selected from the following proteases:

[0013] a) a protease comprising an amino acid sequence which over its entire length has at least 70% sequence identity to the amino acid sequence specified in SEQ ID NO: 1 (B. gibsonii wt) and has an amino acid substitution at at least one position corresponding to position 12, 43, 122, 127, 154, 156, 160, 211, 212 or 222, each based on the numbering according to SEQ ID NO: 1, in particular at least one amino acid substitution is selected from the group consisting of Q12L, I43V, M122L, D127P, N154S, T156A, G160S, M211N, M211L, P212D, P212H or A222S, in each case based on the numbering according to SEQ ID NO: 1, and / or particularly preferably has one of the following amino acid substitution variants, in each case based on the numbering according to SEQ ID NO: 1:

[0014] (i) I43V;

[0015] (ii) M122L, N154S and T156A;

[0016] (iii) M211N and P212D;

[0017] (iv) M211L and P212D;

[0018] (v) G160S;

[0019] (vi) D127P, M211L and P212D;

[0020] (vii) P212H; or

[0021] (viii) Q12L, M122L and A222S;

[0022] b) a protease comprising an amino acid sequence comprising subtilisin 309 from Bacillus lentus, in particular a protease comprising an amino acid sequence which is at least 80%, preferably at least 90%, in particular 100% identical over its entire length to the amino acid sequence specified in SEQ ID NO: 2 and which has at least one amino acid substitution at one of positions 9, 15, 66, 212 and 239 according to the numbering of SEQ ID NO: 2, preferably selected from S9R, A15T, V66A, N212D and Q239R;

[0023] c) a protease comprising an amino acid sequence comprising subtilisin 309 from Bacillus lentus, in particular a protease comprising an amino acid sequence which is at least 80%, preferably at least 90%, in particular 100% identical over its entire length to the amino acid sequence specified in SEQ ID NO: 2, and having an amino acid substitution at position 97 according to the numbering of SEQ ID NO: 2, and an amino acid insertion between the amino acids at positions 97 and 98, preferably selected from S97A and / or S97AD;

[0024] d) a protease comprising an amino acid sequence having an amino acid sequence which over its entire length is at least 80%, preferably at least 90%, in particular 100% identical to the amino acid sequence specified in SEQ ID NO:3 (Bacillus alkalophilus PB92), and optionally having at least one amino acid substitution at one of the following positions 32, 33, 48-54, 58-62, 94-107, 116, 123-133, 150, 152-156, 158-161, 164, 169, 175-186, 197, 198 and 203-216 according to the numbering of SEQ ID NO:3, in particular at least one amino acid substitution at one, two, three or four of the following positions 116, 126, 127, 128 and 160 of NO: 3, preferably at least one of amino acid substitutions G116V, S126L, P127Q and / or S128A, even more preferably a plurality, most preferably each, and / or

[0025] e) a protease comprising an amino acid sequence comprising an alkaline protease from Bacillus lentus DSM 5483, in particular a protease having an amino acid sequence which over its entire length is at least 80%, preferably at least 90%, in particular 100% identical to the amino acid sequence specified in SEQ ID NO:4, and optionally having at least one amino acid substitution at one, two, three or four of the following positions 3, 4, 99 and 199 according to the numbering of SEQ ID NO:4, in particular the amino acid substitution R99E or R99D, and optionally at least one or two, preferably all three, of the further amino acid substitutions S3T, V4I and V199I.

[0026] In the context of the present invention, whereby an enzyme, particularly a protease, has said substituted features means that it contains at least one corresponding amino acid at the corresponding position, i.e. not all 10 positions are otherwise mutated or deleted, e.g. by fragmentation of the enzyme, particularly a protease.

[0027] As used herein, "variant" refers to the natural or artificially generated variation of a natural enzyme, which has an amino acid sequence modified from a reference form. In addition to the amino acid changes discussed above, enzymes according to the present invention can also have other amino acid changes, particularly amino acid substitutions, insertions or deletions. For example, such enzymes are modified by targeted genetics, i.e., developed by mutagenesis methods, and optimized for specific applications or for specific properties (e.g., for its catalytic activity, stability, etc.). In addition, nucleic acids according to the present invention can be introduced into recombinant methods, and therefore can be used to generate enzymes or other polypeptides of completely new types. The purpose is to introduce targeted mutations such as substitutions, insertions or deletions into known molecules, such as to improve the cleaning properties of enzymes. For this purpose, the surface charge and / or isoelectric point of a molecule can be changed in particular, and therefore its interaction with a substrate can be changed. For example, particularly for use in detergents and cleaning agents, the net charge of an enzyme can be changed in order to affect substrate binding. Alternatively or in addition, one or more corresponding mutations can increase the stability or catalytic activity of an enzyme, and therefore improve its cleaning properties. Individual mutations such as the favorable properties of individual substitutions can complement each other. Therefore, it is possible within the scope of the present invention to further develop proteases which have been optimized with respect to certain properties, such as their stability towards surfactants and / or bleach and / or other components.

[0028] For the description of substitutions (amino acid exchanges) related to exactly one amino acid position, the following convention is used herein: first, the naturally occurring amino acid is designated in the form of the internationally used single-letter code, followed by the relevant sequence position and finally the inserted amino acid. Several exchanges within the same polypeptide chain are separated by a slash. For insertions, the additional amino acids are named following the sequence position. In the case of deletions, the missing amino acid is replaced by a symbol such as an asterisk or a dash, or Δ is given before the corresponding position. For example, P14H describes the substitution of a proline at position 14 by a histidine, P14HT describes the insertion of a threonine after the amino acid histidine at position 14, and P14* or ΔP14 describes the deletion of a proline at position 14. This nomenclature is known to those skilled in the art in the field of enzyme technology.

[0029] The identity of nucleotide sequence or amino acid sequence is determined by sequence comparison. The sequence is relatively based on the BLAST algorithm established in the prior art and commonly used (reference for example, Altschul et al. (1990) "Basic local alignment search tool," J.Mol.Biol.215:403-410, and Altschul et al. (1997): "Gapped BLAST and PSI-BLAST:a new generation of protein database search programs," Nucleic Acids Res., 25:3389-3402), and in principle occurs by the nucleotides in the nucleotide sequence or amino acid sequence related to each other or the similar sequence of amino acid. The table format of the involved position is related to be referred to as comparison. Another algorithm available in the prior art is the FASTA algorithm. Use a computer program to create a sequence comparison (comparison), particularly a multiple sequence comparison. For example, the Clustal series (see, e.g., Chenna et al. (2003) "Multiple sequence alignment with the Clustal series of programs," Nucleic Acid Res. 31: 3497-3500), T-Coffee (see, e.g., Notredame et al. (2000) "T-Coffee: A novel method for multiple sequence alignments," J. Mol. Biol. 302: 205-217) or programs based on these programs or algorithms are frequently used. Using the computer program Vector Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with predetermined standard parameters is also possible, the AlignX module of which program for sequence comparison is based on Clustal W. Unless otherwise stated, sequence identities specified herein are determined by the BLAST algorithm.

[0030] In a further embodiment of the present invention the protease for use according to the invention comprises an amino acid sequence which over its entire length has preferably at least 70%, and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 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 98.8% identity with the amino acid sequence specified in SEQ ID NO: 1 . The numbering of NO: 1 corresponds to one or more of the amino acid substitutions 12L, 43V, 122L, 127P, 154S, 156A, 160S, 211N, 211L, 212D, 212H or 222S at at least one of positions 12, 43, 122, 127, 154, 156, 160, 211, 212 or 222.

[0031] In a further embodiment of the invention, the protease for use according to the invention comprises an amino acid sequence which over its entire length has at least 81%, and increasingly preferably at least 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 98.8% identity with the amino acid sequence specified in SEQ ID NO: 2, and preferably has at least one amino acid substitution at one of the positions corresponding to positions 9, 15, 66, 212 and 239 according to the numbering of SEQ ID NO: 2, and has one or more amino acid substitutions preferably selected from 9R, 15T, 66A, 212D or 239R.

[0032] In a further embodiment of the invention, the protease for use according to the invention comprises an amino acid sequence which over its entire length has at least 81%, and increasingly preferably at least 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 98.8% identity with the amino acid sequence specified in SEQ ID NO: 2, and having an amino acid substitution at position 97 according to the numbering of SEQ ID NO: 2 and an amino acid insertion between the amino acids at positions 97 and 98, preferably selected from 97A and / or 97AD.

[0033] In a further embodiment of the present invention the protease for use according to the invention comprises an amino acid sequence which over its entire length has at least 81%, and increasingly preferably at least 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 98.8% identity with the amino acid sequence specified in SEQ ID NO: 3, and preferably in the amino acid sequence specified in SEQ ID NO: 4. NO:3 numbering corresponds to at least one of positions 32, 33, 48-54, 58-62, 94-107, 116, 123-133, 150, 152-156, 158-161, 164, 169, 175-186, 197, 198 and 203-216, in particular having at least one amino acid substitution at one, two, three or four of the following positions 116, 126, 127, 128 and 160 according to the numbering of SEQ ID NO:3, preferably at least one of amino acid substitutions 116V, 126L, 127Q and / or 128A, more preferably multiple, most preferably each.

[0034] In a further embodiment of the invention, the protease for use according to the invention comprises an amino acid sequence which over its entire length has at least 81%, and increasingly preferably at least 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 98.8% identity with the amino acid sequence specified in SEQ ID NO:4, and preferably has the amino acid substitution 99E or 99D at at least one position corresponding to position 3, 4, 99 and 199 according to the numbering of SEQ ID NO:4, and optionally at least one or two, preferably all three, of the further amino acid substitutions 3T, 4I and 199I.

[0035] According to a further particularly preferred embodiment of the present invention, the amount of all proteases is preferably 0.001 to 1000 mg / work, more preferably 0.1 to 600 mg / work, and even more preferably 1.0 to 400 mg / work, based on the amount of active enzyme protein added per wash cycle.

[0036] Particularly preferably, at least one gel phase comprises as enzyme (optionally plus further enzymes) a protease comprising an amino acid sequence which over its entire length has at least 70% sequence identity with the amino acid sequence specified in SEQ ID NO: 1 (Bacillus gibsonii wt) and has an amino acid substitution at at least one position corresponding to position 12, 43, 122, 127, 154, 156, 160, 211, 212 or 222, each based on the numbering according to SEQ ID NO: 1, in particular at least one amino acid substitution is selected from the group consisting of Q12L, I43V, M122L, D127P, N154S, T156A, G160S, M211N, M211L, P212D, P212H or A222S, in each case based on the numbering according to SEQ ID NO: 1, and / or particularly preferably has one of the following amino acid substitution variants, in each case based on the numbering according to SEQ ID NO: 1:

[0037] (i) I43V;

[0038] (ii) M122L, N154S and T156A;

[0039] (iii) M211N and P212D;

[0040] (iv) M211L and P212D;

[0041] (v) G160S;

[0042] (vi) D127P, M211L and P212D;

[0043] (vii) P212H; or

[0044] (viii)Q12L, M122L and A222S.

[0045] The cleaning agents according to the invention very particularly preferably contain 0.001 to 1000 mg, more preferably 0.1 to 600 mg and even more preferably 1.0 to 400 mg per cleaning agent portion (preferably in the gel phase of the cleaning agent) of a protease which comprises an amino acid sequence which over its entire length has at least 70% sequence identity with the amino acid sequence specified in SEQ ID NO: 1 (Bacillus gibsonii wt) and has an amino acid substitution at at least one position corresponding to position 12, 43, 122, 127, 154, 156, 160, 211, 212 or 222, in each case based on the numbering according to SEQ ID NO: 1, in particular at least one amino acid substitution is selected from the group consisting of Q12L, I43V, M122L, D127P, N154S, T156A, G160S, M211N, M211L, P212D, P212H or A222, in each case based on the numbering according to SEQ ID NO: 1, and / or particularly preferably has one of the following amino acid substitution variants, in each case based on the numbering according to SEQ ID NO: 1:

[0046] (i) I43V;

[0047] (ii) M122L, N154S and T156A;

[0048] (iii) M211N and P212D;

[0049] (iv) M211L and P212D;

[0050] (v) G160S;

[0051] (vi) D127P, M211L and P212D;

[0052] (vii) P212H; or

[0053] (viii)Q12L, M122L and A222S.

[0054] According to another object of the present invention, in a detergent, in particular in a single detergent part comprising at least one gel phase and at least one further phase, preferably a solid phase, comprising a granular mixture, particularly a powder, the protease from the protease group directly mentioned above is not incorporated in the gel phase, but can be partially or completely incorporated into at least one further phase, preferably at least one solid phase, particularly preferably at least one further solid phase comprising the granular mixture. The amount to be used based on the detergent part to be used remains unchanged. The embodiments described above or below for the gel phase and the further phase preferably solid phase are also applicable to this embodiment in a similar manner.

[0055] According to a further preferred embodiment of the present invention, the proportion by weight of all proteases, based on the amount of active enzyme protein of all proteases, relative to the total weight of the cleaning agent, is 0.005 to 5% by weight, preferably 0.01 to 2.0% by weight, more preferably 0.05 to 1.5% by weight, and even more preferably 0.01 to 1.0% by weight.

[0056] According to a further preferred embodiment of the present invention, the proportion by weight of all proteases in the at least one gel phase, based on the amount of active enzyme protein, based on the total weight of the gel phase, is from 0.0005 to 20.0 wt.-%, preferably from 0.001 to 15 wt.-%, more preferably from 0.01 to 10.0 wt.-% and even more preferably from 0.1 to 7.5 wt.-%.

[0057] According to a further preferred embodiment of the present invention, the amount of all proteases is preferably 0.001 to 1000 mg / work, more preferably 0.1 to 600 mg / work, and even more preferably 1.0 to 400 mg / work, based on the amount of active enzyme protein added per wash cycle.

[0058] According to a further preferred embodiment, at least one gel phase comprises at least one amylase, optionally together with other enzymes, in particular proteases. Preferred amylases according to the invention are alpha-amylases. Whether an enzyme is an alpha-amylase within the meaning of the present invention is determined by its ability to hydrolyze alpha-(1-4)-glycosidic bonds in polysaccharides, in particular amylose and starch. As a result, they cause the decomposition of starch-containing stains on the items to be cleaned. Dextrins and also maltose, glucose and branched oligosaccharides therefrom are formed as decomposition products.

[0059] Examples of amylases are alpha-amylases from Bacillus licheniformis, Bacillus amyloliquefaciens or Bacillus stearothermophilus, and in particular developments thereof which have been improved for use in detergents or cleaners. The enzyme from Bacillus licheniformis is available from Novozymes under the name and from Danisco / Genencor under the name ST. This α-amylase development product is available from Novozymes under the trade name and ultra, from Danisco / Genencor under the name OxAm, and from Daiwa Seiko Inc. Alpha-amylase from Bacillus amyloliquefaciens is produced by Novozymes under the name and a derivative variant of the alpha-amylase from Bacillus stearothermophilus is also marketed by Novozymes under the name and On the market. In addition, for this purpose, it should be emphasized that the alpha-amylase from Bacillus sp. A7-7 (DSM 12368) and the cyclodextrin glucosyltransferase (CGTase) from Bacillus agaradherens (DSM 9948) are. In addition, the amylolytic enzymes disclosed in the international patent applications WO2003002711, WO2003054177 and WO2007079938 can be used, the disclosures of which are hereby explicitly mentioned or the disclosures of which are hereby explicitly included in the present patent application. It is also possible to use fusion products of all the molecules mentioned. In addition, the amylolytic enzymes disclosed in the international patent applications WO2003002711, WO2003054177 and WO2007079938 can be used. The development of alpha-amylases obtained from Aspergillus niger and Aspergillus oryzae is suitable. Other commercial products that can be used advantageously are for example the AL-AMYLASE ® also from Novozymes. as well as or Stainzyme or Stainzyme Variants of these enzymes which can be obtained by point mutations may also be used according to the invention.

[0060] The alpha-amylase used in the detergent or cleaner according to the invention is preferably selected from:

[0061] i. An alpha-amylase comprising an amino acid sequence which has at least 80%, preferably 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 98.8% identity over its entire length to the amino acid sequence specified in SEQ ID NO: 5, and optionally having At least one amino acid substitution at one of the numbered positions 172, 202, 208, 255 and 261 of NO: 5, preferably selected from M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N, R172Q and combinations thereof; and / or

[0062] ii. an α-amylase comprising an amino acid sequence which corresponds over its entire length to SEQ ID %, 94%, 95%, 96%, 97%, 98%, 99%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%, 111%, 112%, 113%, 114%, 115%, 116%, 117%, 118%, 119%, 120%, 121%, 122%, 123%, 124%, 125%, 126%, 127%, 128%, 129%, 130%, 131%, 132%, 133%, 134%, 135%, 136%, 137%, 138%, 139%, 240%, 241%, 242%, 243%, 244%, 245%, 246%, 247%, 248%, 249%, 250%, 251%, 252%, 253%, 254%, 255%, 256%, 257%, 258%, 259%, 260%, 261%, 262%, 263%, 264%, 265%, 266%, 267%, 268%, 269%, NO:6's numbered position 9, 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 195, 202, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 320, 323, 339, 345, 361, 378, 383, 419, at least one amino acid substitution at one of positions 421, 437, 441, 444, 445, 446, 447, 450, 458, 461, 471, 482 and 484, and / or a deletion at one of positions 183 and 184, preferably at least one amino acid substitution at one of positions 9, 26, 149, 182, 186, 202, 257, 295, 299, 323, 339 and 345, particularly preferably selected from R118K, D183*, G184*, N195F, R320K, R458K and combinations thereof; and / or

[0063] iii. An alpha-amylase comprising an amino acid sequence which is at least 90% identical over its entire length to the amino acid sequence specified in SEQ ID NO: 7, and optionally having at least one substitution and / or deletion at one of the numbered positions 93, 116, 118, 129, 133, 134, 140, 142, 146, 147, 149, 151, 152, 169, 174, 183, 184, 186, 189, 193, 195, 197, 198, 200, 203, 206, 210, 212, 213, 235, 243, 244, 260, 262, 284, 303, 304, 320, 338, 347, 359, 418, 431, 434, 439, 447, 458, 469, 476, and 477 of NO:7.

[0064] In various embodiments of the invention, the amylase comprises an amino acid sequence that is at least 80%, preferably 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 98.8% identical to the amino acid sequence specified in SEQ ID NO:5 over its entire length, and optionally has 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 98.8% identical to the amino acid sequence specified in SEQ ID NO:5 At least one amino acid substitution at one of the numbered positions 172, 202, 208, 255 and 261 of NO:5 is preferably selected from M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N, R172Q and combinations thereof. Preferably, amylases are used which have amino acid substitutions at two, preferably three, of the above-mentioned positions, in particular a substitution at position 202 selected from M202L, M202V, M202S, M202T, M202I, M202Q, M202W, in particular S255N at position 255, and in particular R172Q at position 172. M202L and M202T mutants are very particularly preferred.

[0065] In various embodiments of the invention, the amylase comprises an amino acid sequence that corresponds over its entire length to SEQ ID %, 94%, 95%, 96%, 97%, 98%, 99%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%, 111%, 112%, 113%, 114%, 115%, 116%, 117%, 118%, 119%, 120%, 121%, 122%, 123%, 124%, 125%, 126%, 127%, 128%, 129%, 130%, 131%, 132%, 133%, 134%, 135%, 136%, 137%, 138%, 139%, 240%, 241%, 242%, 243%, 244%, 245%, 246%, 247%, 248%, 249%, 250%, 251%, 252%, 253%, 254%, 255%, 256%, 257%, 258%, 259%, 260%, 261%, 262%, 263%, 264%, 265%, 266%, 267%, 268%, 269%, NO:6 numbered position 9, 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 195, 202, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 320, 323, 339, 345, 361, 378, 383, 4 at least one amino acid substitution at one of positions 19, 421, 437, 441, 444, 445, 446, 447, 450, 458, 461, 471, 482 and 484, and / or a deletion at one of positions 183 and 184, preferably at least one amino acid substitution at one of positions 9, 26, 149, 182, 186, 202, 257, 295, 299, 323, 339 and 345, particularly preferably selected from R118K, D183*, G184*, N195F, R320K, R458K and combinations thereof. In various preferred embodiments, the amylase numbered according to SEQ ID NO: 6 has amino acid substitutions at three or more of positions 9, 26, 149, 182, 186, 202, 257, 295, 299, 323, 339 and 345, and optionally one or more, preferably all, of the substitutions and / or deletions at the following positions: 118, 183, 184, 195, 320 and 458, particularly preferably R118K, D183*, G184*, N195F, R320K and / or R458K.In a particularly preferred embodiment, the amylase numbered according to SEQ ID NO: 6 has the following amino acid substitutions and / or deletions: M9L+M323T; M9L+M202L / T / V / I+M323T; M9L+N195F+M202L / T / V / I+M323T; M9L+R118K+D183*+G184*+R320K+M323T+R458K; M9L+R118K+D183*+G184*+M202L / T / V / I+R320K+M323T+R458K; M9L+G149A+G182T+G186A+M202L+T257I+Y295F+N299Y+M323T+A33 9S+E345R; M9L+G149A+G182T+G186A+M202I+T257I+Y295F+N299Y+M32 3T+A339S+E345R; M9L+R118K+G149A+G182T+D183*+G184*+G186A+M20 2L+T257I+Y295F+N299Y+R320K+M323T+A339S+E345R+R458K; M9L+R11 8K+G149A+G182T+D183*+G184*+G186A+N195F+M202L+T257I+Y295F+N2 99Y+R320K+M323T+A339S+E345R+R458K; M9L+R118K+G149A+G182T+D1 83*+G184*+G186A+M202I+T257I+Y295F+N299Y+R320K+M323T+A339S+ E345R+R458K; M9L+R118K+D183*+D184*+N195F+M202L+R320K+M323T+R458K; M9L+R118K+D183*+D184*+N195F+M202T+R320K+M323T+R458K; M9L+R118K+D183*+D184*+N195F+M202I+R320K+M323T+R458K; M9L+R118K+D183*+D184*+N195F+M202V+R320K+M323T+R458K; M9L+R118K+N150H+D183*+D184*+N195F+M202L+V214T+R320K+M323T+R458K; or M9L+R118K+D183*+D184*+N195F+M202L+V214T+R320K+M323T+E345N+R458K.

[0066] A particularly preferred amylase is sold under the trade name Stainzyme Plus TM (Novozymes A / S, Bagsvaerd, Denmark) commercially available variants.

[0067] In various embodiments of the invention, the amylase comprises an amino acid sequence having at least 90%, preferably 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 98.8% identity over its entire length to the amino acid sequence specified in SEQ ID NO:7, and optionally having at least one substitution and / or deletion at one of the numbered positions 93, 116, 118, 129, 133, 134, 140, 142, 146, 147, 149, 151, 152, 169, 174, 183, 184, 186, 189, 193, 195, 197, 198, 200, 203, 206, 210, 212, 213, 235, 243, 244, 260, 262, 284, 303, 304, 320, 338, 347, 359, 418, 431, 434, 439, 447, 458, 469, 476, and 477 of NO:7. Preferred amino acid substitutions in this regard include: E260A / D / C / Q / L / M / F / P / S / WA / / G / H / I / K / N / R / T / Y, G304R / K / E / Q, W140Y / F, W189E / G / T, D134E, F262G / P, W284D / H / F / Y / R, W347H / F / Y, W439R / G, G476E / Q / R / K, G477E / Q / K / M / R, N195F / Y, N197F / L, Y198N, Y200F, Y203F, I206H / L / N / F / Y, H210Y, E212V / G, V213A, M116T, Q129L, G133E, E134Y, K142R, P14 6S, G147E, G149R, N151R, Y152H, Q169E, N174R, A186R, Y243F, S244Q, G303V, R320N, R359I, N418D and A447V.

[0068] In various preferred embodiments, the cleaning agents according to the invention may contain at least one second amylase which is different from the first amylase and / or at least one second protease which is selected from the above-mentioned group and which is different from the first protease.

[0069] If two amylases are contained, they can preferably be used in a weight ratio of 50:1 to 1:50, preferably 30:1 to 1:10 (in each case based on the amount of active protein amylase 1 / amylase 2). Particular preference is given to using a first amylase / second amylase in a ratio of 20:1 to 2:1, preferably 15:1 to 3:1, particularly preferably 12:1 to 5:1, for example 10:1.

[0070] According to a preferred embodiment of the invention, the proportion by weight of the at least one amylase is 0.0005 to 2 wt.-%, preferably 0.001 to 1.5 wt.-%, more preferably 0.005 to 1.0 wt.-%, and even more preferably 0.001 to 0.8 wt.-%, based on the amount of active enzyme protein of all amylases, relative to the total weight of the cleaning agent.

[0071] Furthermore, lipases or cutinases can be used according to the invention, in particular due to their triglyceride cleavage activity, but also for the in situ generation of peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa ((Thermomyces lanuginosus)) and those which have been further developed, in particular with amino acid exchanges at positions D96L, T213R and / or N233R, particularly preferably all of which have exchanges D96L, T213R and N233R.

[0072] Furthermore, enzymes may be used which may be grouped together under the term "hemicellulase". These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectinesterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and beta-glucanases.

[0073] In order to increase the bleaching effect, according to the invention, oxidoreductases such as oxidases, oxygenases, catalases, peroxidases (e.g. halogen-, chloro-, bromo-, lignin, glucose or manganese peroxidases), dioxygenases or laccases (phenol oxidase, polyphenol oxidase) can be used. Advantageously, an organic compound that interacts with the enzyme, particularly preferably an aromatic compound, is additionally added in order to strengthen the activity of the relevant oxidoreductase (enhancer) or, in the case of greatly different redox potentials, to ensure the flow of electrons between the oxidase and the pollutant (mediator). In particular, during storage, proteins and / or enzymes can be protected from damage, such as inactivation, denaturation or decomposition caused by, for example, physical influences, oxidation or proteolytic cleavage. When proteins and / or enzymes are obtained by microorganisms, it is particularly preferred to inhibit proteolysis, in particular if the agent also contains a protease. For this purpose, the cleaning agent can contain a stabilizer; the provision of such an agent constitutes a preferred embodiment of the present invention.

[0074] Cleaning active proteases and amylases are generally not prepared in the form of pure proteins, but in the form of stable, storable and transportable preparations. These ready-to-use preparations include solid preparations obtained, for example, by granulation, extrusion or freeze drying, or, especially in the case of liquid or gel preparations which are advantageously maximally concentrated, have a low water content and / or are supplemented with stabilizers or other auxiliaries.

[0075] Alternatively, for at least one gel phase, preferably a solid gel phase, the enzyme can also be encapsulated, for example, by spray drying or extruding an enzyme solution together with preferably a natural polymer, or in the form of a capsule, for example, wherein the enzyme is enclosed in those capsules in the solidified gel, or wherein the enzyme-containing core is coated with a core-shell type protective layer impermeable to water, air and / or chemical substances. Other active ingredients such as stabilizers, emulsifiers, pigments, bleaching agents or dyes can be applied with a covering layer in addition. Use methods known per se, for example, by shaking or rolling granulation or in a fluidized bed process, applying such capsules. Advantageously, such particles, for example, have little dust due to the application of polymer film formers, and are stable in storage due to coating.

[0076] Furthermore, two or more enzymes can be formulated together so that a single particle exhibits multiple enzyme activities.

[0077] As is clear from the foregoing, enzyme proteins constitute only a small part of the total weight of conventional enzyme preparations. The protease and amylase preparations used according to the invention contain 1 to 40% by weight, preferably 2 to 30% by weight, particularly preferably 3 to 25% by weight of enzyme proteins. In particular, those cleaning agents which contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight, and in particular 0.5 to 8% by weight of the corresponding enzyme preparation, based on the total weight of the cleaning agent, are preferred.

[0078] A gel-like phase, also referred to below as a gel phase, is understood according to the invention to mean a composition / phase having an internal structured network. This internal structured (spatial) network is formed by a solid but distributed substance having long or highly branched particles and / or a gelling agent dispersed in at least one liquid, the at least one liquid being liquid at 20° C. This gel phase is thermoreversible.

[0079] This gel phase can be, for example, flowable or dimensionally stable. However, according to the present invention, the gel phase is preferably dimensionally stable at room temperature. In the preparation process, the preferred xanthan gum, gelatin or polyvinyl alcohol and / or its derivatives of the gelling agent are contacted with a solvent, the preferred organic solvent of the solvent, preferably one or more polyols. This makes it possible to obtain a flowable mixture, which can be molded into a shape as required. After a period of time, it is obtained to keep a given form, i.e. a dimensionally stable gel phase. This time period (setting time) is preferably 15 minutes or shorter, more preferably 10 minutes or shorter, particularly preferably 5 minutes or shorter. In this case, at least one gel phase yields to pressure, but does not deform, but returns to its initial state after the pressure has stopped. At least one gel phase is preferably elastic, particularly linear elastic.

[0080] At least one gel phase is preferably a shaped body. A shaped body is a unitary body that stabilizes itself in the shape given to it. Such a dimensionally stable body is formed from a molding compound (e.g., a composition) in such a way that the molding compound is intentionally formed into a predetermined shape, for example by pouring a liquid composition into a casting mold and then solidifying the liquid composition, for example as part of a sol-gel process.

[0081] Certain minimum requirements apply to the formulation of at least one gel phase. As mentioned previously, the gel phase must harden in the shortest possible time. Long hardening times will lead to long production times and therefore high costs. According to the invention, the hardening time means the period of time during which at least one gel phase changes from a flowable state to a dimensionally stable state which is non-flowable at room temperature during the production process. Room temperature is to be understood as a temperature of 20°C.

[0082] At least one gel phase is preferably a solid gel phase. It is therefore sliceable. For example, it can be cut with a knife after it solidifies without being destroyed after cutting.

[0083] At least one gel phase is also preferably translucent or transparent, as a result of which a good visual impression is achieved. Preferably, the transmittance of the gel phase (without dye) is in the range of 100% to 20%, 100% to 30%, in particular 100% to 40%. To measure the light transmittance (transmittance), the transmittance (patency) is determined in % at 600 nm at 20° C. against water as a reference. For this purpose, the mass is poured into a specified 11 mm round cuvette and, after a storage period of 12 hours at room temperature, measured in a Lange LICO 300 color measurement system.

[0084] At least one gel phase is low in water. Within the meaning of the present invention, low in water means that small amounts of water can be used to prepare at least one gel phase. The proportion of water in the gel phase is in particular 20% by weight or less, preferably 15% by weight or less, in particular 12% by weight or less, in particular 10 to 5% by weight. The amounts in % by weight are based on the total weight of the gel phase. This has the advantage that small amounts of water in combination with PVOH can have a structure-forming effect or a gel-forming effect.

[0085] According to a preferred embodiment, at least one gel phase is substantially free of water. This means that the gel phase is preferably substantially free of water. In this case, "substantially free" means that the gel phase may contain a small amount of water. For example, this water can be introduced into the phase by means of a solvent or as a result of crystallization water or as components of the phase reacting with each other. However, it is preferred to use only a small amount of water, and in particular no water is used as a solvent for preparing the gel phase. The proportion of water in the gel phase in this embodiment is 4.9% by weight or less, 4% by weight or less, preferably 2% by weight or less, in particular 1% by weight or less, in particular 0.5% by weight or less, in particular 0.1% by weight or 0.05% by weight or less. In this case, the amount in % by weight is based on the total weight of the gel phase.

[0086] By studying the following detailed description and claims, these and other aspects, features and advantages of the present invention will become apparent to those skilled in the art. Any feature from one aspect of the present invention may be used for any other aspect of the present invention. In addition, it is readily understood that the examples contained herein are intended to describe and illustrate rather than limit the present invention, and in particular, the present invention is not limited to these examples. Unless otherwise indicated, all percentages are indicated by weight %. Numerical ranges indicated in the format "from x to y" also include the stated values. If several preferred numerical ranges are indicated in this format, it is readily understood that all ranges resulting from combinations of various endpoints are also included.

[0087] As used herein, "at least one" means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With regard to an ingredient, the expression refers to the type of ingredient, not the absolute number of molecules. "At least one bleach catalyst" thus means, for example, at least one type of bleach catalyst - i.e. one type of bleach catalyst or a mixture of multiple different bleach catalysts can be used. Together with the weight specification, the expression relates to all compounds of the indicated type contained in the composition / mixture, i.e. the composition does not contain any other compound of this type beyond the indicated amount of the corresponding compound.

[0088] When referring to molar masses in this text, unless explicitly stated otherwise, this information always refers to the number-average molar mass M.n The number-average molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 using THF as eluent. w GPC can also be used, such as for M n Describe the determination.

[0089] Unless expressly stated otherwise, all percentages cited in connection with the compositions described herein relate to % by weight, in each case relative to the relevant mixture or phase.

[0090] Furthermore, the gel phase must be storage-stable under normal storage conditions. The gel phase according to the invention is a component of a cleaning agent. Cleaning agents are usually stored for a period of time in the home. They are usually stored near a washing machine or a dishwasher. For such storage, the gel phase should be stable. Thus, the gel phase should be stable at temperatures of up to 40° C., in particular at 30° C., in particular at 25° C. or 20° C., in particular after a storage period of 4 to 12 weeks, in particular 10 to 12 weeks or more, and should not deform or otherwise change consistency during this time.

[0091] If the gel phase and the solid phase, in particular the powder phase, are present in direct contact with one another, the gel phase preferably penetrates by at most 1 mm into the interstices of the underlying powder phase during a storage period of 4 weeks at 25°C.

[0092] Volume changes or shrinkage during storage would be disadvantageous since this would reduce consumer acceptance of the product. Leakage of liquid or components that seep out of the gel phase is also undesirable. Here, on the one hand, the visual impression is also relevant. The stability of the gel phase can be affected by leakage of liquids, such as solvents, so that the components are no longer stably contained and as a result the washing or cleaning effect can also be affected.

[0093] According to a preferred embodiment, the cleaning agent according to the invention, preferably a dishwasher detergent, in particular an automatic dishwasher detergent, contains a gelling agent in the gel phase, which is preferably selected from gelatin, xanthan gum and / or polyvinyl alcohol, in particular gelatin or polyvinyl alcohol, particularly preferably polyvinyl alcohol, in an amount of 4 to 40% by weight, in particular 6 to 30% by weight, particularly preferably in an amount of 7 to 24% by weight, more particularly preferably 8 to 22% by weight, in particular for example 14 to 20% by weight, in each case based on the total weight of the gel phase.

[0094] According to the invention, at least one gel phase particularly preferably comprises PVOH (polyvinyl alcohol) and / or its derivatives. Polyvinyl alcohol is a thermoplastic material which is usually produced as a white to pale yellow powder by hydrolysis of polyvinyl acetate. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohol having a molar mass of 30,000 to 60,000 g / mol is preferred. Within the meaning of the present invention, derivatives of PVOH are preferably copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers. Suitable anionic monomers are preferably vinylacetic acid, alkyl acrylates, maleic acid and its derivatives, in particular monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, fumaric acid and its derivatives, in particular monoalkyl fumarate (in particular monomethyl fumarate), dialkyl fumarate (in particular dimethyl fumarate), fumaric anhydride, itaconic acid and its derivatives, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and its derivatives, monoalkyl citraconic acid esters (especially methyl citraconic acid), dialkyl citraconic acid esters (dimethyl citraconic acid), citraconic anhydride, mesaconic acid (methyl fumaric acid) and its derivatives, monoalkyl mesaconic acid esters, dialkyl mesaconic acid esters, mesaconic anhydride, glutaconic acid and its derivatives, monoalkyl glutaconic acid esters, dialkyl glutaconic acid esters, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, vinyl sulfonic acid, 2-acrylamide-1-methylpropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate and combinations thereof, and alkali metal salts or esters of the monomers mentioned above.

[0095] Particularly preferred PVOH derivatives are those selected from copolymers of polyvinyl alcohol and monomers, the monomers being particularly selected from monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride and combinations thereof, and alkali metal salts or esters of the above monomers. The values ​​stated for the polyvinyl alcohol itself apply to suitable molecular masses. In the context of the present invention, preferably at least one gel phase comprises polyvinyl alcohol and / or its derivatives, preferably polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol %, in particular 80 to 90 mol %, particularly preferably 81 to 89 mol %, and even more preferably 82 to 88 mol %.

[0096] Particularly preferred polyvinyl alcohols are those which are present as white to pale yellow powders or granules, have a degree of polymerization in the range of about 100 to 2,500 (molar mass of about 4,000 to 100,000 g / mol) and a degree of hydrolysis of 80 to 99 mol %, preferably 85 to 90 mol %, in particular 87 to 89 mol %, for example 88 mol %, which accordingly also contain residual contents of acetyl groups.

[0097] PVOH powders having the above-mentioned properties and suitable for use in at least one gel phase are manufactured by Kuraray, for example, under the name or For example, from Kuraray AQ4104 is also suitable. Particularly suitable is Mowiol C30 from Kuraray, grades, in particular grades 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, very particularly preferably Poval 4-88S2, and 4-88.

[0098] The water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Particularly preferably and due to its significantly good solubility in cold water, particularly advantageous polyvinyl alcohols have been produced which can be acetalized or ketalized with aldehyde or ketone groups of sugars or polysaccharides or mixtures thereof. It is extremely advantageous to use the reaction product of polyvinyl alcohol and starch. In addition, by complexing with Ni or Cu salts, or by treating with dichromates, boric acid or borax, the water solubility can be changed and thus set to the desired value in a targeted manner.

[0099] According to a preferred embodiment, at least one or more enzymes are introduced into the gel phase, particularly into the gel phase with a gel forming agent, rather than as a liquid enzyme preparation. It is particularly preferred that the liquid enzyme preparation is not introduced into the gel phase, in which the gel forming agent is selected from gelatin, xanthan gum and / or polyvinyl alcohol, particularly gelatin or polyvinyl alcohol, particularly preferably polyvinyl alcohol. The liquid enzyme preparation is introduced into the gel phase still heated by the production process (particularly in the production of the PVOH gel phase containing high temperature therein) causing the stability of the enzyme in the liquid enzyme preparation to be greatly reduced. The reduction of stability particularly means that the activity of the enzyme is significantly reduced compared with the initial preparation. The reduction of this stability can be, for example, by determining the residual enzyme activity, or by comparing the cleaning performance of the corresponding enzyme, particularly according to the IKW standard, measured. Enzyme is particularly preferably incorporated into the gel phase as particles.

[0100] Surprisingly, PVOH has proven to be particularly suitable for preparing a gel phase that meets the above requirements. Therefore, at least one gel phase having PVOH and at least one polyol in addition to at least one enzyme, in particular at least one enzyme granule, preferably selected from proteases and / or amylases, is particularly preferred. Particularly preferably, at least one gel phase, at least one amylase granule and / or at least one protease granule comprises PVOH and at least one polyol.

[0101] According to the invention, at least one gel phase comprises at least one enzyme, preferably at least one enzyme granules, preferably at least one amylase granules and / or at least one protease granules, in particular at least one protease granules, PVOH and / or its derivatives in a proportion of about 4% to 40% by weight, in particular 6% to 30% by weight, preferably 7 to 24% by weight, particularly preferably 8% to 22% by weight. Significantly lower proportions of PVOH do not lead to the formation of a stable gel phase. These values ​​are in each case based on the total weight of the gel phase.

[0102] According to a particularly preferred embodiment, at least one gel phase comprises PVOH (polyvinyl alcohol). These gel phases prepared in this way are particularly high melting point, dimensionally stable (even at 40° C.), and do not change shape during storage, or only do not change significantly. In particular, they are also less reactive with respect to direct negative interactions with the components of the granular mixture, especially the powder phase. PVOH can also produce low-water or water-free gel phases without difficulty. The use of PVOH as a polymer for at least one gel phase results in a low-viscosity melt at 110-120° C., which can therefore be processed particularly easily, and in particular the filling of the gel phase into a water-soluble wrapper can be carried out quickly and accurately without any adhesion or inaccurate metering of the amount. In addition, the gel phase adheres particularly well to the water-soluble wrapper, especially if it is also made of PVOH. This is also visually advantageous. Due to the rapid hardening of at least one gel phase comprising PVOH, the further processing of the gel phase can be carried out particularly quickly. In addition, the good solubility of the resulting gel phase is particularly conducive to the overall solubility of the detergent. In addition, a gel phase with such a short hardening time is advantageous because the at least one solid phase metered thereon and containing the granular mixture, in particular a powder, does not sink into the gel which has not yet completely solidified or is still too soft. This results in a less visually attractive detergent portion.

[0103] In the multiphase disposable parts according to the invention comprising at least one solid phase, it is particularly important that at least one second phase is dimensionally stable so that as few interactions as possible can occur between the solid phase and the gel phase. If at least one gel phase comprises gelatin plus PVOH, the toughness of the gel phase during the production process is surprisingly increased.

[0104] A further preferred object of the present invention relates to cleaning agents, preferably dishwasher detergents, in particular automatic dishwasher detergents, which, in addition to at least one enzyme, preferably at least one enzyme granulate, contain in the gel phase at least one organic solvent, in particular selected from 1,2-propylene glycol, 1,3-propylene glycol, glycerol, 1,1,1-trimethylolpropane, triethylene glycol, dipropylene glycol, polyethylene glycol and / or mixtures thereof.

[0105] At least one gel phase preferably comprises at least one polyol. In addition to the preparation of a flowable gel phase, at least one polyol also enables the preparation of a dimensionally stable, non-flowable gel phase within a short setting time of 15 minutes or less, in particular 10 minutes or less. Polyols within the meaning of the present invention are hydrocarbons in which two, three or more hydrogen atoms are replaced by OH groups. Each OH group is bonded to a different carbon atom. No carbon atom has two OH groups. This is in contrast to (simple) alcohols in which only one hydrogen atom in the hydrocarbon is replaced by an OH group. Polyols with two OH groups are called alkanediols, while polyols with three OH groups are called alkantriols. Polyols therefore correspond to the general formula [KW](OH) X , wherein KW represents that it is a linear or branched, saturated or unsaturated, substituted or unsubstituted hydrocarbon. For example, substitution can be carried out with -SH or -NH- groups. Preferably, KW is a linear or branched, saturated or unsaturated, unsubstituted hydrocarbon. KW contains at least two carbon atoms. The polyol contains 2, 3 or more OH groups (x=2, 3, 4, ...), wherein only one OH group is bonded to each C atom of KW. Particularly preferably, KW contains 2 to 10, i.e. 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Polyols in which x=2, 3 or 4 (for example, pentaerythritol in which x=4) can be used in particular. Preferably, x=2 (alkanediol) and / or x=3 (alkanediol).

[0106] Particularly preferably, at least one gel phase comprises as polyol at least one alkanetriol and / or at least one alkanediol, in particular at least one C 3 To C 10 Alkantriol and / or at least one C 3 To C 10 Alkanediol, preferably at least one C 3 To C 8 Alkantriol and / or at least one C 3 To C 8 Alkanediol, in particular at least one C 3 To C 6 Alkantriol and / or at least one C 3 To C 5 Preferably, it comprises as at least one polyol one alkanetriol and one alkanediol. In a preferred embodiment, at least one gel phase therefore comprises at least one polymer, in particular PVOH or PVOH with gelatin, and at least one alkanediol and at least one alkanetriol, in particular one alkanetriol and one alkanediol. Likewise preferred are gel phases comprising at least one polymer, PVOH or PVOH with gelatin, and C 3 To C 8 Alkanediol and C 3 To C8 The gel phase comprises at least one polymer, in particular PVOH or PVOH and gelatin, and C 3 To C 5 Alkanediol and C 3 To C 6 The gel phase of alkantriol is more preferred. According to the present invention, the polyol does not contain any derivatives thereof, such as ethers, esters, etc.

[0107] Surprisingly, it has been shown that particularly short setting times can be achieved when the corresponding triols (alkanetriols) are combined with the corresponding diols (alkanediols). In addition, the gel phase obtained is transparent and has a glossy surface, which provides an attractive visual impression for the cleaning agent according to the invention. The terms "diol" and "alkanediol" are used synonymously in this document. The same applies to "triols" and "alkanetriols".

[0108] According to a particularly preferred embodiment, the cleaning agents according to the invention, preferably dishwasher detergents, in particular automatic dishwasher detergents, contain at least one organic solvent in the gel phase in an amount of 30 to 90% by weight, in particular 40 to 85% by weight, more preferably 50 to 80% by weight, based on the total weight of the gel phase.

[0109] The amount of one or more polyols used in the gel phase according to the invention is preferably at least 45% by weight, in particular 55% by weight or more. The preferred amount range is 45% to 85% by weight, in particular 50% to 80% by weight, based on the total weight of the gel phase.

[0110] Preferably, C 3 To C 6 The alkanetriol is glycerol and / or 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (also known as 1,1,1-trimethylolpropane) and / or 2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS, trimethylolaminoethane) and / or 1,3,5-pentanetriol.

[0111] C 3 To C 6 The alkanetriol is particularly preferably glycerol and / or 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (also known as 1,1,1-trimethylolpropane). 3 To C 5The alkanediols are, for example, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,3-propylene glycol and / or 1,2-propylene glycol, preferably 1,3-propylene glycol and / or 1,2-propylene glycol. Surprisingly, it has been found that the chain length of the diols and, in particular, the position of the OH groups have an influence on the transparency of the gel phase. Therefore, the OH groups of the diols are preferably not arranged on adjacent C atoms. In particular, three or four carbon atoms, particularly preferably three carbon atoms, are positioned between the two OH groups of the diols. Particularly preferably, the diol is 1,3-propylene glycol. Surprisingly, it has been found that particularly good results are obtained with mixtures comprising glycerol and 1,3-propylene glycol and / or 1,2-propylene glycol, in particular glycerol and 1,3-propylene glycol.

[0112] According to the invention, polyethylene glycols with an average molar mass of 200 to 600 g / mol are preferably also used in at least one or more gel phases. In combination with polyvinyl alcohol, polyethylene glycols with an average molar mass of about 200 to about 600 g / mol, preferably 300 to 500 g / mol, in particular 350 to 450 g / mol, for example around 400 g / mol (INCI: PEG 400) are used. Thus, the detergent parts according to the invention are characterized in that they contain polyethylene glycols with an average molar mass of 300 to 500 g / mol, in particular 350 to 450 g / mol.

[0113] According to the invention, at least one gel phase comprises at least one enzyme, preferably at least one enzyme granules, preferably at least one amylase granules and / or at least one protease granules, in particular at least one protease granules, PVOH and / or a derivative thereof, preferably in a proportion of about 4% to 40% by weight, in particular 6% to 30% by weight, preferably 7 to 24% by weight, particularly preferably 8% to 22% by weight, and at least one polyol, optionally further polyethylene glycol having an average molecular mass of about 200 to 600 g / mol, in an amount of 5 to 30% by weight, preferably 8 to 26% by weight, in particular 10 to 22% by weight, based on the total weight of the at least one gel phase.

[0114] Surprisingly, it has been found that adding polyethylene glycol, particularly those polyethylene glycols having an average molar mass of 200 to 600 g / mole, to at least one gel phase, particularly a gel phase comprising polyvinyl alcohol, results in an acceleration of the setting time of the gel phase. Values ​​of several minutes and even less than one minute can be achieved. This is particularly highly advantageous for production sequences, since further processing of the gel phase in a hardened state can be carried out much faster, and therefore is generally more cost-effective. Surprisingly, it has been found that in combination with polyvinyl alcohol and / or its derivatives, the presence of polyethylene glycols having an average molar mass of 200 to 600 g / mole significantly contributes to reducing the setting time. Without being bound by theory, it is assumed that such polyethylene glycols, particularly those having a molar mass of 350 to 450 g / mole, particularly about 400 g / mole, increase the sol-gel temperature.

[0115] In a particularly preferred embodiment, the amount of polyethylene glycol having an average molar mass of 350 to 450 g / mol, for example about 400 g / mol, is 10 to 22% by weight, based on the total weight of the gel phase.

[0116] According to the invention, at least one gel phase comprises at least one enzyme, preferably at least one enzyme granules, preferably at least one amylase granules and / or at least one protease granules, in particular at least one protease granules, PVOH and / or derivatives thereof in a proportion of about 4% to 40% by weight, in particular 6% to 30% by weight, preferably 7 to 24% by weight, particularly preferably 8% to 22% by weight, polyethylene glycol with an average molar mass of 200 to 600 g / mol as polyol, and 1,3-propylene glycol and glycerol or 1,1,1-trimethylolpropane. Particularly preferred gel phases comprise gelatin or PVOH as polymers and 1,3-propylene glycol and glycerol or 1,1,1-trimethylolpropane as polyols. If the gel phase comprises an alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, based in each case on the total weight of the gel phase, the proportion of the alkanetriol, in particular glycerol or 1,1,1-trimethylolpropane, is 3 to 75% by weight, preferably 5 to 70% by weight, in particular 10 to 65% by weight, in particular 20 to 40% by weight, based on the total weight of the gel phase.

[0117] If the gel phase optionally comprises a plurality of alkantriols, the total proportion of the alkantriols is 3 to 75% by weight, preferably 5 to 70% by weight, in particular 10 to 65% by weight, in particular 20 to 40% by weight, based on the total weight of the gel phase.

[0118] If glycerol is contained as alkantriol in the gel phase, the proportion of glycerol is preferably 5 to 70% by weight, in particular 10 to 65% by weight, in particular 20 to 40% by weight, based on the total weight of the gel phase.

[0119] If 1,1,1-trimethylolpropane is contained in the gel phase, the proportion of 1,1,1-trimethylolpropane is preferably 5 to 70% by weight, in particular 10 to 65% by weight, particularly preferably 18 to 45% by weight, particularly preferably 20 to 40% by weight, based on the total weight of the gel phase.

[0120] If 2-amino-2-hydroxymethyl-1,3-propanediol is present in the gel phase, the proportion of 2-amino-2-hydroxymethyl-1,3-propanediol is preferably 5 to 70% by weight, in particular 10 to 65% by weight, in particular 20 to 40% by weight, based on the total weight of the gel phase.

[0121] If a plurality of alkanediols are optionally present in the gel phase, the proportion of the alkanediols is preferably 5% to 70% by weight, in particular 7% to 65% by weight, in particular 10% to 40% by weight, based on the total weight of the gel phase.

[0122] If the gel phase comprises, in addition to at least one enzyme, preferably at least one enzyme granule, preferably at least one amylase granule and / or at least one protease granule, in particular at least one subtilisin-containing protease granule, at least one alkanediol, in particular 1,3-propanediol or 1,2-propanediol, in each case based on the total weight of the gel phase, the proportion of the alkanediol, in particular 1,3-propanediol or 1,2-propanediol, is preferably 5% to 70% by weight, in particular 10% to 65% by weight, in particular 20% to 45% by weight, based on the total weight of the gel phase. If 1,3-propanediol is present in the gel phase, the proportion of 1,3-propanediol is in particular 10% to 65% by weight, in particular 20% to 45% by weight, based on the total weight of the gel phase.

[0123] Based on the total weight of the gel phase, a gel phase containing, in addition to at least one enzyme, preferably at least one enzyme granule, preferably at least one amylase granule and / or at least one protease granule, in particular at least one subtilisin-containing protease granule, 20 to 45% by weight of 1,3-propanediol and / or 1,2-propanediol and 10 to 65% by weight of 2-amino-2-hydroxymethyl-1,3-propanediol (in each case based on the total weight of the gel phase) is preferred. Also preferred are gel phases containing 20 to 45% by weight of 1,3-propanediol and / or 1,2-propanediol and 10 to 65% by weight of 1,1,1-trimethylolpropane (in each case based on the total weight of the gel phase). In particular, a gel phase containing 20 to 45% by weight of 1,3-propanediol and / or 1,2-propanediol and 10 to 65% by weight of glycerol (in each case based on the total weight of the gel phase) is preferred.

[0124] It has been found that within these ranges, rapid solidification of the gel phase is possible at 20° C. and results in a phase which is stable and transparent on storage. In particular, the glycerol proportion has an influence on the setting time.

[0125] If, in addition to at least one enzyme, preferably at least one enzyme granulate, preferably at least one amylase granulate and / or at least one subtilisin-containing protease granulate, in particular at least one subtilisin-containing protease granulate, the at least one gel phase according to the invention has C 3 To C 6 Alkanetriol and C 3 To C 5 In particular, when glycerol and 1,3-propylene glycol are present as polyols, the weight ratio is 2:1 to 1:1.5, preferably 1.5:1 to 1:1.2, preferably 1.3 to 1:1. Surprisingly, it has been found that using these weight ratios, a storage-stable, glossy, transparent gel phase can be obtained at 20° C. with a short setting time of 10 minutes or less. In combination with a polyethylene glycol having an average molar mass of 200 to 600 g / mol, the preferred weight ratios mentioned above, in particular a weight ratio of 1.5:1 to 1:1.2 (C 3 To C 6 Alkanetriol / C 3 To C 5 Alkanediol), allowing the setting time to be reduced to 5 minutes or less.

[0126] According to a further preferred embodiment, in addition to the alkanols mentioned above, triethylene glycol may also be present in at least one gel phase, in particular in the gel phase described as preferred above, especially if the phase contains PVOH and optionally present polyethylene glycol with an average molar mass of 200 to 600 g / mol. Triethylene glycol advantageously accelerates the hardening of the gel phase. It also causes the resulting gel phase to exchange very little (if any) liquid with the environment in an imperceptible manner. This particularly improves the visual impression of the resulting detergent portion. If, in each case, based on the total weight of the gel phase, in addition to at least one enzyme, preferably at least one enzyme granule, preferably at least one amylase granule and / or at least one protease granule, in particular at least one protease granule containing subtilisin, at least one gel phase also contains 1,3 and / or 1,2-propylene glycol, particularly preferably 1 to 3.5% by weight of 1,3-propylene glycol, and 0.1 to 20% by weight of glycerol, preferably 1 to 15% by weight, in particular 5 to 12% by weight, for example 8 to 11% by weight of triethylene glycol, then this is particularly preferred.

[0127] In addition, at least one gel phase preferably comprises another anionic polymer, particularly polycarboxylic acid ester. These can serve as builders and / or thickening polymers. According to the present invention, at least one gel phase can further comprise anionic polymers or copolymers with builder properties. This is preferably polycarboxylic acid ester. Copolymerized polyacrylates, preferably sulfopolymers, preferably copolymerized polysulfonates, preferably hydrophobically modified copolymerized polysulfonates, are preferably used as polycarboxylic acid esters. Copolymers can have two, three, four or more different monomer units. In addition to the sulfonic acid-containing monomers, preferred copolymerized polysulfonates also contain at least one monomer from the unsaturated carboxylic acid group.

[0128] According to a particularly preferred embodiment, the low hydrogel phase contains a polymer which comprises at least one monomer containing sulfonic acid groups.

[0129] As the unsaturated carboxylic acid, it is particularly preferred to use 1 (R 2 )C=C(R 3 )COOH unsaturated carboxylic acid, wherein R 1 To R 3 Independently represent -H, -CH 3 , a linear or branched saturated alkyl functional group having 2 to 12 carbon atoms, a linear or branched monounsaturated or polyunsaturated alkenyl functional group having 2 to 12 carbon atoms, an alkyl or alkenyl functional group as defined above substituted with -NH2, -OH or -COOH-, or represents -COOH or -COOR 4 , where R 4 It is a saturated or unsaturated, linear or branched hydrocarbon functional group having 1 to 12 carbon atoms.

[0130] Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, unsaturated dicarboxylic acids can also be used.

[0131] For monomers containing sulfonic acid groups, the formula R 5 (R 6 )C=C(R 7 )-X-SO 3 Those monomers of H are preferred, wherein R 5 To R 7 Independently represent -H, -CH 3 , a linear or branched saturated alkyl functional group having 2 to 12 carbon atoms, a linear or branched monounsaturated or polyunsaturated alkenyl functional group having 2 to 12 carbon atoms, -NH 2 , -OH or -COOH-substituted alkyl or alkenyl functional groups, or represents -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, linear or branched hydrocarbon functional group having 1 to 12 carbon atoms, and X represents an optional spacer group selected from -(CH 2 ) n -, wherein k = 1 to 6 -COO-(CH 2 ) k -、-C(O)-NH-C(CH 3 ) 2 -、-C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 2 CH 3 )-CH 2 -.

[0132] Among these monomers, 2 C=CH-X-SO 3 H.H 2 C=C(CH 3 )-X-SO 3 H or HO 3 SX-(R 6 )C=C(R 7 )-X-SO 3 Those monomers of H are preferred, wherein R 6 and R 7 are independently selected from -H, -CH3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 and -CH(CH 3 ) 2 , and X represents an optional spacer group selected from -(CH 2 ) n -, wherein k = 1 to 6 -COO-(CH 2 ) k -、-C(O)-NH-C(CH 3 ) 2 -、-C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.

[0133] According to a particularly preferred embodiment, the gel phase comprises a polymer which comprises acrylamidopropanesulfonic acid, methacrylamidomethylpropanesulfonic acid or acrylamidomethylpropanesulfonic acid as monomer containing sulfonic acid groups.

[0134] Particularly preferred monomers containing sulfonic acid groups are 1-acrylamide-1-propanesulfonic acid, 2-acrylamide-2-propanesulfonic acid, 2-acrylamide-2-methyl-1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, 3-methacrylamide-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and mixtures of the above acids or their water-soluble salts. The sulfonic acid groups may be present in the polymer in completely or partially neutralized form, i.e. the acidic hydrogen atoms of the sulfonic acid groups may be replaced by metal ions, preferably alkali metal ions, and in particular sodium ions in some or all of the sulfonic acid groups. The use of partially or completely neutralized sulfonic acid group-containing copolymers is preferred according to the invention.

[0135] In copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, the monomer distribution of the copolymers preferably used according to the invention is preferably in each case 5 to 95% by weight; particularly preferably, the proportion of monomers containing sulfonic acid groups is 50 to 90% by weight and the proportion of monomers containing carboxylic acid groups is 10 to 50% by weight, wherein the monomers are preferably selected from the monomers mentioned above. The molar mass of the sulfonic copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred cleaning agents are characterized in that the copolymers have a molecular weight of 2,000 to 200,000 gmol -1 , preferably 4,000 to 25,000 gmol -1 , and particularly 5,000 to 15,000 gmol -1 The molar mass of .

[0136] In another preferred embodiment, the copolymer contains not only carboxyl-containing monomers and sulfonic acid-containing monomers, but also at least one nonionic, preferably hydrophobic monomer. In particular, the rinse performance of the dishwasher detergents according to the invention can be improved by the use of these hydrophobically modified polymers.

[0137] Particularly preferably, at least one gel phase further comprises an anionic copolymer comprising a copolymer of:

[0138] i) Monomers containing carboxylic acid groups

[0139] ii) Sulfonic acid group-containing monomer

[0140] iii) Used as nonionic monomers, especially hydrophobic monomers, for anionic copolymers.

[0141] As nonionic monomers, preferably used are 1 (R 2 )C=C(R 3 )-XR 4 The monomers, R 1 To R 3 Independently represent -H, -CH 3 or -C 2 H 5 , X represents a group selected from -CH 2 -, -C(O)O- and -C(O)-NH-, and R 4 represents a straight-chain or branched, saturated alkyl function having 2 to 22 carbon atoms, or an unsaturated, preferably aromatic, function having 6 to 22 carbon atoms.

[0142] Particularly preferred nonionic monomers are butene, isobutylene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexene, 1-octene, α-olefins having 10 or more carbon atoms (e.g., 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C 6-olefins). 22 α-olefins), 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N-(meth)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N-(2-ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, N-(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, N-(lauryl)acrylamide, octadecyl acrylate, octadecyl methacrylate, N-(stearoyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

[0143] Surprisingly, it has also been found that PVOH and / or its derivatives together with anionic polymers or copolymers, particularly copolymers containing sulfonic acid groups, lead to the formation of a gel phase with an insensitive surface. Such surfaces can be touched by the final consumer without material adhering to their hands. No corrosion of the material occurs in the packaging either. Therefore, in addition to at least one enzyme, preferably at least one enzyme granule, the gel phase preferably also comprises PVOH, polyethylene glycol with an average molar mass of 200 to 600 g / mol, at least one polyol and anionic copolymer / polymer. Based on the gross weight of the gel phase, the proportion of anionic polymers is preferably 1 wt % to 35 wt %, particularly 3 wt % to 30 wt %, particularly 4 wt % to 25 wt %, preferably 5 wt % to 20 wt %, for example 10 wt %. In addition to the monomer containing sulfonic acid groups, at least one monomer from the unsaturated carboxylic acid group, particularly acrylic acid sulfonic polymers, particularly preferred copolymerized polysulfonates, also provide excellent gloss on the surface. More importantly, fingerprints will not be left. Thus, the proportion of sulfopolymers, in particular sulfopolymers containing not only sulfonic acid group-containing monomers but also at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, in particular said sulfopolymers with AMPS as sulfonic acid group-containing monomers, such as Acusol 590, Acusol 588 or Sokalan CP50, based on the weight of the gel phase, is preferably from 1% to 25% by weight, in particular from 3% to 18% by weight, in particular from 4% to 15% by weight, preferably from 5% to 12% by weight. In a particularly preferred embodiment, at least one gel phase therefore comprises PVOH and sulfopolymers, in particular preferably copolymerized polysulfonates containing not only sulfonic acid group-containing monomers but also at least one monomer from the group of unsaturated carboxylic acids, in particular acrylic acid, and at least one polyol, in addition to at least one enzyme, preferably at least one enzyme granulate, preferably at least one amylase granulate and / or at least one protease granulate, in particular at least one subtilisin-containing protease granulate.

[0144] According to another embodiment, in addition to the polyethylene glycol having an average molar mass of 200 to 600 g / mol, further polyalkylene glycols (in particular further polyethylene glycols) having an average molar mass of about 800 to 8,000 may be contained in at least one gel phase. The polyethylene glycols mentioned above are particularly preferably used in an amount of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 15 to 25% by weight, preferably in each case based on the total weight of the gel phase.

[0145] A particularly preferred embodiment of the present invention comprises, in addition to at least one enzyme, preferably at least one enzyme granule, preferably at least one amylase granule and / or at least one protease granule, in particular at least one subtilisin-containing protease granule, as at least one gel phase (in each case based on the total weight of the gel phase), 8 to 22% by weight of PVOH, 15 to 40% by weight of 1,3-propylene glycol, 20 to 40% by weight of glycerol, 5-15% by weight of a polyacrylate copolymer containing sulfonic acid groups and 8 to 22% by weight, in particular 10 to 20% by weight of polyethylene glycol with an average molar mass of 200 to 600 g / mol, optionally 2 to 10% by weight of 1,2-propylene glycol and optionally 2 to 15% by weight of triethylene glycol, in each case based on the total weight of the gel phase.

[0146] According to another particularly preferred embodiment, the cleaning agent, preferably a dishwasher detergent, in particular an automatic dishwasher detergent, is a cleaning agent portion in a water-soluble package having one or more chambers / compartments. The cleaning agent is preferably packaged as a separate cleaning agent portion so that it is used to perform a dishwasher cycle and is (as far as possible) substantially consumed in the process.

[0147] The water-soluble wrapper is preferably made of a water-soluble film material selected from a polymer or a polymer mixture. The wrapper can be made of one layer or two or more layers of water-soluble film material. The water-soluble film material of the first layer and the additional layer (if present) can be the same or different.

[0148] Preferably the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. The water-soluble coating containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibits good stability accompanied by a sufficiently high level of water solubility, especially cold water solubility.

[0149] Suitable water-soluble films for producing water-soluble wrappings are preferably based on polyvinyl alcohol or polyvinyl alcohol copolymers having a molecular weight of between 10,000 and 1,000,000 gmol. -1 , preferably 20,000 to 500,000 gmol -1 , particularly preferably 30,000 to 100,000 gmol -1 , and particularly 40,000 to 80,000 gmol -1 within the range.

[0150] Polyvinyl alcohol is usually prepared by hydrolysis of polyvinyl acetate, since a direct synthetic route is not possible. The same applies to polyvinyl alcohol copolymers, which are correspondingly prepared from polyvinyl acetate copolymers. Preferably, at least one layer of the water-soluble coating comprises polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.

[0151] In a preferred embodiment, the water-soluble package consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight of polyvinyl alcohol having a degree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.

[0152] In addition, a polymer selected from (co)polymers containing (meth) acrylic acid, polyacrylamide, oxazoline polymers, polystyrene sulfonate, polyurethane, polyester, polyether, polylactic acid or a mixture of said polymers can be added to the film material containing polyvinyl alcohol, which is suitable for producing a water-soluble wrap. Polylactic acid is a preferred additional polymer.

[0153] Preferred polyvinyl alcohol copolymers also comprise dicarboxylic acids as further monomers in addition to vinyl alcohol. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred. Polyvinyl alcohol copolymers which, in addition to vinyl alcohol, also comprise ethylenically unsaturated carboxylic acids or salts or esters thereof are also preferred. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters or mixtures thereof.

[0154] The film material may preferably contain further additives. The film material may contain a plasticizer, such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerine, sorbitol, mannitol or a mixture thereof. Further additives include, for example, a demoulding aid, a filler, a cross-linking agent, a surfactant, an antioxidant, a UV absorber, an anti-caking agent, an anti-adhesive agent or a mixture thereof.

[0155] Suitable water-soluble films for use in the water-soluble wrapping of water-soluble packaging according to the present invention are films sold by MonoSol LLC, for example, under the names M8720, M8630, M8312, M8440, M7062, C8400 or M8900. Films sold by Nippon Gohsei under the names SH2601, SH2504, SH2707 or SH2701 are also suitable. Other suitable films include those sold under the names SH2601, SH2504, SH2707 or SH2701 from Aicello Chemical Europe GmbH. PT, GA, KC or membrane from KL, or VF-HP membrane from Kuraray.

[0156] The water-soluble coating preferably at least partially has a bittern with a bitterness value of 1,000 to 200,000, in particular those bitterns selected from quinine sulfate (bitterness value = 10,000), naringin (bitterness value = 10,000), sucrose octaacetate (bitterness value = 100,000), quinine hydrochloride and mixtures thereof. In particular, the outer surface of the water-soluble coating is at least partially coated with a bittern with a bitterness value of 1,000 to 200,000. In this regard, it is particularly preferred that the water-soluble coating is coated at least 50%, preferably at least 75%, and very particularly preferably at least 90% with a bittern with a bitterness value of 1,000 to 200,000. The application of the bittern with a bitterness value of 1,000 to 200,000 can be carried out, for example, by means of printing, spraying or painting.

[0157] According to the invention, the water-soluble wrapper has at least one continuous peripheral sealing seam which is substantially located in one plane. From a process point of view, this is advantageous because for the peripheral sealing seam which is substantially located in one plane, only a single sealing step is required, which may only use a single sealing tool. Compared with those wrappers with multiple sealing seams, the continuous circumferential sealing seam leads to a better closure and to an excellent sealing of the sealing seam and therefore the wrapper itself. Leakage of the product out of the wrapper, for example onto the surface of the part, would be harmful because the consumer would then come into contact with the product. Specifically, this situation should be avoided as much as possible for the detergent part comprising the water-soluble wrapper.

[0158] The water-soluble wrapper can preferably be produced from at least two packaging parts. Preferably, at least two packaging parts are water-soluble so that no packaging part remains in the dishwasher, which can subsequently cause problems in the dishwasher. At least two packaging parts do not have to be different. These can preferably be produced from the same material and in the same manner. In a preferred embodiment, they are two parts of a water-soluble film, in particular two parts of a water-soluble film with the same composition.

[0159] In another embodiment, at least two packaging parts can be made of different materials, for example, by different films or by materials with two different properties (for example, films soluble in hot and cold water). In this embodiment, preferably a water-soluble film is combined with another packaging part prepared by injection molding.

[0160] According to a particularly preferred embodiment of the present invention, the water-soluble wrapper comprises at least one at least partially plastically deformed film. In particular, this plastic deformation of the film can be produced by methods known to those skilled in the art, such as thermoforming (with and without the application of vacuum), blow molding or stamping. In particular, the water-soluble wrapper comprises at least one at least partially plastically deformed film that has been produced by thermoforming.

[0161] At least one solid phase and at least one gel phase can be arranged in the water-soluble wrapper in any combination with each other. Therefore, the solid phase can be arranged on or beside the gel phase. In this embodiment, the cleaning agent according to the present invention comprises a solid phase and a gel phase. It is also conceivable that the solid phase is surrounded by the gel phase. It is also contemplated that one phase is embedded in another phase according to the present invention. In a further particularly preferred arrangement, the gel phase takes a cast form, such as the form of a gel core, and is surrounded by a solid phase. There can also be two or more cavities separated from each other, which are filled with at least one gel phase. In this embodiment, the cleaning agent particularly comprises two gel phases, and it is possible that the two gel phases have different compositions.

[0162] According to a preferred embodiment, there are three, four, five or six or more cavities separated from each other, which are filled with one or more gel phases. Preferably, such a cleaning agent comprises three, four, five or six or more gel phases, it being possible that the gel phases have the same or different compositions.

[0163] A preferred object of the present invention relates to cleaning agents, preferably dishwasher detergents, in particular automatic dishwasher detergents, which additionally comprise at least one solid phase, in particular a particulate phase and optionally at least one further liquid / gel phase or solid phase.

[0164] "Solid" in this context means that the composition takes a solid form under standard conditions (temperature 25°C, pressure 1013 mbar). Suitable solid phases are particularly granular mixtures of solid compositions, such as powders and / or granules, particularly powder phases. According to the present invention, solid compositions / phases having increased dimensional stability compared to loose granular mixtures (especially powders), for example, by the restoring force of the film after thermoforming, such as powder or granular preparations that have been compacted by compression before or after introduction into the film, or directly compressed compositions, such as compressed products or tablets, are also suitable. This at least one solid phase can be in direct contact with the gel phase. According to the present invention, detergent parts, particularly multi-chamber bags, are also used, in which the solid phase and the gel phase are spatially close to each other but separated from each other. The two chambers can be separated, for example, by a film, particularly a water-soluble film, or by a sealed seam (preferably a sealed seam of 3 mm or less). According to the present invention, the chambers of the multi-chamber bag are therefore above each other and beside each other. In addition, mixtures of single-chamber or multi-chamber bags comprising a gel phase according to the invention and at least one solid phase separated therefrom, which are arranged in contact, for example by folding and fixing the bags, or by storing at a distance of less than 3 mm in, for example, a packaging bag or a device for portioning.

[0165] Within the meaning of the present invention, a powder phase is to be understood as a granular mixture. According to the present invention, the term powder phase encompasses powders and / or granules according to this definition.

[0166] Within the meaning of the present invention, a granular mixture is formed from a plurality of loose solid particles, which in turn comprise so-called grains.

[0167] Fine particles are the name for the particulate components of powders (fine particles are loose solid particles), dusts (fine particles are loose solid particles), granules (loose solid particles are agglomerates of several fine particles) and other granular mixtures.

[0168] A preferred embodiment of the particulate mixture of the solid phase composition is a powder and / or granules; when referring to "powder" or "granules", this also includes mixtures of different powders or different granules. Accordingly, powders and granules are also intended to mean mixtures of different powders with different granules. The solid particles of the particulate mixture in turn preferably have a particle size X of 10 to 1,500 μm, more preferably 200 μm to 1,200 μm, particularly preferably 600 μm to 1,100 μm. 50.3(volume average). The particle size can be determined by sieving or by means of a Camsizer particle size analyzer from the company Retsch. The granular mixture of the solid composition of the invention serving as the solid phase is preferably presented in a free-flowing form, in particular as a free-flowing powder and / or free-flowing granules. Thus, the average of the portions according to the invention comprises at least one solid phase, in particular a powder, of the free-flowing granular mixture of the solid composition, and at least one gel phase as previously defined.

[0169] A particularly preferred object of the present invention relates to detergents, in particular detergent fractions, in which a gel phase is in direct contact, for example in a chamber containing at least one solid phase.

[0170] Furthermore, it is preferred that at least one solid phase and at least one gel phase are in direct contact with one another. In this case, there should be essentially no interaction, in particular no negative interaction, between the solid phase and the gel phase. Essentially no negative interaction means in particular that essentially no components or solvents (less than 20% by weight, preferably less than 10% by weight, in particular less than 5% by weight) pass from one phase into the other, or that the stability, in particular the storage stability, preferably the stability at a storage temperature of 4 weeks and 30° C., in particular the cleaning performance after such storage, decreases by less than 30%, preferably less than 20%, in particular less than 10% after such storage, and / or the aesthetics of the product is not impaired in a noticeable manner, for example by color changes, the formation of wet edges, fuzzy boundaries between the two phases, etc. For example, the absence of negative interactions here means that no components or solvents pass from one phase into the other, or that the stability, in particular the storage stability, preferably the stability at a storage temperature of 4 weeks and 30° C., in particular with regard to the cleaning performance, and / or the aesthetics of the product is not impaired in any way, for example by color changes, the formation of wet edges, fuzzy boundaries between the two phases, etc.

[0171] Surprisingly, it has been shown that this object can be achieved by formulating a gel phase, preferably a dimensionally stable gel phase, in combination with a granular mixture of a solid composition, in particular a powder phase, the gel phase comprising at least one enzyme, preferably at least one enzyme granule, preferably at least one amylase granule and / or at least one protease granule, in particular at least one protease granule containing subtilisin. It is particularly suitable that the granular mixture of the solid composition, in particular the powder phase is free-flowing, because due to this process, the water-soluble inclusions can be filled in a more targeted manner, in particular when filling the cavities produced by thermoforming. In addition, the visual appearance of the granular mixture of the solid composition, in particular the powder, can be better modified compared to compressed tablets; in particular, texture differences, such as coarse and fine particles and particles or regions with different colors - intact or as colored spots - can be used to improve the visually pleasing appearance. In addition, the granular mixture of the solid composition, in particular the powder, also provides improved solubility compared to compressed tablets, even without the addition of disintegrants.

[0172] Within the meaning of the present invention, a phase is a spatial region in which physical parameters and chemical composition are uniform. One phase is different from another phase by its different characteristics, such as composition, physical properties, appearance, etc. Preferably, different phases can be visually distinguished from each other. At least one solid phase can therefore be clearly distinguished from at least one gel phase by consumers. If the cleaning agent according to the present invention has more than one solid phase, the phases can also be distinguished from each other by the naked eye, for example, due to their different colors. If there are two or more gel phases, the same applies. In this case, for example, based on differences in color or transparency, visual distinction of the phases is also possible. Within the meaning of the present invention, phases are therefore independent regions that can be visually distinguished from each other by the naked eye by consumers. Each phase can have different properties when used, such as the speed at which the phase dissolves in water and the release rate and order of the components contained in the specific phase.

[0173] At least one solid phase of the invention comprises a granular mixture of a solid composition; in particular, it is powdery and free-flowing. Thus, the cleaning agent according to the invention comprises at least one solid powdery and free-flowing phase, and at least one gel phase comprising at least one enzyme, preferably at least one enzyme granule, preferably at least one amylase granule and / or at least one protease granule, in particular at least one subtilisin-containing protease granule, and as a gelling agent at least one polyvinyl alcohol, which comprises at least PVOH and / or a derivative thereof, particularly preferably at least PVOH, and at least one polyol.

[0174] The free-flowing capacity of a granular mixture, in particular a powdered solid, a powder phase, preferably a powder and / or granules, relates to its ability to flow freely under its own weight. The free-flowing capacity is determined by the outflow time of 1,000 ml of detergent powder leaving a standardized flow test funnel, which is initially closed in its discharge direction and has an outlet with a diameter of 16.5 mm, by measuring the time for the granular mixture, in particular a powder phase, preferably a powder and / or granules, such as a powder, to completely flow out after opening the outlet, and comparing it with the outflow rate (in seconds) of a standard test sand whose outflow rate is defined as 100%. The defined sand mixture used for calibrating the flow instrument is dry sea sand. For example, sea sand with a particle size of 0.4 to 0.8 mm, which can be obtained from Carl Roth, Germany, CAS number [14808-60-7], is used. For drying, the sea sand is dried on a plate with a maximum layer height of 2 cm in a drying cabinet at 60° C. for 24 hours before measurement.

[0175] Preferred embodiments of the solid phase according to the invention have an angle of repose / tilt of 26 to 35, 27 to 34, 28 to 33, determined according to the method mentioned below after 24 hours after preparation of the granular mixture of the solid composition, in particular a powdered solid phase, preferably a powder and / or granules, and storage at 20° C. Such an angle of repose has the advantage that the cavity can be filled relatively quickly and precisely with at least one solid phase.

[0176] In order to determine the angle of repose (also referred to as the angle of inclination) of at least one solid phase, a powder funnel with a capacity of 400 ml and an outlet diameter of 25 mm is simply suspended in a tripod. The funnel is moved upward at a speed of 80 mm / min by means of a manually operated rolling wheel so that a granular mixture, in particular a powder phase, preferably powder and / or particles, such as a powder flows out. As a result, a so-called conical pile is formed. Conical pile height and conical pile diameter are determined for each solid phase. The angle of inclination is calculated by the quotient of the conical pile height and the conical pile diameter*100.

[0177] Particulate mixtures of solid compositions, in particular powder phases, preferably powders and / or granules, such as powders, are particularly suitable, having a free-flowing capacity in % of more than 40%, preferably more than 50%, in particular more than 55%, more preferably more than 60%, particularly preferably from 63% to 80%, for example from 65% to 75%, compared to the above-mentioned standard test substances. Particulate mixtures of solid compositions, in particular powders and / or granules, such as powders, are particularly suitable, having a free-flowing capacity in % of more than 40%, preferably more than 45%, in particular more than 50%, more preferably more than 55%, particularly preferably more than 60%, compared to the above-mentioned standard test substances, the free-flowing capacity being measured 24 hours after preparation of the powder and storage at 20°C.

[0178] Lower values ​​for free-flowing capacity are quite unsuitable, since from a process point of view, an accurate metering of the granular mixture, in particular the particulate phase, preferably a powder and / or granules, such as a powder, is necessary. In particular, values ​​of greater than 50%, in particular greater than 55%, preferably greater than 60% (wherein the measurement of the free-flowing capacity is carried out 24 hours after the preparation of the powder and storage at 20° C.) have proven to be advantageous, since a good metering capacity of the granular mixture, in particular the powder phase, preferably a powder and / or granules, such as a powder, leads to only minor fluctuations in the metered quantity or composition. More accurate metering leads to consistent product properties and thus avoids economic losses due to over-metering. It is further advantageous that the granular mixture, in particular the powder phase, preferably a powder and / or granules, such as a powder, is well metered, so that a faster sequence of the metering process can be achieved. In addition, such a good free-flowing capacity makes it easier to avoid a situation whereby the granular mixture, in particular the powder phase, preferably a powder and / or granules, such as a powder, reaches part of the water-soluble wrapping, which is provided for producing a sealing seam and should therefore be kept as free of fine particles, in particular free of powder, as possible.

[0179] The granular mixture of the solid composition of the present invention acting as a solid phase is preferably presented in a free-flowing form (especially as a free-flowing powder and / or free-flowing granules). Therefore, the agent in the part according to the present invention comprises at least one solid phase, in particular a powder, of a free-flowing granular mixture of a solid composition, and at least one gel phase as previously defined. The cleaning agent according to the present invention preferably comprises at least one surfactant. This surfactant is selected from anionic, nonionic and cationic surfactants. The cleaning agent according to the present invention can also contain a mixture of several surfactants selected from the same group.

[0180] According to the present invention, at least one solid phase and / or at least one gel phase comprises at least one surfactant. It is possible that only at least one solid phase or only at least one gel phase comprises at least one surfactant. If both phases comprise surfactants, they are preferably surfactants different from each other. However, it is also possible that the solid phase and the gel phase have the same one or more surfactants. According to the present invention, at least one solid phase and / or the gel phase preferably contains at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. It is preferred to use low-foaming nonionic surfactants, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants, such as alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides or amine oxides. Particularly preferred nonionic surfactants are described in more detail below.

[0181] Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

[0182] Particular preference is given to using ethoxylated nonionic surfactants obtained from C 6-20 Monohydroxyalkanol or C 6-20 Alkylphenol or C 16-20 Fatty alcohol and more than 12 mol, preferably more than 15 mol, and in particular more than 20 mol of ethylene oxide per mole of alcohol. Particularly preferred nonionic surfactants are derived from straight-chain fatty alcohols (C 16-20 Alcohol), preferably C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

[0183] The surfactants preferably used are from the group of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants, such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

[0184] In the context of the present invention, low-foaming nonionic surfactants having alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred.

[0185] Among these, in turn, surfactants having EO-AO-EO-AO blocks are preferred, in which 1 to 10 EO groups or AO groups are bonded to each other before the subsequent block of the other group. Here, nonionic surfactants of the following general formula are preferred,

[0186]

[0187] Where R 1 represents a straight or branched chain, saturated or monounsaturated or polyunsaturated C 6-24 - an alkyl or alkenyl functional group; each R 2 and R 3 The groups are independently selected from -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 -CH 3 、-CH(CH 3) 2 ; and the indices w, x, y and z independently represent integers from 1 to 6.

[0188] The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohol R 1 -OH and ethylene oxide or alkylene oxide. 1 The functional group may vary depending on the origin of the alcohol. If a natural source is used, then R 1 The functional group has an even number of carbon atoms and is generally unbranched, with linear functional groups of alcohols of natural origin having 12 to 18 C atoms, such as coconut alcohol, palmityl alcohol, tallow alcohol or oleyl alcohol being preferred. Some examples of alcohols obtainable from synthetic sources are Guerbet alcohols or functional groups which are methyl branched in the 2-position or linear and methyl branched in a mixture, such as those typically present in oxo alcohol functional groups. Independent of the type of alcohol used to prepare the nonionic surfactant contained in the reagent, wherein R in the above formula is 1 Nonionic surfactants representing alkyl functions having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms are preferred.

[0189] In addition to propylene oxide, butylene oxide is particularly worthy of consideration as an alkylene oxide unit which is contained alternately with ethylene oxide units in the preferred nonionic surfactants. 2 and R 3 are independently selected from -CH 2 CH 2 -CH 3 and -CH(CH 3 ) 2 Other alkylene oxides of the above formula are also suitable. Preferably, a nonionic surfactant of the above formula is used, wherein R 2 and R 3 Representative-CH 3 functional group; w and x independently represent a value of 3 or 4; and y and z independently represent a value of 1 or 2.

[0190] The solid phase nonionic surfactant preferably used is of the general formula R 1 O(AlkO) x M(OAlk) y OR 2 A nonionic surfactant, wherein

[0191] R 1 and R 2represents independently of one another a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl functional group having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl functional group having 2 to 4 carbon atoms; x and y represent independently of one another a value from 1 to 70; and M represents a radical from CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 The alkyl functional group, R 3 and R 4 independently of one another represent branched or unbranched, saturated or unsaturated alkyl functions having 1 to 18 carbon atoms.

[0192] Preferred in this case are nonionic surfactants of the general formula

[0193] R 1 -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y -CH 2 CH(OH)-R 2 ,

[0194] Among them, R 1 and R 2 Each independently represents an alkyl group or an alkenyl group having 6 to 22 carbon atoms; and each independently represents a value of 1 to 40.

[0195] Particularly preferred in this case are compounds of the general formula

[0196] R 1 -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y O-CH 2 CH(OH)-R 2 ,

[0197] wherein R represents a linear, saturated alkyl function having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently represent a value of 20 to 30. For example, by making an alkyl glycol HO-CHR-CH 2 Such compounds can be obtained by reaction of -OH with ethylene oxide followed by reaction with an alkyl epoxide in order to block the free OH function during the formation of the dihydroxy ether.

[0198] In this case, the preferred nonionic surfactant is a surfactant having the general formula R 1 -CH(OH)CH 2 O-(AO) w -(AO) x -(A"O) y -(A"'O) z -R 2 Those nonionic surfactants, among which

[0199] -R 1 represents a straight or branched chain, saturated or monounsaturated or polyunsaturated C 6-24 Alkyl or alkenyl functional groups;

[0200] -R 2 represents hydrogen or a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms;

[0201] -A, A', A" and A'" independently represent a 2 CH 2 、-CH 2 CH 2 -CH 2 、-CH 2 -CH(CH 3 ),-CH 2 -CH 2 -CH 2 -CH 2 、-CH 2 -CH(CH 3 )-CH 2 -、-CH 2 -CH(CH 2 -CH 3 )

[0202] w, x, y and z represent values ​​from 0.5 to 120, wherein x, y and / or z may also be 0.

[0203] By adding the above mentioned general formula R 1 -CH(OH)CH 2 O-(AO) w -(A'O)x -(A"O) y -(A'"O) z -R 2 Based on the nonionic surfactants of the invention (hereinafter also referred to as "hydroxy mixed ethers"), surprisingly, the cleaning performance of the preparations according to the invention can be significantly improved compared to systems without surfactant and compared to systems with alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

[0204] By using these nonionic surfactants which have one or more free hydroxyl groups on one or both terminal alkyl functions, the stability of the enzymes comprised in the detergent formulations according to the invention can be significantly improved.

[0205] In particular, those end-capped poly(oxyalkylated) nonionic surfactants are preferred, according to the formula,

[0206]

[0207] In addition to the functional group R which represents a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional group having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms 1 In addition, the poly(oxyalkylated) nonionic surfactant also has a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional group R containing 1 to 30 carbon atoms. 2 , wherein n represents a value from 1 to 90, preferably a value from 10 to 80 and in particular a value from 20 to 60. wherein R 1 Represents C 7 To C 13 , n represents a natural integer from 16 to 28, and R 2 Represents C 8 To C 12 The surfactants of the above formula are particularly preferred.

[0208] Formula R 1 O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2 Surfactants of the type R 1 represents a linear or branched aliphatic hydrocarbon functional group having 4 to 18 carbon atoms or a mixture thereof, R 2represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms or a mixture thereof, x represents a value of 0.5 to 1.5 and y represents a value of at least 15. These groups of nonionic surfactants include, for example, C 2-26 Fatty alcohol (PO) 1 -(EO) 15-40 -2-Hydroxyalkyl ethers, especially C 8-10 Fatty alcohol (PO) 1 -(EO) 22 -2-Hydroxydecyl ether.

[0209] In particular, formula R 1 O[CH 2 CH 2 O] x [CH 2 CH(R 3 )O] y CH 2 CH(OH)R 2 The end-capped poly(oxyalkylated) nonionic surfactants are preferred, wherein R 1 and R 2 independently represent a linear or branched, saturated or monounsaturated or polyunsaturated hydrocarbon functional group having 2 to 26 carbon atoms, R 3 are independently selected from -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 -CH 3 、-CH(CH 3 ) 2 , but preferably represents -CH 3 , and x and y independently represent values ​​from 1 to 32, wherein R 3 =-CH 3 And nonionic surfactants having values ​​for x of from 15 to 32 and for y of from 0.5 to 1.5 are very particularly preferred.

[0210] A further nonionic surfactant which can preferably be used is of the formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 The end-capped poly(oxyalkylated) nonionic surfactant, wherein R 1 and R 2represents a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional group having 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl functional group, x represents a value from 1 to 30, and k and j represent values ​​from 1 to 12, preferably from 1 to 5. If the value x>2, then the above formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 Each R in 3 Can be different. 1 and R 2 Preference is given to linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 6 to 22 carbon atoms, with functional groups having 8 to 18 carbon atoms being particularly preferred. 3 , H, -CH 3 or -CH 2 CH 3 Particularly preferred values ​​for x are in the range of 1 to 20, in particular 6 to 15.

[0211] As mentioned above, if x>2, then each R in the above formula 3 can be different. In this way, the alkylene oxide units in the square brackets can vary. For example, if x represents 3, the functional group R can be selected 3 In order to form ethylene oxide (R 3 =H) or propylene oxide (R 3 =CH 3 ) units, which may be linked together in any order, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 has been chosen for x here as an example, and can of course be larger, in which case the range increases with increasing x values ​​and includes, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.

[0212] Particularly preferred capped poly(oxyalkylated) alcohols of the above formula have values ​​of k=1 and j=1, and thus the preceding formula simplifies to R 1 O[CH 2 CH(R 3 )O] X CH 2CH(OH)CH 2 OR 2 In the last mentioned formula, R 1 , R 2 and R 3 As defined above, and x represents a number from 1 to 30, preferably from 1 to 20, and in particular from 6 to 18. wherein the functional group R 1 and R 2 With 9 to 14 C atoms, R 3 Surfactants wherein R represents H and x takes values ​​from 6 to 15 are particularly preferred. Finally, it has been found that 1 -CH(OH)CH 2 O-(AO) w -R 2 Nonionic surfactants are particularly effective, among which

[0213] -R 1 represents a linear or branched, saturated or mono- or poly-unsaturated C6-24 alkyl or alkenyl functional group;

[0214] -R 2 represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms;

[0215] -A represents the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ) is preferably a functional group representing CH 2 CH 2 ,and

[0216] -w represents a value of 1 to 120, preferably 10 to 80, in particular 20 to 40.

[0217] These groups of nonionic surfactants include, for example, C 4-22 Fatty alcohol-(EO) 10-80 -2-Hydroxyalkyl ethers, especially C 8-12 Fatty alcohol-(EO) 22 -2-Hydroxydecyl ether and C 4-22 Fatty alcohol-(EO) 40-80 -2-Hydroxyalkyl ether.

[0218] Preferably, at least one solid phase and / or at least one gel phase contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the proportion by weight of the nonionic surfactant is preferably 0.5% to 30% by weight, more preferably 5% to 25% by weight and in particular 10% to 20% by weight, relative to the total weight of the gel phase.

[0219] In another preferred embodiment, the nonionic surfactant of the solid phase and / or gel phase is selected from the group consisting of 1 -O(CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 A nonionic surfactant, wherein R 1 and R 2 R independently represent an alkyl group or an alkenyl group having 4 to 22 carbon atoms; 3 and R 4 Each independently represents H or an alkyl or alkenyl group having 1 to 18 carbon atoms, and each independently represents a value of 1 to 40.

[0220] In particular, the general formula R 1 -O(CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 Compounds are preferred, wherein R 3 and R 4 represents H, and the indices x and y independently of one another take values ​​from 1 to 40, preferably from 1 to 15.

[0221] In particular, the general formula R 1 -O(CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 Compounds are particularly preferred in which the functional group R 1 and R 2independently of one another represent a saturated alkyl function having 4 to 14 carbon atoms, and the indices x and y independently of one another take values ​​from 1 to 15 and in particular from 1 to 12.

[0222] In addition, the general formula R 1 -O(CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 Compounds of this type are preferred, wherein the functional group R 1 and R 2 One is branched.

[0223] Most particularly preferred are the general formula R 1 -O(CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 A compound in which the exponents x and y independently of one another take values ​​from 8 to 12.

[0224] The indicated C chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical averages which may be integers or fractions for a given product. Due to the production process, the commercial products of the formula mentioned above generally do not consist of individual representatives but of mixtures, for which reason averages and fractions resulting therefrom may occur for the C chain lengths and for the degrees of ethoxylation and alkoxylation.

[0225] Naturally, the above-mentioned nonionic surfactants may be used not only as a single substance but also as a surfactant mixture of two, three, four or more surfactants.

[0226] In at least one solid phase, nonionic surfactants with a melting point above room temperature are particularly preferred. Nonionic surfactants with a melting point above 20°C, preferably above 25°C, particularly preferably from 25 to 60°C, and in particular from 26.6 to 43.3°C are particularly preferred.

[0227] Suitable nonionic surfactants having a melting point or softening point in the temperature range mentioned above include, for example, low foaming nonionic surfactants, which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants at room temperature are used, it is preferred that they have a viscosity higher than 20 Pa·s, preferably higher than 35 Pa·s, and especially higher than 40 Pa·s. Nonionic surfactants having a waxy consistency at room temperature are also preferred.

[0228] Nonionic surfactants that are solid at room temperature preferably have propylene oxide (PO) units in the molecule. Preferably, such PO units constitute up to 25% by weight of the total molar mass of the nonionic surfactant, particularly preferably up to 20% by weight, and in particular up to 15% by weight. Particularly preferred nonionic surfactants are ethoxylated monohydroxy alkanols or alkylphenols that additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules preferably constitutes more than 30% by weight of the total molar mass of such nonionic surfactants, particularly preferably more than 50% by weight, and in particular more than 70% by weight. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, wherein the propylene oxide units in the molecules constitute up to 25% by weight of the total molar mass of the nonionic surfactant, preferably up to 20% by weight, and in particular up to 15% by weight.

[0229] Another particularly preferred nonionic surfactant to be used in the solid phase having a melting point above room temperature contains 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene having 17 moles of ethylene oxide and 44 moles of propylene oxide, and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

[0230] In a preferred embodiment, the proportion by weight of the nonionic surfactants, relative to the total weight of the solid phase, is 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight and in particular 2.5 to 10% by weight.

[0231] All anionic surface-active substances are suitable for use as anionic surfactants in dishwasher detergents. These are characterized by water-soluble anionic groups, such as carboxylate, sulfate or sulfonate groups, and lipophilic alkyl groups with about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, esters, ethers and amide groups and hydroxyls can be included in the molecule. Suitable anionic surfactants are preferably present in the form of sodium salts, potassium salts and ammonium salts, and mono-, di- and tri-alkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but zinc, manganese (II), magnesium, calcium or their mixtures can also serve as counterions. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

[0232] Cationic surfactants and / or amphoteric surfactants such as betaines or quaternary ammonium compounds may also be used instead of the above mentioned surfactants or in combination therewith. However, it is preferred not to use cationic surfactants and / or amphoteric surfactants.

[0233] Surfactants influence the opacity of the gel phase. In another embodiment, the gel phase is therefore free of nonionic surfactants, in particular free of surfactants. "Free" means that the gel phase contains less than 1.0% by weight, and in particular less than 0.1% by weight of surfactants, preferably no surfactants or no nonionic surfactants. Preferred cleaning agents according to the invention are also characterized in that they contain less than 1.0% by weight, and in particular less than 0.1% by weight of surfactants, and preferably no anionic surfactants in at least one solid phase and / or at least one gel phase, in particular in the solid phase.

[0234] According to a particularly preferred embodiment, the cleaning agents according to the invention are characterized in that at least one gel phase comprises less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight, of anionic surfactants, in each case based on the total weight of the gel phase.

[0235] The at least one gel phase is preferably substantially free of anionic surfactants. Substantially free means that the at least one gel phase comprises less than 0.05% by weight of anionic surfactants, based in each case on the total weight of the gel phase.

[0236] In this context, it has been found that the presence of 1% by weight of anionic surfactants in at least one gel phase leads to poorer foaming behavior and poorer rinsing behavior of the overall composition. In addition, higher amounts of anionic surfactants adversely affect coagulation. According to a particularly preferred embodiment, the gel phase contains less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.05% by weight of fatty acid salts or soaps.

[0237] According to another embodiment, at least one gel phase may contain sugar. According to the present invention, sugar includes sugar alcohols, monosaccharides, disaccharides and oligosaccharides. In a preferred embodiment, at least one gel phase contains at least one sugar alcohol, preferably at least one monosaccharide or disaccharide sugar alcohol, except glycerol. In particular, mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol and xylitol are preferred. Particularly preferred monosaccharide sugar alcohols are pentitols and / or hexitols. Xylitol and / or sorbitol are very particularly preferred.

[0238] In another embodiment, the gel phase can contain disaccharides, in particular sucrose. The sucrose proportion is 0% to 30% by weight, in particular 5% to 25% by weight, particularly preferably 10% to 20% by weight, relative to the weight of the gel phase. In larger quantities, the sugar cannot be completely dissolved in the gel phase and causes it to be turbid. By using sugar, in particular in a proportion of 10% to 15% by weight, the development of moisture is reduced and thus the adhesion to the at least one solid phase is improved.

[0239] The use of builder materials (builders) such as silicates, aluminium silicates (especially zeolites), salts of organic di- and polycarboxylic acids, and mixtures of these materials, preferably water-soluble builder materials, may be advantageous.

[0240] In a particularly preferred embodiment according to the invention, the use of phosphates (including polyphosphates) is largely or completely omitted. In this embodiment, the agent preferably contains less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight of phosphates. Particularly preferably, the agent in this embodiment is completely free of phosphates, i.e., the agent contains less than 0.1% by weight of phosphates.

[0241] Builders include in particular carbonates, citrates, phosphonates (if permitted by legislation), organic builders and silicates. The proportion by weight of total builders is preferably from 15 to 80% by weight, and in particular from 20 to 70% by weight, relative to the total weight of the agent according to the invention.

[0242] Some examples of suitable organic builders according to the present invention are polycarboxylic acids (polycarboxylates) that can be used in the form of their sodium salts, wherein polycarboxylic acids are understood to be those polycarboxylic acids that carry more than one, particularly two to eight acid functional groups, preferably two to six, particularly two, three, four or five acid functional groups in the entire molecule. As polycarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, particularly di-, tri- and tetracarboxylic acids are therefore preferred. For example, polycarboxylic acids can also carry other functional groups, such as hydroxyl or amino groups. For example, they include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldar acids, such as galactaric acid and glucaric acid), aminocarboxylic acids, particularly aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamic acid-N, N-diacetic acid (also referred to as N, N-bis(carboxymethyl)-L-glutamic acid or GLDA), methylglycine diacetic acid (MGDA) and derivatives and mixtures thereof. Preferred salts are salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.

[0243] Other materials suitable as organic builders are polymeric polycarboxylates (organic polymers having a plurality (especially more than ten) carboxylic acid functions in the macromolecule), polyaspartates, polyacetals and dextrins.

[0244] In addition to their builder effect, the free acids generally also have the quality of an acidifying component. Particular mention may be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

[0245] Particularly preferred cleaning agents according to the invention, in particular dishwasher detergents, preferably automatic dishwasher detergents, contain one or more salts of citric acid, i.e. citrates, as one of their essential builders. These are preferably contained in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, in particular 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to 20% by weight, in each case based on the total weight of the agent.

[0246] Particular preference is also given to using carbonates and / or bicarbonates, preferably alkali metal carbonates, particularly preferably sodium carbonate (soda ash), in amounts of 2 to 50% by weight, preferably 4 to 40% by weight and in particular 10 to 30% by weight, very particularly preferably 10 to 24% by weight, in each case based on the weight of the reagent.

[0247] Particularly preferred cleaning agents according to the invention, in particular dishwasher detergents, preferably automatic dishwasher detergents, are characterized in that they contain at least two builders from the group of silicates, phosphonates (if permitted by law), carbonates, aminocarboxylic acids and citrates, wherein the proportion by weight of these builders, based on the total weight of the cleaning agent according to the invention, is preferably 5 to 70% by weight, more preferably 15 to 60% by weight, and in particular 20 to 50% by weight. Combinations of two or more builders from the above-mentioned groups have proven to be advantageous for the cleaning and rinsing performance of the cleaning agents according to the invention, in particular dishwasher detergents, preferably automatic dishwasher detergents. In addition to the builders mentioned here, one or more other builders may also be contained.

[0248] Preferred cleaning agents, in particular dishwasher detergents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate. In a very particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, wherein the amount of carbonate is preferably 5 to 40% by weight, in particular 10 to 35% by weight, very particularly preferably 15 to 30% by weight, and the amount of citrate is preferably 5 to 35% by weight, in particular 10 to 25% by weight, very particularly preferably 15 to 20% by weight, in each case based on the total amount of the cleaning agent, wherein the total amount of the two builders is preferably 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight. In addition, one or more further builders may be contained in addition.

[0249] If permitted by law, cleaning agents according to the invention, in particular dishwasher detergents, preferably automatic dishwasher detergents, may contain in particular phosphonates as further builders (if permitted by law). Preferably, hydroxyalkane and / or aminoalkane phosphonates are used as phosphonate compounds. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Possible preferred aminoalkane phosphonates include ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. The phosphonates are preferably contained in the agents according to the invention (if permitted by law) in an amount of 0.1 to 10% by weight, in particular 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight, in each case based on the total weight of the agent.

[0250] The combined use of citrates, carbonates (bicarbonates) and phosphonates (if permitted by regulations) is particularly preferred. These can be used in the amounts mentioned above. In particular, in this combination, 10 to 25% by weight of citrates, 10 to 30% by weight of carbonates (or bicarbonates) and 2.5 to 7.5% by weight of phosphonates are used, in each case based on the total weight of the reagents.

[0251] Further particularly preferred cleaning agents, in particular dishwasher detergents, preferably automatic dishwasher detergents, are characterized in that, in addition to citrates and (bi)carbonates and optionally phosphonates, they contain at least one further phosphorus-free builder. In particular, it is selected from aminocarboxylic acids, wherein the further phosphorus-free builder is preferably selected from methylglycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA. An example of a particularly preferred combination is citrate, (bi)carbonate and MGDA and optionally phosphonates (if permitted by regulations).

[0252] The proportion of other phosphorus-free builders, especially MGDA and / or GLDA by weight is preferably 0 to 40% by weight, especially 5 to 30% by weight, more especially 7 to 25% by weight. It is particularly preferred to use MGDA or GLDA, especially MGDA as particles. Advantageous in this regard are MGDA particles that contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25° C., normal pressure) than non-granular powders. A combination of at least three, especially at least four builders from the group mentioned above has been shown to be advantageous for the cleaning and rinsing performance of the cleaning agent according to the invention, especially dishwasher detergents, preferably automatic dishwasher detergents. In addition to these, other builders may also be contained.

[0253] Polymeric polycarboxylates are also suitable as organic builders. These are, for example, alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g / mole. Suitable polymers are in particular polyacrylates, which preferably have a molecular mass of 1,000 to 20,000 g / mole. Due to their excellent solubility, short-chain polyacrylates from this group with a molar mass of 1,100 to 10,000 g / mole, and particularly preferably 1,200 to 5,000 g / mole, may be preferred.

[0254] The content of (homo)polymeric polycarboxylates in the cleaning agents according to the invention, in particular dishwasher detergents, preferably automatic dishwasher detergents, is preferably from 0.5 to 20% by weight, preferably from 2 to 15% by weight and in particular from 4 to 10% by weight.

[0255] The cleaning agents according to the invention, in particular dishwasher detergents, preferably automatic dishwasher detergents, may also contain as a builder the general formula NaMSi x O 2x+1 ·y H 2 O, wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, wherein 2, 3 or 4 are particularly preferred values ​​for x, and y represents a number from 0 to 33, preferably from 0 to 20. The use of Na 2 O:SiO 2 Amorphous sodium silicates having moduli of 1:2 to 1:3.3, preferably 1:2 to 1:2.8, and especially 1:2 to 1:2.6 are also possible, which preferably exhibit delayed dissolution and secondary wash properties.

[0256] In addition to the above-mentioned builders, the cleaning agents according to the invention may also contain alkali metal hydroxides. These alkali metal carriers are preferably used in the cleaning agent and in particular in at least one gel phase only in small amounts, preferably in an amount of less than 10% by weight, preferably less than 6% by weight, more preferably less than 5% by weight, particularly preferably in an amount of 0.1 to 5% by weight and in particular in an amount of 0.5 to 5% by weight, in each case based on the total weight of the cleaning agent. The alternative cleaning agents according to the invention do not contain alkali metal hydroxides.

[0257] In addition to the components described above, at least one solid phase and / or at least one gel phase of the cleaning agent according to the invention may contain further ingredients. These include, for example, anionic, cationic and / or amphoteric surfactants, bleaches, bleach activators, bleach catalysts, other solvents, thickeners, sequestrants, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam suppressors, dyes, fragrances (in particular in at least one solid phase), additives for improving flow and drying behavior, for adjusting viscosity, for stabilization, UV stabilizers, preservatives, antimicrobial active ingredients (disinfectants), pH adjusters, in amounts generally not exceeding 5% by weight.

[0258] The agent according to the invention preferably contains at least one alkanolamine as an additional solvent. The alkanolamine is preferably selected from monoethanolamine, diethanolamine, triethanolamine and propanolamine and mixtures thereof. The alkanolamine is preferably contained in the agent according to the invention in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight. In preferred cleaning agents, at least one gel phase is substantially free of alkanolamine, i.e. at least one gel phase contains less than 1% by weight, in particular less than 0.5% by weight, preferably less than 0.1% by weight, particularly preferably less than 0.05% by weight of alkanolamine, and the alkanolamine is contained only in at least one solid phase.

[0259] According to a further preferred embodiment, at least one gel phase of the cleaning agent, in particular a dishwasher detergent, preferably an automatic dishwasher detergent, contains at least one water-soluble zinc salt, preferably zinc chloride, zinc sulfate and / or zinc acetate, particularly preferably zinc acetate, for example anhydrous zinc acetate, preferably in an amount of 0.05 to 3% by weight, in particular 0.1 to 2.4% by weight, particularly preferably 0.2 to 1.0% by weight, based on the total weight of the gel phase.

[0260] For good incorporation capability of zinc salts, in particular zinc sulfate and / or zinc acetate, in particular zinc acetate (e.g. in the anhydrous form of the salt) into the low water gel phase with carboxylate and / or sulfonic acid group-containing polymers, it is particularly preferred that the amount of zinc salt in the anhydrous gel phase is selected to be 0.2 to 1.0% by weight, for example 0.5% by weight.

[0261] In addition to the zinc salts mentioned above, polyethylene imine or polyvinyl amine, for example, may be named Those obtained from BASF are preferably used as glass corrosion inhibitors in amounts of 0 to 5% by weight, in particular 0.01 to 2% by weight.

[0262] Polymers suitable as additives are in particular maleic acid acrylic acid copolymer sodium salt (for example, available from BASF, Ludwigshafen (Germany) CP 5), modified polyacrylic acid sodium salt (e.g., by BASF, Ludwigshafen (Germany) CP 10), modified polycarboxylic acid sodium salts (e.g., by BASF, Ludwigshafen (Germany) HP 25), polyalkylene oxides, modified heptamethyltrisiloxane (e.g., from BASF, Ludwigshafen (Germany) L-77), polyalkylene oxide, modified heptamethyltrisiloxane (e.g., by BASF, Ludwigshafen (Germany) L-7608), and polyether siloxanes (copolymers of polymethylsiloxane with ethylene oxide / propylene oxide segments (polyether blocks), preferably water-soluble, linear polyether siloxanes with terminal polyether blocks, such as those available from Evonik, Essen (Germany) 5840, 5843, 5847, 5851, 5863 or 5878. Suitable builders as additives are in particular sodium polyaspartate, ethylenediamine triacetate cocoalkyl acetamide (e.g. from Evonik, Essen (Germany) CHT 12), trisodium methylglycine diacetate and acetylphosphonic acid. 5843 and In the case of Tegopren 5843 and 5863, mixtures with surface active or polymeric additives show synergistic effects. However, the use of Tegopren types 5843 and 5863 on hard surfaces made of glass, in particular glass tableware, is less preferred because these silicone surfactants can adhere to the glass. In a particular embodiment of the invention, the above mentioned additives are omitted.

[0263] Preferred cleaning agents, in particular automatic dishwasher detergents, preferably also contain bleaching agents, in particular oxygen bleaching agents, and optionally bleach activators and / or bleach catalysts. To the extent that they are present, they are contained only in at least one solid phase.

[0264] As preferred bleaching agents, the cleaning agents according to the invention contain oxygen bleaches from the group of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. Further examples of bleaching agents that can be used are peroxypyrophosphates, citrate perhydrates and H-generating 2 O 2 The bleaching agents of the present invention are preferably peroxy peroxides or peracids, for example peroxybenzoates, peroxy phthalates, diperazelaic acid, phthaloiminoperacid or diperdodecane diacid. In addition, bleaching agents from the group of organic bleaches can also be used. Common organic bleaches are diacyl peroxides, for example dibenzoyl peroxide. Other common organic bleaches are peroxy acids, of which alkyl peroxy acids and aryl peroxy acids are particularly worth mentioning as examples. Sodium percarbonate is particularly preferred due to its good bleaching properties. A particularly preferred oxygen bleach is sodium percarbonate.

[0265] Compounds which under perhydrolysis conditions lead to aliphatic peroxycarboxylic acids preferably having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acids can be used as bleach activators. Substances carrying O- and / or N-acyl groups and / or optionally substituted benzoyl groups with the stated number of carbon atoms are suitable. Multiply acylated alkylenediamines are preferred, of which tetraacetylethylethylenediamine (TAED) has proven to be particularly suitable.

[0266] The bleaching catalyst is a transition metal salt or transition metal complex which promotes bleaching, for example a Mn-, Fe-, Co-, Ru- or Mo-salene complex or -carbonyl complex. Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- and Cu complexes with N-containing tripod ligands, as well as Co-, Fe-Cu- and Ru-ammine complexes can also be used as bleaching catalysts. Particular preference is given to using complexes of manganese in oxidation stage II, III, IV or IV, which preferably contain one or more macrocyclic ligands with donor functions N, NR, PR, O and / or S. Preferably, ligands with nitrogen donor functions are used. Particular preference is given to using bleach catalysts in the agents according to the invention which contain as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn III 2 (μ-O) 1 (μ-OAC) 2 (TACN) 2 ](CIO 4 ) 2 、[Mn III Mn lv (μ-O) 2 (μ-O Ac) 1 (TACN) 2 ](BPh 4 ) 2 、[Mn lv 4 (μ-O) 6 (TACN) 4 ](CIO 4 ) 4 、[Mn III 2 (μ-0) 1(μ-OAc) 2 (Me-TACN) 2 ](CIO 4 ) 2 、[Mn III Mn lv (μ-0) 1 (μ-0Ac) 2 (Me-TACN) 2 ](CIO 4 ) 3 、[Mn lv 2 (μ-O) 3 (Me-TACN) 2 ](PF 6 ) 2 and [Mn lv 2 (μ-O) 3 (Me / Me-TACN) 2 ](PF 6 ) 2 (where OAc=OC(O)CH 3 ).

[0267] The cleaning agent according to the invention preferably comprises at least one solid phase and at least one gel phase. The cleaning agent can therefore have one, two, three or more different solid phases; it can also have one, two, three or more different gel phases. The cleaning agent according to the invention preferably comprises one solid phase and one gel phase. The cleaning agent particularly preferably comprises two solid phases and one gel phase. It preferably comprises two solid phases and two gel phases. An embodiment in which the cleaning agent comprises three solid phases and one or two gel phases is also preferred.

[0268] In this case, the weight ratio of the whole of at least one solid phase to the whole of at least one gel phase is generally 40: 1 to 2: 1, in particular 20: 1 to 4: 1, preferably 14: 1 to 6: 1, for example 12: 1 to 8: 1. The total weight of all phases in the detergent part can be 8 to 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 13 to 17 g per cleaning part. This weight ratio provides a good concentration of the respective components of the solid phase and the gel phase during the cleaning process.

[0269] According to a preferred embodiment, the protease enzyme is contained in the detergent part in a total amount of 0.001 to 1,000 mg, more preferably 0.1 to 600 mg, and even more preferably 1.0 to 400 mg enzyme protein (based on active enzyme protein).

[0270] According to the present invention, at least one solid phase and at least one gel phase are adjacent to each other on all or part of their surfaces. In this respect, preferably two phases are adjacent. If at least one solid phase and at least one gel phase are directly adjacent to each other on all or part of their surfaces, then stability is also important except the shortest possible hardening time of at least one gel phase. Here, stability means that the components contained in the gel phase do not cross into at least one solid phase, but at least one solid phase and the gel phase remain visually separated from each other even after long-term storage, and do not interact with each other, for example, by diffusion of liquid components from one phase to another phase or reaction of components of one phase with components in another phase.

[0271] The present application also relates to a method for cleaning hard surfaces, in particular dishes, wherein the surfaces are acted upon in a manner known per se using a cleaning agent according to the invention. In particular, the surfaces are brought into contact with the cleaning agent according to the invention. Cleaning is carried out in particular using a cleaning machine, preferably a dishwasher.

[0272] The invention also relates to the use of a cleaning agent as described above for cleaning hard surfaces, in particular dishes, in particular in an automatic dishwasher. What has been disclosed above specifically with respect to the cleaning agent also applies to the use and the method.

[0273] A particularly preferred embodiment of the present invention relates to a cleaning agent comprising at least one enzyme, preferably enzyme granules, polyethylene glycol with an average molecular weight of 200 to 600 g / mol, glycerol, PVOH and at least one C 3 To C 5 A single detergent part in a water-soluble package is preferably provided, which contains at least one enzyme, preferably enzyme particles, polyethylene glycol having an average molecular weight of 200 to 600 g / mole, glycerol, PVOH and at least one C 3 To C 5 Alkanediol.

[0274] Insofar as it is stated in the present application that a cleaning agent according to the invention comprises certain substances in their entirety or in at least one solid phase or in at least one gel phase, this should also be considered as disclosing the fact that the cleaning agent or the relevant phase may consist of it. In the following practical examples, a cleaning agent according to the invention is described in a non-limiting manner.

[0275] Implementation plan:

[0276] Cleaning agents according to the invention comprising a solid phase and a gel phase were prepared. Different geometries were produced in the process. In addition, cleaning agents comprising two solid phases and one gel phase were prepared. Cleaning agents comprising one solid phase and three, four and five gel phases (with the same or different compositions) were also prepared. The following quantities refer to the weight % of active substance based on the total weight of the phase concerned (unless otherwise stated).

[0277] Table 1 : A solid particulate mixture of a solid composition, especially a powder and a free-flowing phase, has the following preferred composition:

[0278]

[0279] Table 2: The gel phase used had the following composition (the amounts in each case are based on the total amount of gel phase):

[0280] The solid phase and the gel phase can be combined as desired. The spatial configuration of the gel phase, which is liquid after the ingredients are mixed and dimensionally stable within a setting time of up to 10 minutes, is predetermined by the spatial configuration of the solid phase and a commercially available or self-designed mold. The water-soluble wrapping in the form of an open pouch is produced by thermoforming a film containing PVOH. The liquid composition is poured into the open cavity and the gel phase is obtained after setting, and then the solid phase in the form of a free-flowing solid is poured into a pouch containing polyvinyl alcohol, which is then sealed by applying a second film and sealing by heat sealing.

[0281] Table 3: Composition of the gel phase in wt %

[0282]

[0283] The corresponding formulations were prepared according to Table 3. The gel phase was stirred at a temperature of 110° C. Shortly before metering in the gel phase, the protease granules 1 or 2 were metered into the still hot composition.

[0284] The corresponding gel phase (1.5 g) was then packaged in individual portions (sachets) as described under Table 2 together with the solid phase according to Table 4 (17.0 g) with a total weight of 18.5 g.

[0285] Table 4: Composition of gel phase:

[0286]

[0287] Cleaning performance:

[0288] Using the individual portions prepared in this way (gel phase G1, solid phase, Table 4), the cleaning performance of the compositions was determined according to the IKW method in the Miele GSL, Eco 45° program at 21° dH.

[0289] Table 5:

[0290] Cleaning performance Creme brulee yolk spaghetti E1 G1+Protease Granules 1 (30 mg / working) 7.2 4.7 3.5 E2 G1+Protease Granules 2 (30 mg / working) 8.4 8.0 4.5

[0291] Both protease enzyme granules contain 30 mg of active protein per serving (corresponding to an active enzyme protein content per serving, suitable for cleaning applications).

[0292] Protease Granule 1 contains Protease 1a (protease according to SEQ ID NO: 6 from WO2016000973) and Protease 1b ( from Novozymes).

[0293] Protease Granule 2 contains the protease according to SEQ ID NO: 5 from WO2017215925.

[0294] Surprisingly, it was found that the protease was able to withstand the high temperature (>90°C) remaining in the gel formulation before it hardened. Furthermore, it was surprisingly found that when using Protease Granule 2, in addition to a particularly good cleaning performance on protein-containing stains, an effect on starch-based stains pasta could also be observed.

[0295] In corresponding further experiments with the same parameters only lower amounts of protease were used in the gel phase (see Table 6):

[0296] Table 6:

[0297] Cleaning performance Burnt minced meat yolk E3 G1+Protease Granules 1 (15 mg / working) 4.2 3.2 E4 G1+Protease Granules 2 (15 mg / working) 6.9 5.6

[0298] Both protease enzyme granules contain 15 mg of active protein per serving (corresponding to the content of active enzyme protein per serving, suitable for cleaning applications).

[0299] Protease Granule 1 contains Protease 1a (protease according to SEQ ID NO: 6 from WO2016000973) and Protease 1b ( from Novozymes).

[0300] Protease Granule 2 contains the protease according to SEQ ID NO: 5 from WO2017215925.

[0301] Here too, it was surprisingly found that both proteases gave good results on protease-sensitive stains, in particular when using Protease Granule 2, particularly good cleaning performances could be observed, in particular on egg yolk and burnt minced meat. Sequence Listing <110> Henkel AG & Co. KGaA <120> Cleaners containing enzymes <130> 2019P00253WO <150> EP19187523.6 <151> 2019-07-22 <160> 7 <170> PatentIn version 3.5 <210> 1 <211> 269 <212> PRT <213> Bacillus gibsonii <400> 1 Gln Gln Thr Val Pro Trp Gly Ile Thr Arg Val Gln Ala Pro Thr Val 1 5 10 15 His Asn Arg Gly Ile Thr Gly Ser Gly Val Lys Val Ala Ile Leu Asp 20 25 30 Thr Gly Ile Ala Gln His Ser Asp Leu Thr Ile Arg Gly Gly Ala Ser 35 40 45 Phe Val Pro Gly Glu Ser Thr Thr Ala Asp Leu Asn Gly His Gly Thr 50 55 60 His Val Ala Gly Thr Val Ala Ala Leu Asn Asn Ser Ile Gly Val Ile 65 70 75 80 Gly Val Ala Pro Ser Ala Asp Leu Tyr Ala Val Lys Val Leu Gly Ala 85 90 95 Asn Gly Arg Gly Ser Val Ser Gly Ile Ala Gln Gly Leu Glu Trp Ala 100 105 110 Ala Thr Asn Asn Met His Ile Ala Asn Met Ser Leu Gly Ser Asp Ala 115 120 125 Pro Ser Thr Thr Leu Glu Arg Ala Val Asn Tyr Ala Thr Ser Arg Gly 130 135 140 Val Leu Val Ile Ala Ala Thr Gly Asn Asn Gly Thr Gly Ser Ile Gly 145 150 155 160 Tyr Pro Ala Arg Tyr Ala Asn Ala Met Ala Val Gly Ala Thr Asp Gln 165 170 175 Asn Asn Arg Arg Ala Ser Phe Ser Gln Tyr Gly Thr Gly Ile Asp Ile 180 185 190 Val Ala Pro Gly Val Gly Ile Gln Ser Thr Tyr Leu Asn Asn Ser Tyr 195 200 205 Ala Ser Met Pro Gly Thr Ser Met Ala Thr Pro His Val Ala Gly Val 210 215 220 Ala Ala Leu Val Lys Gln Lys Asn Pro Ser Trp Asn Ala Thr Gln Ile 225 230 235 240 Arg Asn His Leu Lys Asn Thr Ala Thr Asn Leu Gly Asn Ser Ser Gln 245 250 255 Phe Gly Ser Gly Leu Val Asn Ala Asp Ala Ala Thr Arg 260 265 <210> 2 <211> 269 <212> PRT <213> Bacillus lentus <400> 2 Ala Gln Ser Val Pro Trp Gly Ile Ser Arg Val Gln Ala Pro Ala Ala 1 5 10 15 His Asn Arg Gly Leu Thr Gly Ser Gly Val Lys Val Ala Val Leu Asp 20 25 30 Thr Gly Ile Ser Thr His Pro Asp Leu Asn Ile Arg Gly Gly Ala Ser 35 40 45 Phe Val Pro Gly Glu Pro Ser Thr Gln Asp Gly Asn Gly His Gly Thr 50 55 60 His Val Ala Gly Thr Ile Ala Ala Leu Asn Asn Ser Ile Gly Val Leu 65 70 75 80 Gly Val Ala Pro Ser Ala Glu Leu Tyr Ala Val Lys Val Leu Gly Ala 85 90 95 Ser Gly Ser Gly Ser Val Ser Ser Ile Ala Gln Gly Leu Glu Trp Ala 100 105 110 Gly Asn Asn Gly Met His Val Ala Asn Leu Ser Leu Gly Ser Pro Ser 115 120 125 Pro Ser Ala Thr Leu Glu Gln Ala Val Asn Ser Ala Thr Ser Arg Gly 130 135 140 Val Leu Val Val Ala Ala Ser Gly Asn Ser Gly Ala Gly Ser Ile Ser 145 150 155 160 Tyr Pro Ala Arg Tyr Ala Asn Ala Met Ala Val Gly Ala Thr Asp Gln 165 170 175 Asn Asn Asn Arg Ala Ser Phe Ser Gln Tyr Gly Ala Gly Leu Asp Ile 180 185 190 Val Ala Pro Gly Val Asn Val Gln Ser Thr Tyr Pro Gly Ser Thr Tyr 195 200 205 Ala Ser Leu Asn Gly Thr Ser Met Ala Thr Pro His Val Ala Gly Ala 210 215 220 Ala Ala Leu Val Lys Gln Lys Asn Pro Ser Trp Ser Asn Val Gln Ile 225 230 235 240 Arg Asn His Leu Lys Asn Thr Ala Thr Ser Leu Gly Ser Thr Asn Leu 245 250 255 Tyr Gly Ser Gly Leu Val Asn Ala Glu Ala Ala Thr Arg 260 265 <210> 3 <211> 269 <212> PRT <213> Bacillus alkalophilus <400> 3 Ala Gln Ser Val Pro Trp Gly Ile Ser Arg Val Gln Ala Pro Ala Ala 1 5 10 15 His Asn Arg Gly Leu Thr Gly Ser Gly Val Lys Val Ala Val Leu Asp 20 25 30 Thr Gly Ile Ser Thr His Pro Asp Leu Asn Ile Arg Gly Gly Ala Ser 35 40 45 Phe Val Pro Gly Glu Pro Ser Thr Gln Asp Gly Asn Gly His Gly Thr 50 55 60 His Val Ala Gly Thr Ile Ala Ala Leu Asn Asn Ser Ile Gly Val Leu 65 70 75 80 Gly Val Ala Pro Asn Ala Glu Leu Tyr Ala Val Lys Val Leu Gly Ala 85 90 95 Ser Gly Ser Gly Ser Val Ser Ser Ile Ala Gln Gly Leu Glu Trp Ala 100 105 110 Gly Asn Asn Gly Met His Val Ala Asn Leu Ser Leu Gly Ser Pro Ser 115 120 125 Pro Ser Ala Thr Leu Glu Gln Ala Val Asn Ser Ala Thr Ser Arg Gly 130 135 140 Val Leu Val Val Ala Ala Ser Gly Asn Ser Gly Ala Gly Ser Ile Ser 145 150 155 160 Tyr Pro Ala Arg Tyr Ala Asn Ala Met Ala Val Gly Ala Thr Asp Gln 165 170 175 Asn Asn Asn Arg Ala Ser Phe Ser Gln Tyr Gly Ala Gly Leu Asp Ile 180 185 190 Val Ala Pro Gly Val Asn Val Gln Ser Thr Tyr Pro Gly Ser Thr Tyr 195 200 205 Ala Ser Leu Asn Gly Thr Ser Met Ala Thr Pro His Val Ala Gly Ala 210 215 220 Ala Ala Leu Val Lys Gln Lys Asn Pro Ser Trp Ser Asn Val Gln Ile 225 230 235 240 Arg Asn His Leu Lys Asn Thr Ala Thr Ser Leu Gly Ser Thr Asn Leu 245 250 255 Tyr Gly Ser Gly Leu Val Asn Ala Glu Ala Ala Thr Arg 260 265 <210> 4 <211> 269 <212> PRT <213> Bacillus lentus <400> 4 Ala Gln Ser Val Pro Trp Gly Ile Ser Arg Val Gln Ala Pro Ala Ala 1 5 10 15 His Asn Arg Gly Leu Thr Gly Ser Gly Val Lys Val Ala Val Leu Asp 20 25 30 Thr Gly Ile Ser Thr His Pro Asp Leu Asn Ile Arg Gly Gly Ala Ser 35 40 45 Phe Val Pro Gly Glu Pro Ser Thr Gln Asp Gly Asn Gly His Gly Thr 50 55 60 His Val Ala Gly Thr Ile Ala Ala Leu Asn Asn Ser Ile Gly Val Leu 65 70 75 80 Gly Val Ala Pro Ser Ala Glu Leu Tyr Ala Val Lys Val Leu Gly Ala 85 90 95 Asp Gly Arg Gly Ala Ile Ser Ser Ile Ala Gln Gly Leu Glu Trp Ala 100 105 110 Gly Asn Asn Gly Met His Val Ala Asn Leu Ser Leu Gly Ser Pro Ser 115 120 125 Pro Ser Ala Thr Leu Glu Gln Ala Val Asn Ser Ala Thr Ser Arg Gly 130 135 140 Val Leu Val Val Ala Ala Ser Gly Asn Ser Gly Ala Ser Ser Ile Ser 145 150 155 160 Tyr Pro Ala Arg Tyr Ala Asn Ala Met Ala Val Gly Ala Thr Asp Gln 165 170 175 Asn Asn Asn Arg Ala Ser Phe Ser Gln Tyr Gly Ala Gly Leu Asp Ile 180 185 190 Val Ala Pro Gly Val Asn Val Gln Ser Thr Tyr Pro Gly Ser Thr Tyr 195 200 205 Ala Ser Leu Asn Gly Thr Ser Met Ala Thr Pro His Val Ala Gly Ala 210 215 220 Ala Ala Leu Val Lys Gln Lys Asn Pro Ser Trp Ser Asn Val Gln Ile 225 230 235 240 Arg Asn His Leu Lys Asn Thr Ala Thr Ser Leu Gly Ser Thr Asn Leu 245 250 255 Tyr Gly Ser Gly Leu Val Asn Ala Glu Ala Ala Thr Arg 260 265 <210> 5 <211> 485 <212> PRT <213> Bacillus species <400> 5 His His Asn Gly Thr Asn Gly Thr Met Met Gln Tyr Phe Glu Trp Tyr 1 5 10 15 Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Asn Ser Asp Ala Ser 20 25 30 Asn Leu Lys Ser Lys Gly Ile Thr Ala Val Trp Ile Pro Pro Ala Trp 35 40 45 Lys Gly Ala Ser Gln Asn Asp Val Gly Tyr Gly Ala Tyr Asp Leu Tyr 50 55 60 Asp Leu Gly Glu Phe Asn Gln Lys Gly Thr Val Arg Thr Lys Tyr Gly 65 70 75 80 Thr Arg Ser Gln Leu Gln Ala Ala Val Thr Ser Leu Lys Asn Asn Gly 85 90 95 Ile Gln Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Ala Asp 100 105 110 Ala Thr Glu Met Val Arg Ala Val Glu Val Asn Pro Asn Asn Arg Asn 115 120 125 Gln Glu Val Thr Gly Glu Tyr Thr Ile Glu Ala Trp Thr Arg Phe Asp 130 135 140 Phe Pro Gly Arg Gly Asn Thr His Ser Ser Phe Lys Trp Arg Trp Tyr 145 150 155 160 His Phe Asp Gly Val Asp Trp Asp Gln Ser Arg Arg Leu Asn Asn Arg 165 170 175 Ile Tyr Lys Phe Arg Gly His Gly Lys Ala Trp Asp Trp Glu Val Asp 180 185 190 Thr Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Ala Asp Ile Asp Met 195 200 205 Asp His Pro Glu Val Val Asn Glu Leu Arg Asn Trp Gly Val Trp Tyr 210 215 220 Thr Asn Thr Leu Gly Leu Asp Gly Phe Arg Ile Asp Ala Val Lys His 225 230 235 240 Ile Lys Tyr Ser Phe Thr Arg Asp Trp Ile Asn His Val Arg Ser Ala 245 250 255 Thr Gly Lys Asn Met Phe Ala Val Ala Glu Phe Trp Lys Asn Asp Leu 260 265 270 Gly Ala Ile Glu Asn Tyr Leu Gln Lys Thr Asn Trp Asn His Ser Val 275 280 285 Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Ala Ser Lys Ser Gly 290 295 300 Gly Asn Tyr Asp Met Arg Asn Ile Phe Asn Gly Thr Val Val Gln Arg 305 310 315 320 His Pro Ser His Ala Val Thr Phe Val Asp Asn His Asp Ser Gln Pro 325 330 335 Glu Glu Ala Leu Glu Ser Phe Val Glu Glu Trp Phe Lys Pro Leu Ala 340 345 350 Tyr Ala Leu Thr Leu Thr Arg Glu Gln Gly Tyr Pro Ser Val Phe Tyr 355 360 365 Gly Asp Tyr Tyr Gly Ile Pro Thr His Gly Val Pro Ala Met Arg Ser 370 375 380 Lys Ile Asp Pro Ile Leu Glu Ala Arg Gln Lys Tyr Ala Tyr Gly Lys 385 390 395 400 Gln Asn Asp Tyr Leu Asp His His Asn Ile Ile Gly Trp Thr Arg Glu 405 410 415 Gly Asn Thr Ala His Pro Asn Ser Gly Leu Ala Thr Ile Met Ser Asp 420 425 430 Gly Ala Gly Gly Ser Lys Trp Met Phe Val Gly Arg Asn Lys Ala Gly 435 440 445 Gln Val Trp Ser Asp Ile Thr Gly Asn Arg Thr Gly Thr Val Thr Ile 450 455 460 Asn Ala Asp Gly Trp Gly Asn Phe Ser Val Asn Gly Gly Ser Val Ser 465 470 475 480 Ile Trp Val Asn Lys 485 <210> 6 <211> 485 <212> PRT <213> Bacillus species <400> 6 His His Asn Gly Thr Asn Gly Thr Met Met Gln Tyr Phe Glu Trp Tyr 1 5 10 15 Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Ser Asp Ala Ser 20 25 30 Asn Leu Lys Asp Lys Gly Ile Ser Ala Val Trp Ile Pro Pro Ala Trp 35 40 45 Lys Gly Ala Ser Gln Asn Asp Val Gly Tyr Gly Ala Tyr Asp Leu Tyr 50 55 60 Asp Leu Gly Glu Phe Asn Gln Lys Gly Thr Ile Arg Thr Lys Tyr Gly 65 70 75 80 Thr Arg Asn Gln Leu Gln Ala Ala Val Asn Ala Leu Lys Ser Asn Gly 85 90 95 Ile Gln Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Ala Asp 100 105 110 Ala Thr Glu Met Val Arg Ala Val Glu Val Asn Pro Asn Asn Arg Asn 115 120 125 Gln Glu Val Ser Gly Glu Tyr Thr Ile Glu Ala Trp Thr Lys Phe Asp 130 135 140 Phe Pro Gly Arg Gly Asn Thr His Ser Asn Phe Lys Trp Arg Trp Tyr 145 150 155 160 His Phe Asp Gly Val Asp Trp Asp Gln Ser Arg Lys Leu Asn Asn Arg 165 170 175 Ile Tyr Lys Phe Arg Gly Asp Gly Lys Gly Trp Asp Trp Glu Val Asp 180 185 190 Thr Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Ala Asp Ile Asp Met 195 200 205 Asp His Pro Glu Val Val Asn Glu Leu Arg Asn Trp Gly Val Trp Tyr 210 215 220 Thr Asn Thr Leu Gly Leu Asp Gly Phe Arg Ile Asp Ala Val Lys His 225 230 235 240 Ile Lys Tyr Ser Phe Thr Arg Asp Trp Ile Asn His Val Arg Ser Ala 245 250 255 Thr Gly Lys Asn Met Phe Ala Val Ala Glu Phe Trp Lys Asn Asp Leu 260 265 270 Gly Ala Ile Glu Asn Tyr Leu Asn Lys Thr Asn Trp Asn His Ser Val 275 280 285 Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Ala Ser Lys Ser Gly 290 295 300 Gly Asn Tyr Asp Met Arg Gln Ile Phe Asn Gly Thr Val Val Gln Arg 305 310 315 320 His Pro Met His Ala Val Thr Phe Val Asp Asn His Asp Ser Gln Pro 325 330 335 Glu Glu Ala Leu Glu Ser Phe Val Glu Glu Trp Phe Lys Pro Leu Ala 340 345 350 Tyr Ala Leu Thr Leu Thr Arg Glu Gln Gly Tyr Pro Ser Val Phe Tyr 355 360 365 Gly Asp Tyr Tyr Gly Ile Pro Thr His Gly Val Pro Ala Met Lys Ser 370 375 380 Lys Ile Asp Pro Ile Leu Glu Ala Arg Gln Lys Tyr Ala Tyr Gly Arg 385 390 395 400 Gln Asn Asp Tyr Leu Asp His His Asn Ile Ile Gly Trp Thr Arg Glu 405 410 415 Gly Asn Thr Ala His Pro Asn Ser Gly Leu Ala Thr Ile Met Ser Asp 420 425 430 Gly Ala Gly Gly Asn Lys Trp Met Phe Val Gly Arg Asn Lys Ala Gly 435 440 445 Gln Val Trp Thr Asp Ile Thr Gly Asn Arg Ala Gly Thr Val Thr Ile 450 455 460 Asn Ala Asp Gly Trp Gly Asn Phe Ser Val Asn Gly Gly Ser Val Ser 465 470 475 480 Ile Trp Val Asn Lys 485 <210> 7 <211> 485 <212> PRT <213> Bacillus species <400> 7 His His Asn Gly Thr Asn Gly Thr Met Met Gln Tyr Phe Glu Trp His 1 5 10 15 Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Asp Asp Ala Ser 20 25 30 Asn Leu Arg Asn Arg Gly Ile Thr Ala Ile Trp Ile Pro Pro Ala Trp 35 40 45 Lys Gly Thr Ser Gln Asn Asp Val Gly Tyr Gly Ala Tyr Asp Leu Tyr 50 55 60 Asp Leu Gly Glu Phe Asn Gln Lys Gly Thr Val Arg Thr Lys Tyr Gly 65 70 75 80 Thr Arg Ser Gln Leu Glu Ser Ala Ile His Ala Leu Lys Asn Asn Gly 85 90 95 Val Gln Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Ala Asp 100 105 110 Ala Thr Glu Asn Val Leu Ala Val Glu Val Asn Pro Asn Asn Arg Asn 115 120 125 Gln Glu Ile Ser Gly Asp Tyr Thr Ile Glu Ala Trp Thr Lys Phe Asp 130 135 140 Phe Pro Gly Arg Gly Asn Thr Tyr Ser Asp Phe Lys Trp Arg Trp Tyr 145 150 155 160 His Phe Asp Gly Val Asp Trp Asp Gln Ser Arg Gln Phe Gln Asn Arg 165 170 175 Ile Tyr Lys Phe Arg Gly Asp Gly Lys Ala Trp Asp Trp Glu Val Asp 180 185 190 Ser Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Ala Asp Val Asp Met 195 200 205 Asp His Pro Glu Val Val Asn Glu Leu Arg Arg Trp Gly Glu Trp Tyr 210 215 220 Thr Asn Thr Leu Asn Leu Asp Gly Phe Arg Ile Asp Ala Val Lys His 225 230 235 240 Ile Lys Tyr Ser Phe Thr Arg Asp Trp Leu Thr His Val Arg Asn Ala 245 250 255 Thr Gly Lys Glu Met Phe Ala Val Ala Glu Phe Trp Lys Asn Asp Leu 260 265 270 Gly Ala Leu Glu Asn Tyr Leu Asn Lys Thr Asn Trp Asn His Ser Val 275 280 285 Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Ala Ser Asn Ser Gly 290 295 300 Gly Asn Tyr Asp Met Ala Lys Leu Leu Asn Gly Thr Val Val Gln Lys 305 310 315 320 His Pro Met His Ala Val Thr Phe Val Asp Asn His Asp Ser Gln Pro 325 330 335 Gly Glu Ser Leu Glu Ser Phe Val Gln Glu Trp Phe Lys Pro Leu Ala 340 345 350 Tyr Ala Leu Ile Leu Thr Arg Glu Gln Gly Tyr Pro Ser Val Phe Tyr 355 360 365 Gly Asp Tyr Tyr Gly Ile Pro Thr His Ser Val Pro Ala Met Lys Ala 370 375 380 Lys Ile Asp Pro Ile Leu Glu Ala Arg Gln Asn Phe Ala Tyr Gly Thr 385 390 395 400 Gln His Asp Tyr Phe Asp His His Asn Ile Ile Gly Trp Thr Arg Glu 405 410 415 Gly Asn Thr Thr His Pro Asn Ser Gly Leu Ala Thr Ile Met Ser Asp 420 425 430 Gly Pro Gly Gly Glu Lys Trp Met Tyr Val Gly Gln Asn Lys Ala Gly 435 440 445 Gln Val Trp His Asp Ile Thr Gly Asn Lys Pro Gly Thr Val Thr Ile 450 455 460 Asn Ala Asp Gly Trp Ala Asn Phe Ser Val Asn Gly Gly Ser Val Ser 465 470 475 480 Ile Trp Val Lys Arg 485

Claims

1. A detergent for automatically cleaning dishes, comprising at least one low-water gel phase, the gel phase containing at least one protease granule, wherein the at least one protease granule contains a protease according to SEQ ID NO: 5 from WO2017215925; wherein the gel phase contains 8-30 wt % of a gelling agent based on the total weight of the gel phase, the gelling agent being selected from gelatin, xanthan gum and / or polyvinyl alcohol, the detergent further comprising at least one solid phase, the detergent being a detergent portion in a water-soluble enclosure having one or more chambers / compartments, and the gel phase contained being in direct contact with the at least one solid phase in the chambers / compartments.

2. Cleaning agent according to claim 1, wherein the proportion by weight of all enzymes in the at least one gel phase is 0.0005 to 20.0% by weight, based on the amount of active enzyme protein, based on the total weight of the gel phase.

3. The cleaning agent according to claim 1, characterized in that The proportion by weight of the at least one protease, based on the amount of active enzyme protein of all proteases, relative to the total weight of the cleaning agent, is 0.005 to 5% by weight.

4. The cleaning agent according to claim 1, characterized in that The proportion by weight of all proteases in the at least one gel phase is from 0.0005 to 20.0% by weight, based on the amount of active enzyme protein, based on the total weight of the gel phase.

5. The cleaning agent according to claim 1, characterized in that Based on the amount of active enzyme protein added per wash cycle, all proteases were added in amounts ranging from 0.001 to 1,000 mg / work.

6. The cleaning agent according to claim 1 or 2, characterized in that The cleaning agent also comprises an alpha-amylase.

7. The cleaning agent according to claim 6, characterized in that The alpha-amylase is selected from: a) an alpha-amylase comprising an amino acid sequence that is at least 80% identical over its entire length to the amino acid sequence specified in SEQ ID NO: 5, and optionally has at least one amino acid substitution at one of positions 172, 202, 208, 255 and 261 according to the numbering of SEQ ID NO: 5; and / or b) an alpha-amylase comprising an amino acid sequence that is at least 60% identical over its entire length to the amino acid sequence specified in SEQ ID NO: 6, and optionally has at least one amino acid substitution at one of positions 172, 202, 208, 255 and 261 according to the numbering of SEQ ID NO: NO:6 The numbered position is 9, 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 195, 202, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 3 at least one amino acid substitution at one of positions 18, 319, 320, 323, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 458, 461, 471, 482 and 484, and / or a deletion at one of positions 183 and 184; and / or c) an alpha-amylase comprising an amino acid sequence that, over its entire length, corresponds to SEQ The amino acid sequence specified in SEQ ID NO:7 has at least 90% identity and optionally has at least one substitution and / or deletion at one of positions 93, 116, 118, 129, 133, 134, 140, 142, 146, 147, 149, 151, 152, 169, 174, 183, 184, 186, 189, 193, 195, 197, 198, 200, 203, 206, 210, 212, 213, 235, 243, 244, 260, 262, 284, 303, 304, 320, 338, 347, 359, 418, 431, 434, 439, 447, 458, 469, 476, and 477 according to the numbering of SEQ ID NO:

7.

8. The cleaning agent according to claim 7, characterized in that In a), the at least one amino acid substitution is selected from the group consisting of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N, R172Q, and combinations thereof.

9. The cleaning agent according to claim 7, characterized in that In b), the at least one amino acid substitution is at one of positions 9, 26, 149, 182, 186, 202, 257, 295, 299, 323, 339 and 345.

10. The cleaning agent according to claim 7, characterized in that In b), the at least one amino acid substitution is selected from the group consisting of R118K, D183*, G184*, N195F, R320K, R458K, and combinations thereof.

11. The cleaning agent according to claim 1 or 2, characterized in that The amount of the gelling agent is 8 to 22 wt %, based on the total weight of the gel phase.

12. The cleaning agent according to claim 1 or 2, characterized in that At least one organic solvent is contained in the gel phase.

13. The cleaning agent according to claim 12, characterized in that The at least one organic solvent is present in the gel phase in an amount of 30 to 90 wt %, based on the total weight of the gel phase.

14. The cleaning agent according to claim 1 or 2, characterized in that The gel phase contains a polymer comprising a monomer containing a sulfonic acid group.

15. The cleaning agent according to claim 1 or 2, characterized in that The cleaning agent comprises at least one liquid phase or else a gel phase or a solid phase.

16. Use of a cleaning agent according to any one of claims 1 to 15 for automatic cleaning of dishes.

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