WO2016198446A1

WO2016198446A1 - Phosphate-free dishwashing liquid

Info

Publication number: WO2016198446A1
Application number: PCT/EP2016/063023
Authority: WO
Inventors: Thomas Weber; Sven Müller; Hans Hartmut Janke; Johannes Zipfel
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2015-06-12
Filing date: 2016-06-08
Publication date: 2016-12-15
Also published as: DE102015210828A1

Abstract

The invention relates to a phosphate-free dishwashing liquid that has an improved stability and cleaning performance in particular for enzyme-sensitive marks, as well as to the use of said dishwashing product and to a method for washing dishes in a dishwasher using said dishwashing product.

Description

Phosphate-free liquid dishwashing detergent

The present invention relates to a phosphate-free, liquid dishwashing detergent which exhibits improved stability and cleaning performance, in particular of enzyme-sensitive soiling, the use of this dishwashing detergent and a method for machining

Dishwashing using this dishwashing detergent.

The most important criterion in automatic dishwashing is the cleaning performance on a wide variety of soiling, which are introduced into the dishwasher in the form of food residues. In this respect, there is generally a need for dishwashing detergents with increased cleaning performance. In addition, a general trend for reasons of environmental protection in machine dishwashing to dispense with phosphates is observed. The problem thus arises of providing phosphate-free automatic dishwashing detergents without the

Cleaning performance or stability is impaired.

To effectively remove baked stains, a dishwashing detergent requires alkalinity. Many other dried-on food residues require enzymes, such as amylases and proteases. However, there is the problem that alkalinity and enzymes together can not be stably formulated.

Liquid dishwashing detergents also require special stabilizers to stabilize the enzymes. These include, inter alia, calcium salts and especially for proteases additionally polyols and / or boric acid.

Finally, to optimize the performance of the dishwashing detergent, builders, e.g.

Aminocarboxylates, in particular glutamic diacetic acid (GLDA) or methylglycinediacetic acid (MGDA), and complexing agents required. As complexing agents in particular phosphonates, such as 1-hydroxyethane (1, 1-diphosphonic acid) (HEDP), are suitable.

However, if HEPP is formulated with a calcium salt in a phosphate-free formulation, calcium phosphonate may precipitate. This is undesirable on the one hand for aesthetic reasons, because the appearance of the product suffers from the white precipitates, and on the other hand, the reduced Enzyme performance through the loss of enzyme stabilizer. Furthermore, it is difficult to incorporate stable amounts of aminocarboxylates into liquid or gel formulations. The insufficient stability is particularly evident by phase separations, which are undesirable for aesthetic reasons.

Consumers also prefer multifunctional products which, in addition to the cleaning action, also provide rinse aid surfactant and salt replacement function. These requirements, however, aggravate the stability problems of existing formulations.

The object of the present invention was therefore to provide a phosphate-free, liquid dishwashing detergent which overcomes the stated stability problems and has a good cleaning performance.

It has now been found that a stable and thus visually appealing

Dishwashing agent formulation can be provided when the phosphonate used as a complexing agent is formulated spatially separated from enzymes and enzyme stabilizers and has a specific composition.

A first subject of the present invention is therefore a phosphate-free, liquid

Dishwashing detergent, preferably automatic dishwashing detergent, characterized in that the automatic dishwashing detergent comprises two spatially separate liquid

Compositions A and B, wherein

(a) Composition A is phosphonate-free, has a pH of less than 8.5, preferably 8 or less, more preferably 7 to 8, in particular about 7.5, and comprises:

(i) at least one enzyme, preferably a protease and / or amylase;

(ii) at least one for stabilizing the at least one enzyme

suitable enzyme stabilizer, wherein the at least one

Enzyme stabilizer based on the total weight of

Composition A comprises less than 0.1% by weight of boric acid and / or borate, preferably is free from boric acid and / or borate; and

(Iii) at least one builder, wherein the at least one builder based on the total weight of the composition A comprises less than 9 wt .-% glutamic diacetic acid (GLDA), preferably less than 5% by weight, in particular free of GLDA, and wherein the at least one builder preferably comprises methylglycinediacetic acid (MGDA); and (b) Composition B is enzyme- and calcium-free, has a pH greater than 9, preferably greater than 10, in particular greater than 10 to less than 11.5, and comprises:

(i) at least one phosphonate, in particular 1-hydroxyethane- (1, 1-diphosphonic acid) (HEDP); and

(ii) at least one builder, wherein the at least one builder based on the total weight of composition A comprises less than 3% by weight of glutamic diacetic acid (GLDA), preferably is free of GLDA, and wherein the at least one builder is preferably selected from methylglycinediacetic acid ( MGDA), soda, citrate and combinations thereof.

Likewise provided by the present invention is the use of a dishwashing agent according to the invention in a machine dishwashing process, in particular the use for improving the cleaning performance of enzyme-sensitive soiling on dishes during its cleaning in an automatic dishwashing machine.

Finally, the present invention is also directed to a machine dishwashing process in which a dishwashing composition according to the invention, in particular for the purpose, the

To improve cleaning performance of enzyme-sensitive stains, is used.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. All percentages are by weight unless otherwise specified. Numeric ranges specified in the format "from x to y" include the above values.If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints, also be recorded.

"At least one" as used herein includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more. With respect to an ingredient, the indication refers to the type of ingredient, not the absolute number Thus, for example, "at least one builder" means at least one type of builder, that is, one type of builder or a mixture of several different builders. The term "weight" refers to all compounds of the type indicated, those in the composition / mixture ie that the composition contains no further compounds of this type beyond the indicated amount of the corresponding compounds.

When referring to molecular weights herein, these references always refer to the number average molecular weight M _n , unless explicitly stated otherwise. The number average molecular weight can be determined, for example, by means of gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 with THF as the eluent. The mass average molecular weight M _w can also be determined by GPC, as described for M _n .

As used herein, "phosphate-free" or "phosphonate-free" means that the composition in question is substantially free of phosphates or phosphonates, i.

in particular phosphates or phosphonates in amounts less than 0.1 wt .-%, preferably less than 0.01 wt .-%, based on the respective composition contains.

"Calcium-free" as used herein means that the subject composition is in the

Substantially free of calcium salts, i. in particular calcium salts in amounts less than 0.1 wt .-%, preferably less than 0.07 wt .-%, more preferably less than 0.05 wt .-%, preferably less than 0.03 wt .-%, particularly preferably less than 0.01 wt .-%, based on the composition B contains.

"Enzyme-free" as used herein means that the corresponding composition is substantially free of enzymes, ie in particular enzymes or enzyme preparations or preparations in amounts less than 0.1% by weight, preferably less than 0.05% by weight. -%, preferably less than 0.01 wt .-%, in particular less than 0.001 wt .-% based on the respective composition, here composition B contains.

"Borate or boric acid free" as used herein means that the composition in question is substantially free of borates or boric acid, ie in particular borates or boric acid in amounts less than 0.05% by weight, preferably less than 0.01% by weight .-%, in particular less than 0.001 wt .-% based on the composition.

"GLDA-free" or "free of GLDA" as used herein means that the subject

Composition is substantially free of glutamic diacetic acid (GLDA), ie in particular GLDA in amounts less than 1 wt .-%, preferably less than 0.1 wt .-%, in particular less than 0.01 wt .-% based on the composition , The corresponding information also covers the salts of GLDA. "Monoethanolamine-free" as used herein means that the composition in question is substantially free of ethanolamine, ie in particular ethanolamine in amounts less than 0.1% by weight, preferably less than 0.01% by weight, in particular less than Contains 0.001 wt .-% based on the composition.

"NaOH-free" as used herein means that the composition in question is in the

Essentially no sodium hydroxide (NaOH) was added. In certain embodiments, the composition contains NaOH in amounts less than 0.5% by weight, preferably less than 0.1% by weight of the particular composition. However, it is to be understood that these amounts do not refer to agents or compositions in which sodium and hydroxide ions are dissociated and in which the corresponding ions may also be derived, for example, from KOH and sodium citrate.

"Liquid" as used herein includes liquids and gels.

The stated pH of the respective composition in the different

Embodiments refers to the pH measured with a standard electrode in the undiluted state at 25 ° C.

The term "spatially separated" with respect to the compositions as used herein means that the compositions can not come into contact with each other prior to use. Usually, the dishwashing detergent is provided in a multi-compartment package such as a bottle or pouch for this purpose. in particular a two-chamber bottle or a Zweichammerpouch, wherein the respective composition is separate from the other composition (s) in a separate chamber.

Preferably, composition A contains at least one amylase and at least one protease. In further embodiments, composition A additionally contains at least one further enzyme. Suitable enzymes include, but are not limited to, proteases, lipases, hemicellulases, particularly pectinases and / or mannanases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.

These enzymes and the amylases and proteases used are in principle of natural origin; starting from the natural molecules are available for use in

Dishwashing improved variants are available, which are used according to preferred. Dishwashing compositions according to the invention preferably contain the respective enzymes in total amounts of from 1 × 10 ^-6 to 5% by weight, based in each case on active protein and the

Total weight of the respective composition. The protein concentration can help with known methods, for example the BCA method or the biuret method.

Proteases are among the most technically important enzymes of all. For detergents and dishwashing detergents, they are the longest established enzymes and contained in virtually all modern, powerful detergents and dishwashing detergents. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. An overview of this family is provided, for example, by the article "Subtilases: Subtilisin-like Proteases" by R. Siezen, pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996. Subtilases are naturally occurring formed by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.

Examples of the subtilisin-type proteases preferably used in washing and dishwashing detergents are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483,

Subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7 attributable to the subtilases, but no longer to the subtilisins in the narrower sense, as well as variants of said proteases which have an altered amino acid sequence compared to the starting protease. Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in dishwashing detergents. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens

(DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to obtain peracids in situ from suitable precursors produce. These include, for example, the lipases which are obtainable or further developed from Humicola lanuginosa (Thermomyces lanuginosus), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, particularly preferably T213R and N233R.

Furthermore, enzymes can be used which are termed hemicellulases

be summarized. These include, for example, mannanases, xanthanlyases,

Pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or

Chemical-impermeable protective layer is coated. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating. Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention each contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and

in particular between 0.8 and 10% by weight of the enzyme protein.

Preference is given in particular to those dishwashing detergent compositions, in particular composition A, which, based in each case on their total weight, contains from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight contain each enzyme preparation.

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.

For this purpose, the dishwashing agents may contain, for example, calcium salts as stabilizers. Water-soluble calcium salts useful as enzyme stabilizers include, but are not limited to, calcium chloride (CaCk), calcium lactate or calcium acetate. Also suitable are other salts of calcium with alpha-hydroxycarboxylic acids or alpha-amino acids.

Suitable calcium salts for stabilizing enzymes are in various

Embodiments in Composition A in an amount of 0.05 to 2 wt .-%, in particular 0.1 to 0.6 wt .-%, based on the total weight of the composition A included.

In addition to or as an alternative to the calcium salts, the dishwashing detergent may comprise further stabilizers, in particular selected from boronic acids, their salts and esters, peptides, peptide derivatives, peptide adducts, polyols and combinations of the abovementioned. Preferred polyols are in particular glycerol, propylene glycol and / or sorbitol. preferred

Boronic acid compounds are phenylboronic acid derivatives, in particular the phenylboronic acid derivative 4-formyl-phenylboronic acid (4-FPBA). Further preferred phenylboronic acid derivatives may also have further chemical modifications on the phenyl ring, in particular they may contain one or more methyl, amino, nitro, chloro, fluoro, bromo, hydroxyl, formyl, ethyl , Acetyl, t-butyl, anisyl, benzyl, trifluoroacetyl, N-hydroxysuccinimide, t-butyloxycarbonyl, benzoyl, 4-methylbenzyl, thioanizyl, thiocresyl, benzyloxymethyl, 4-nitrophenyl,

Benzyloxycarbonyl, 2-nitrobenzoyl, 2-nitrophenylsulphenyl, 4-toluenesulphonyl,

Pentafluorophenyl, diphenylmethyl, 2-chlorobenzyloxycarbonyl, 2,4,5-trichlorophenyl, 2-bromobenzyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, triphenylmethyl, 2,2,5,7,8-pentamethylchroman-6-sulphonyl Contain radicals or groups or combinations thereof. Generally, the term "boronic acids" as used herein includes all compounds of the formula R-B (OH) 2 in which R is an organic radical and salts and esters thereof in which one or both of the hydrogens are cations or an organic radical are replaced.

In various embodiments, the compounds of the general structural formula can furthermore be used as enzyme stabilizers

ZA- (A) _n -NH-CH (R) -Y (I) wherein A is an amino acid residue (preferred amino acid residues A are selected from Ala, Gly, Val, Ile, Leu, Phe, Lys); Y is -C (O) -X or CHOH-SOsB, B is hydrogen or a suitable cation, in particular (alkali) metal cation, X is hydrogen or CF 3; Z is an N-capping moiety selected from phosphoramidate [(R'O) 2 (O) P-], sulfenamide [(SR ') 2-],

Sulfonamide [(R '(O) ₂ S-], sulfonic acid [SO3H], phosphinamide [(R') 2 (O) P-], sulfamoyl derivatives

[R'0 (0) ₂ S-], thiourea [(R ') ₂ N (O) C-], thiocarbamate [R'0 (S) C-], phosphonate [R'-P (0) OH] , Amidophosphate [R'0 (OH) (O) P-], carbamate (R'O (O) C-) and urea (R'NH (O) C-), where each R 'is independently selected from straight chain or branched C1-C6 unsubstituted alkyl, phenyl, C7-C9 alkylaryl and cycloalkyl radicals, wherein the cycloalkyl ring is a C4-C8

May be cycloalkyl and may contain one or more heteroatoms selected from O, N, and S; R is selected from straight-chain or branched C1-C6 unsubstituted alkyl, phenyl and C7-C9 alkylaryl radicals, in particular -CH2-phenyl or -CH2- (4-hydroxyphenyl); and n is 0, 1 or 2, preferably 0 or 1, wherein when n is not 0 the amino acids are linked via a peptide bond.

Preferred radicals R are selected from methyl, isopropyl, sec-butyl, isobutyl, C6H5, -CH2-C6H5, -CH2-C6H4OH (in particular CH2- (4-hydroxyphenyl), and -CH2-CH2-C6H5, such that the -NH-CH (R) -Y portion of the compound of formula (I) is derived from the amino acids Ala, Val, Ile, Leu, Tyr, PGIy (phenylglycine), Phe and HPhe (homophenylalanines) by the carboxyl group Although such residues are therefore not amino acids (although they may be synthesized from an amino acid precursor), for convenience herein exemplified enzyme stabilizers are the aldehyde moiety of the inhibitors. the one of the corresponding amino acids is denoted by the suffix "H" after the analogous amino acid (eg, "-AlaH" represents the radical "-NHCH (CH ₃ ) C (O) H"). Trifluoromethylketone are likewise characterized by the additive "CF3" after the analogous amino acid (eg, standing "-AlaCF _3" for the radical "-NHCH _(CH3) C (0) CF _3"). Finally, the bisulfite adducts of aldehydes by adding "SO3H" or "S0 ₃ Na" after the analogous amino acid referred to (for example, "-TyrSOsH" represents the radical "-NHCH (CH2C6H ₄ OH) CHOH-S0 ₃ H" ).

The aldehydes of the present invention can be prepared from the corresponding amino acids by converting the C-terminal carboxyl group of the amino acid into an aldehyde group. Such aldehydes may be prepared by known methods, e.g. in U.S. Pat. Pat. No. 5015627, EP 0 185 930, EP 0 583 534 and DE 3200812.

The trifluoromethyl ketones can also be prepared from the corresponding amino acids by converting the C-terminal carboxyl group into a trifluoromethyl ketone group. Such trifluoromethyl ketones can be prepared by known methods, for example as described in EP 0 583 535.

The N-terminal end of the enzyme stabilizers is protected by a protecting group capping the N-terminus, the group being selected from carbamates, ureas,

Sulfonamides, phosphonamides, thioureas, sulfenamides, sulfonic acids, phosphinamides, thiocarbamates, amidophosphates and phosphonamides. In a preferred embodiment, however, the N-terminal end is replaced by a methyl, ethyl or benzyl carbamate group [CH 3 O- (O) C-; CH ₃ CH ₂ O- (0) C-; or C 6 H 5 CH ₂ O- (O) C-], a methyl, ethyl or benzyl urea group [CH ₃ NH- (O) C-; CH ₃ CH ₂ NH- (O) C-; or CeH ₅ CH ₂ NH- (O) C-], a methyl, ethyl or

Benzylsulfonamide group [CH ₃ S0 ₂ -; CH ₃ CH ₂ S0 ₂ -; or CeHsChhSOH, or a methyl, ethyl or benzylamidophosphate group [CH ₃ O (OH) (O) P-; CH ₃ CH ₂ 0 (OH) (0) P-; or C ₆ H ₅ CH ₂ O (OH) (O) P-].

For example, the synthesis of the N-capping groups can be found in the following documents: Protective Groups in Organic Chemistry, Greene, T., Wuts, P., John Wiley & Sons, New York, 1991, pp 309-405; March, J, Advanced Organic Chemistry, Wiley Interscience, 1985, pp. 445, 469, Carey, F. Sundberg, R., Advanced Organic Chemistry, Part B, Plenum Press, New York, 1990, p. 686-89; Atherton, E., Sheppard, R., Solid Phase Peptide Synthesis, Pierce Chemical, 1989, pp. 3-4; Grant, G., Synthetic Peptides, W.H. Freeman & Co. 1992, pp. 77-103; Stewart, J., Young, J., Solid Phase Peptide Synthesis, 2nd Edition, IRL Press, 1984, pp. 3,5,11, 14-18, 28-29. Bodansky, M., Principles of Peptide Synthesis, Springer-Verlag, 1988, pp. 62, 203, 59-69; Bodansky, M., Peptide Chemistry, Springer-Verlag, 1988, pp. 74-81, Bodansky, M.,

Bodansky, A., The Practice of Peptide Synthesis, Springer-Verlag, 1984, pp. 9-32. Exemplary enzyme stabilizers that can be used in the present invention include, but are not limited to: CH ₃ O- (0) C-Leu-LeuH; CH ₃ 0- (0) C-Ala-LeuH; CH ₃ CH ₂ 0- (0) C-Ala-LeuH; C6H ₅ CH ₂ 0- (0) C-Ala-LeuH; CH ₃ O- (0) C-Ala-Leu CF ₃ ; CH ₃ CH ₂ 0- (0) C-Ala-LeuCF _3;

C6H ₅ CH ₂ 0- (0) C-Ala-LeuCF _3; CH ₃ O- (0) C-Al-AlH; CH ₃ CH ₂ 0- (0) C-Ala-LLEH; C ₆ H ₅ CH20- (0) C-Ala NeH; CH ₃ O- (0) C-Ala-Ile CF ₃ ; CH ₃ CH ₂ 0- (0) C-Ala-lleCF _3; C6H ₅ CH ₂ 0- (0) C-Ala-lleCF _3; CH ₃ 0- (0) C-Gly-LeuH; CH ₃ CH ₂ 0- (0) C-Gly-LeuH; C ₆ H ₅ CH ₂ O- (0) C-Gly-LeuH; CH ₃ 0- (0) C-Gly-LeuCF _3;

CH ₃ CH ₂ 0- (0) C-Gly-LeuCF _3; C ₆ H ₅ CH ₂ O- (0) C-Gly-LeuCF ₃ ; CH ₃ 0- (0) C-Gly-LLEH; CH ₃ CH ₂ 0- (0) C-Gly-LLEH; C6H ₅ CH ₂ O- (0) C-Gly-LH; CH ₃ 0- (0) C-Gly-lleCF _3; CH ₃ CH ₂ 0- (0) C-Gly-lleCF _3; C ₆ H ₅ CH ₂ O- (0) C-Gly-Ile CF ₃ ; CH ₃ NH- (0) C-Ala-LeuH; CH ₃ CH ₂ NH- (0) C-Ala-LeuH; C ₆ H ₅ CH ₂ NH- (O) C-Ala-LeuH; CH ₃ NH- (0) C-Ala-LeuCF _3; CH ₃ CH ₂ NH- (0) C-Ala-LeuCF _3; C ₆ H ₅ CH ₂ NH- (O) C-Ala-LeuCF ₃ ; CH ₃ NH- (O) C-AlAlH; CH ₃ CH ₂ NH- (O) C-AlAlH; C ₆ H ₅ CH ₂ NH- (O) C-Al-AlH; CH ₃ NH- (O) C-Ala-1le CF ₃ ; CH ₃ CH ₂ NH- (O) C-Ala-1le CF ₃ ; C6H ₅ CH ₂ NH- (0) C-Ala-lleCF _3; CH ₃ NH- (0) C-Gly-LeuH; CH ₃ CH ₂ NH- (O) C-Gly-LeuH; C ₆ H ₅ CH ₂ NH- (0) C-Gly-LeuH; CH ₃ NH- (0) C-Gly-LeuCF _3; CH ₃ CH ₂ NH- (0) C-Gly- LeuCF _3; C ₆ H ₅ CH ₂ NH- (0) C-Gly-LeuCF ₃ ; CH ₃ NH- (0) C-Gly-H; CH ₃ CH ₂ NH- (0) C-Gly-LLEH;

C ₆ H ₅ CH ₂ NH- (0) C-Gly-H; CH ₃ NH- (0) C-Gly-lleCF _3; CH ₃ CH ₂ NH- (0) C-Gly-lleCF _3; C ₆ H ₅ CH ₂ NH- (0) C-Gly-lleCF _3; CH ₃ S0 ₂ -Ala-LeuH; CH ₃ CH ₂ S0 ₂ -Ala-LeuH; C ₆ H ₅ CH ₂ S0 ₂ Ala-LeuH; CH ₃ S0 ₂ -Ala- LeuCF ₃ ; CH ₃ CH ₂ SO ₂ -Ala-LeuCF ₃ ; C ₆ H ₅ CH ₂ S ₂ -Ala-LeuCF ₃ ; CH ₃ S0 ₂ -Ala-LH; CH ₃ CH ₂ S0 ₂ -Ala-LH; C6H ₅ CH ₂ S0 ₂ -Ala-LH; CH ₃ S0 ₂ -Ala-lleCF ₃ ; CH ₃ CH ₂ S0 ₂ -Ala-lleCF ₃ ; C6H ₅ CH ₂ S0 ₂ -Ala-lleCF _3;

CH ₃ S0 ₂ -Gly-LeuH; CH ₃ CH ₂ S0 ₂ -Gly-LeuH; C ₆ H ₅ CH ₂ S0 ₂ -Gly-LeuH; CH ₃ S0 ₂ -Gly-LeuCF ₃ ;

CH ₃ CH ₂ SO ₂ -Gly-LeuCF ₃ ; C ₆ H ₅ CH ₂ S0 ₂ -Gly-LeuCF _3; CH ₃ S0 ₂ -Gly-LH; CH ₃ CH ₂ S0 ₂ -Gly-LLEH;

C ₆ H ₅ CH ₂ S0 ₂ -Gly-LLEH; CH ₃ S0 ₂ -Gly-IleCF ₃ ; CH ₃ CH ₂ S0 ₂ -Gly-lleCF _3; C6H ₅ CH ₂ S0 ₂ -Gly-lleCF _3;

_CH3 0 (OH) (0) P-Ala-LeuH; CH ₃ CH ₂ 0 (OH) (0) P-Ala-LeuH; C ₆ H ₅ CH ₂ O (OH) (O) P-Ala-LeuH;

CH ₃ O (OH) (O) P-Ala-Leu CF ₃ ; CH ₃ CH ₂ 0 (OH) (0) P-Ala-LeuCF _3; C ₆ H ₅ CH ₂ 0 (OH) (0) P-Ala-LeuCF _3; CH ₃ O (OH) (O) P-Al-AlH; CH ₃ CH ₂ O (OH) (O) P-AladalH; C ₆ H5CH ₂ 0 (OH) (0) P-allyl;

_CH3 0 (OH) (0) P-Ala-lleCF _3; CH ₃ CH ₂ 0 (OH) (0) P-Ala-lleCF _3; C ₆ H5CH ₂ 0 (OH) (0) P-Ala-1le CF ₃ ;

_CH3 0 (OH) (0) P-Gly-LeuH; CH ₃ CH ₂ 0 (OH) (0) P-Gly-LeuH; C ₆ H ₅ CH ₂ O (OH) (0) P-Gly-LeuH;

_CH3 0 (OH) (0) P-Gly-LeuCF _3; CH ₃ CH ₂ 0 (OH) (0) P-Gly-LeuCF _3; C ₆ H ₅ CH ₂ O (OH) (0) P-Gly-LeuCF ₃ ; _CH3 0 (OH) (0) P-Gly-LLEH; CH ₃ CH ₂ 0 (OH) (0) P-Gly-LLEH; C ₆ H5CH ₂ O (OH) (0) P-Gly-H;

_CH3 0 (OH) (0) P-Gly-lleCF _3; CH ₃ CH ₂ 0 (OH) (0) P-Gly-lleCF _3; C6H ₅ CH ₂ O (OH) (0) P-Gly-IleCF ₃ ; CH ₃ 0- (0) C-Val-Ala-LeuS0 ₃ Na; C ₆ H ₅ CH ₂ O- (0) C-Gly-Ala-TyrH; C ₆ H ₅ CH ₂ O- (0) C-Gly-Ala-TyrSO ₃ H;

C ₆ H ₅ CH ₂ O- (0) C-Gly-Ala-TyrS0 ₃ Na; C ₆ H ₅ O- (0) C-Gly-Ala-TyrSO ₃ H; and C ₆ H ₅ O- (0) C-Gly-Ala-TyrSO ₃ Na. In the above compounds, the terminology described above will be used to identify the aldehyde or trifluoromethyl ketone groups, respectively.

In various embodiments, the invention also encompasses all stereoisomers,

in particular enantiomers and diastereomers, tautomers and salts of the above

described compounds. In general, the peptide derivatives and peptide adducts used as stabilizers can be selected from those disclosed in the patent publications WO 2013/004636 A1, WO 2014/173980 A2, WO 2013/004635 A1, WO2014 / 124927 A2, WO2009 / 118375 A2, US Pat. No. 6,165,966 and US Pat

US2011 / 0039752 A1 are described.

Since it has now been found that boric acid and its salts adversely affect the stability of the agents, the agents of the invention contain based on the total weight of the

Composition A less than 0.3 wt .-% boric acid and / or borate, in particular less than 0.1 wt .-% boric acid and / or borate, preferably they are free of boric acid and / or borate.

Particularly preferred according to the invention is the use of calcium salts, polyols, boronic acids and / or peptide derivatives / adducts, in particular a combination of

Calcium salts, in particular calcium chloride, and polyols, in particular sorbitol, with

Boronic acids, such as 4-FPBA, or with peptide adducts, such as those described above. The

Calcium salts are used in the amounts described above. The polyols are usually used in amounts of 5-10% by weight, based on the total weight of the composition, of the boronic acids / peptide adducts in amounts of up to 1% by weight,

typically up to 0.1% by weight.

As a phosphonate, all are generally suitable as complexing agents for dishwashing detergents

Phosphonates can be used. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are present in the compositions preferably in amounts of from 0.5 to 3% by weight, in particular in amounts of from 1 to 2.6% by weight, in each case based on the total weight of the composition B. In preferred embodiments, the amount is not more than 300 mg phosphorus / job.

The dishwashing agents described herein are of a liquid nature and may, in particular, be present as homogeneous solutions or suspensions. In a further preferred

Embodiment of the invention, the dishwashing detergent is in a pre-portioned form. The automatic dishwashing detergent has several spatially separate compositions, making it possible, on the one hand, to separate incompatible ingredients from one another, and, on the other hand, to offer compositions in combination which are used at different times in the dishwasher. The dishwashing agents further comprise at least one builder in the form that composition A contains at least one builder, wherein the at least one builder based on the total weight of the composition A less than 9 wt .-%

Glutamic diacetic acid (GLDA) or salts thereof, preferably less than 5% by weight, in particular less than 2% by weight glutamine diacetic acid (GLDA) or its salts, and very particularly preferably is free from GLDA, and composition B contains at least one builder in which the at least one builder, based on the total weight of the composition A, comprises less than 3% by weight, in particular less than 2% by weight of glutamic diacetic acid (GLDA) or salts thereof, preferably is free of GLDA.

Among the usable builders include in particular carbonates, citrates, phosphonates, organic builders and silicates. The proportion by weight of the total builders at

Total weight of compositions according to the invention is preferably 10 to 80 wt .-%, more preferably 15 to 70 wt .-% and in particular 20 to 50 wt .-%.

Suitable organic builders according to the invention are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five

Carry acid functions throughout the molecule. Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and

Glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), aspartic diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), and derivatives thereof, and mixtures of this, wherein glutamine-N, N-diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA) as described above is preferably excluded. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, MGDA and mixtures thereof.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the

Macromolecule), polyaspartates, polyacetals and dextrins. In addition to their builder effect, the free acids typically also have the property of an acidifying component and can thus also serve to adjust the pH.

In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

In various preferred embodiments, the at least one builder is in

Composition A and / or B methylglycinediacetic acid (MGDA). In further

In embodiments, composition B contains two or more builders, such as soda and / or citrate, optionally in combination with MGDA. Generally, the term MGDA, as used herein, encompasses both the free acid and the corresponding salts.

In various embodiments, dishwasher detergents according to the invention contain as one of their essential builders one or more salts of citric acid, ie citrates, for example sodium or potassium citrate. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 25 wt .-%, particularly preferably 10 to 20 wt .-%, most preferably 12 to 17 wt .-%, each based on the total weight of the respective composition A or B. In various embodiments, composition A contains no citrate. In different others

Embodiments comprises composition B citrate, especially sodium citrate, preferably in an amount of 10 to 20% by weight, in particular 12 to 17% by weight, for example about 14% by weight.

Also preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate (soda), in amounts of from 2 to 50% by weight, preferably from 4 to 30% by weight. % and in particular from 5 to 20 wt .-%, most preferably 6 to 15 wt .-%, each based on the weight of the composition A or B. In various embodiments, composition A contains no

Carbonate / bicarbonate. Contains in various other embodiments

Composition B Carbonates / bicarbonates, in particular soda, preferably in an amount of 6 to 15 wt .-%, in particular 7 to 12 wt .-%.

Particularly preferred dishwashing agents according to the invention, preferably mechanical

Dishwashing detergent, are characterized in that composition B contains at least two builders from the group of silicates, phosphonates, carbonates, MGDA and citrates, wherein the weight fraction of these builders, based on the total weight of

Composition, preferably 5 to 70 wt .-%, preferably 10 to 50% by weight and in particular 15 to 40 wt .-% is. The combination of two or more builders from the above-mentioned group has for the cleaning and rinsing performance according to the invention Detergents, in particular dishwashing detergents, preferably automatic dishwasher detergents, have proven to be advantageous. In addition to the builders mentioned here, one or more other builders may additionally be present.

Preferred dishwashing detergents are characterized by a builder combination in composition B of citrate and carbonate and / or bicarbonate. In such embodiments, a mixture of carbonate and citrate is used, wherein the amount of carbonate preferably 3 to 30 wt .-% and in particular from 4 to 20 wt .-%, most preferably 5 to 15 wt .-%, and the amount to citrate preferably from 2 to 40 wt .-%, in particular from 3 to 30 wt .-%, particularly from 4 to 25 wt .-%, particularly preferably 5 to 20 wt .-%, most preferably 7 to 17 wt. -%, in each case based on the total weight of

Composition B, is, wherein the total amount of these two builders is preferably 10 to 40 wt .-%, more preferably 15 to 30 wt .-%, in particular not more than 25 wt .-%.

Particularly preferred are those agents in which composition B additionally contains MGDA in addition to the citrate and the soda. The wt .-% - proportion of MGDA in such

Compositions B is preferably 0 to 20 wt .-%, in particular 1 to 15 wt .-%, especially 2 to 8 wt .-%. In various embodiments of the invention contains

Composition B up to 5 wt .-%, for example 2 to 4 wt .-% MGDA. The particularly preferred amounts of citrate and soda are as described in the preceding paragraph.

Composition A in various embodiments contains at least one builder, which builder is MGDA. Composition A may contain additional builders, in particular citrate, but in various embodiments no further builder is included. The amount of MGDA in Composition A is preferably up to 25% by weight, more preferably 2 to 20% by weight, especially 8-15% by weight. In certain embodiments

Composition A up to 13% by weight of MGDA.

As organic builders which can be used according to the invention, polymeric polycarboxylates are furthermore suitable; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol. Suitable polymers are, in particular, polyacrylates, which are preferably a

Have molecular weight of 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group. Geschirrspülmitte according to the invention can as a builder also crystalline layered silicates of general formula NaMSix02x + i ^■ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and secondary wash properties. In preferred cleaning agents according to the invention, in particular dishwashing detergents, preferably dishwasher detergents, the content of silicates, based on the total weight of the detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight , It is particularly preferred that the agents are free of silicates, "free" in this context meaning that the amount is limited to less than 0.1% by weight.

In addition to the aforementioned builders, the inventive

Dishwashing agent, in particular composition B, further alkali metal hydroxides as alkali source. These alkali carriers are particularly preferred in the compositions and especially in the second phases (composition B) only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-% between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the composition used. In various other embodiments, Composition B contains less than 1.71% by weight, based on the total weight of Composition B, of NaOH, preferably less than 1.0% by weight of NaOH, more preferably Composition B is free of NaOH. In different

Embodiments therefore contain composition B instead of NaOH potassium hydroxide (KOH) as alkali source, preferably in the amounts indicated above, in particular up to 3.5 wt .-%. In particular, the alkali metal hydroxides, especially KOH, are used in amounts such that the pH values of the compositions according to the invention are achieved.

The dishwashing agents preferably also contain at least one surfactant. In this case, the surfactants may be contained both in composition A and in composition B or both. However, the at least one surfactant is preferably present in composition A, most preferably in amounts of up to 4% by weight, based on the total weight of composition A.

The surfactants contained are preferably nonionic surfactants. As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. With particular preference, the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.

Particular preference is given to nonionic surfactants which have a melting point above

Have room temperature. Nonionic (s) surfactants having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In the context of the present invention, particularly preferred nonionic surfactants have been low-foaming nonionic surfactants which contain alternating ethylene oxide and ethylene oxide

Have alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

Ri-O- (CH ₂ -CH ₂ -O) - (CH ₂ -CH-O) - (CH ₂ -CH ₂ -O) - (CH 1 -C H-0) -H

R2 R3

in which R is a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24-alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6.

Thus, particularly preferred are nonionic surfactants having a C9-alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units, followed by 1 to 4

Ethylene oxide units followed by 1 to 4 propylene oxide units.

Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH 2 O- (AO) w- (AO) x- (A "O) _y - (A"'O) z R ² , in which

R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical;

R ^{2 is} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, Α ', A "and A'" independently of one another are radicals from the group -CH 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 ),

w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.

By the addition of the aforementioned nonionic surfactants of the general formula R - CH (OH) CH20 - (AO) w - (AO) x - (A "0) y - (A '" 0) zR ² , hereinafter also referred to as

"Hydroxymix ether", the cleaning performance of the invention

Preparations are significantly improved both in comparison to surfactant-free system as well as compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

Preference is given in particular to those end-capped, poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 0 [CH ₂ CH ₂ O] xCH ₂ CH (OI-l) R ² , in addition to a radical R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic

Hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22

Carbon atoms, further having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, wherein x for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60 stands.

Particular preference is given to surfactants of the formula R 0 [CH 2 CH (CH 3) O] x [CH ² CH ² O] yCH ² CH (OH) R ² in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear one or branched

Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands.

The group of these nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i (EO) iso-4o-2-hydroxyalkyl ethers, in particular also the ceria fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH ₂ O] x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² in which R and R ² independently of one another are linear or branched , saturated or single or multiple

unsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH 3, -CH 2 CH 3, -CH 2 CH 2 -CH 3, -CH (CH 3) 2, but preferably is -CH 3, and x and y independently of each other for between values 1 and 32, with nonionic surfactants with R ³ = -CH ³ and values for x of 15 to 32 and y of 0.5 and 1.5 being very particularly preferred. Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH (R ³ ) O] x [CH ₂ ] k CH (OH) [CH ² ] jOR ² where R and R ^{2 are} linear or branched , saturated or unsaturated, aliphatic or aromatic

Hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is Values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5. When the value x> 2, each R ³ in the above formula R 0 [CH ₂ CH (R ³ ) O] x [CH ₂ ] k CH (OH) [CH ² ] jOR ^{2 may be} different. R and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22

Carbon atoms, with radicals having 8 to 18 carbon atoms are particularly preferred. For the radical R ³ , H, -Chta or -CH 2 CH ³ are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ³ ) units which may be joined 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 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula zu

RO [CH ₂ CH (R ³ ) O] x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula R 1, R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R and R ² Have 9 to 14 carbon atoms, R ^{3 is} H and x assume values of 6 to 15.

Finally, the nonionic surfactants of the general formula R -CH (OH) CH ₂ O- (AO) wR ^{2 have} proven to be particularly effective, in which

R for a straight-chain or branched, saturated or on or

polyunsaturated C6-24 alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26

Carbon atoms; A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ),

preferably CH 2 CH 2, and

w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40

The group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.

In various embodiments of the invention, instead of the above-defined end-capped hydroxy mixed ethers, the corresponding ones can not

end-capped hydroxy mixed ethers. These may satisfy the above formulas, but R ² is hydrogen and R, R ³ , A, Α ', A ", A'", w, x, y and z are as defined above.

Preferred dishwashing detergents are characterized in that the dishwashing detergent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant on the

Total weight of the dishwashing agent is preferably 0.1 to 10 wt .-%, preferably 0.5 to 8.0 wt .-% and in particular 1, 0 to 4.0 wt .-%.

The dishwashing compositions according to the invention, in particular composition A, may further comprise at least one sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the composition is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 15 wt .-%, particularly preferably 1, 0 to 10 wt .-%, in particular from 2 to 8 Wt .-%, especially from 3 to 6 wt .-%. Very particular preference is given to compositions which contain up to 6% by weight of sulfopolymer. The sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymers.

The sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.

The copolymers may have two, three, four or more different monomer units.

Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)

Monomer (s) at least one monomer from the group of unsaturated carboxylic acids. Unsaturated carboxylic acid (s) used are / are unsaturated carboxylic acids of the formula R (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12

Carbon atoms, with -NH2, -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid,

Maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ independently of one another are -H, -CH 3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH 2, -OH or -COOH, or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched

Is hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from - (CH 2) n - with n = 0 to 4, -COO- (CH 2) k - with k = 1 to 6, - C (0) -NH-C (CH ₃₎ ₂ -, -C (0) -NH-C (CH ₃₎ 2 CH ₂ - and -C (0) -NH-CH (CH ₃₎ -CH ₂ -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H in which R ⁶ and R ^{7 are} independently selected

from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X is an optional

Spacer group which is selected from - (CH 2) n - with n = 0 to 4, -COO- (CH 2) k - with k = 1 to 6, -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 -. Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized

Sulfonsäuregruppenhaltigen copolymers is inventively preferred.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the share of

Carboxylic acid-containing monomers 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred dishwashing detergents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably of 4,000 to 25,000 gmol and in particular of 5,000 to 15,000 gmol ^-1 .

In another preferred embodiment, the copolymers include besides

Carboxyl-containing monomer and sulfonic acid-containing monomer further at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention. The nonionic monomers used are preferably monomers of the general formula R (R ² ) C =C (R ³ ) -XR ⁴ , in which R to R ^3, independently of one another, is -H, -CH ₃ or -C 2 H 5, X is an optional one existing spacer group which is selected from -CH 2 -, -C (0) 0- and -C (0) -NH-, and R ^{4 is} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, 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-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22 alpha-olefin, 2-styrene, alpha Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid pentyl ester,

Acrylic acid hexyl ester, methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (meth) acrylate. Lauryl) acrylamide, acrylic acid stearyl ester, methacrylic acid stearyl ester, N- (stearyl) acrylamide, acrylic acid behenyl ester, methacrylic acid behenyl ester and N- (behenyl) acrylamide or mixtures thereof.

The monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.

In general, the pH of the dishwashing detergent can be adjusted by means of customary pH regulators. In various embodiments, the pH (neat, measured at 25 ° C.) of the composition A is in a range from 5.5 to 8.5, preferably 6.5 to 8.0, particularly preferably from 7.0 to 8, 0, in particular at about 7.5, and the pH of the composition B is in a range of 9.0 to 12, preferably 10.0 to 11, 5, preferably greater than 10, in particular 10.5 to 11, 5 , The pH adjusting agents used are acids and / or alkalis, preferably Alkalis. Suitable acids are in particular organic acids such as acetic acid,

Citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, but also the mineral acids

Hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof are used.

Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides

and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide is preferred. Particularly preferably, the above-described alkali source is used to adjust the pH. Even if volatile alkali, for example in the form of ammonia and / or

Alkanolamines which may contain up to 9 carbon atoms in the molecule can be used to adjust the pH, wherein the alkanolamine is hereby selected from the group consisting of mono-, di-, triethanol- and -propanolamine and their Mixtures, is preferably dispensed with such volatile alkali, in particular ethanolamines. Thus, in various embodiments, the compositions contain less than 1.75% by weight of alkanolamine, especially monoethanolamine, most preferably they are free thereof. It has been found that omitting such alkanolamines, the stability of the

Increases compositions.

"Approximately" as used herein in connection with a numerical value means

Numerical value ± 5%. "About 7.5", therefore means 7.125 to 7.875.

To adjust and / or stabilize the pH, the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which at the same time complexing agents or even

Chelating agents (chelators, INCI chelating agents) are. Particularly preferred buffer substances are citric acid or citrates, in particular the sodium and potassium lead,

for example, trisodium citrate2H20 and tripotassium citrate Ή2Ο.

The agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, in particular anionic surfactants, bleaching agents, bleach activators,

Bleach catalysts, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances and antimicrobial agents.

Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), especially sulfosuccinic acid mono- and di-Cs-O-alkyl esters, sulfosuccinamates,

Sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides),

Fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ^ XR ^ XR ^ N ⁺ ChhCOO- in which R ⁱ is an optionally interrupted by hetero atoms or hetero atom groups alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^v are identical or different Alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula

(R ^VI ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^" , in which R ^vi to R ^ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X ^" for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Other suitable cationic surfactants are the quaternary

surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of bismuth, magnesium and zinc salts as well as the magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in dishwashing detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt. the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 to 1 wt.%, preferably between 0.02 and 0.5 wt.% and in particular between 0.04 and 0.2 wt. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent. In particular, for example, zinc acetate can be used. Additionally or alternatively to the abovementioned salts (in particular the zinc salts), polyethyleneimines, such as are obtainable, for example, under the name Lupasol® (BASF), preferably in an amount of 0 to 5 wt .-%, in particular 0.01 to 2 wt .-%, as

Glaskorrosioninhibitoren be used.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

The thickeners used are preferably xanthan or polyacrylates. In various embodiments, at least one of the compositions, preferably both, contains at least one thickener, for example a polyacrylate, typically in an amount sufficient to adjust the desired viscosity, for example, in an amount of from 0.5 to 1.5 wt. %, preferably 0.75 to 1, 0 wt .-% based on the total weight of

Composition.

In various embodiments of the invention, composition A contains:

(i) at least one amylase and at least one protease and optionally at least one further enzyme selected from the group consisting of lipases, hemicellulases, in particular pectinases and / or mannanases, cellulases, perhydrolases and oxidoreductases, (ii) at least one calcium salt, in particular calcium chloride (CaCb ), in an amount of 0.05 to 2 wt .-%, in particular 0.1 to 0.6 wt .-% based on composition A, (iii) at least one further enzyme stabilizer is selected from boronic acids, their salts and esters , in particular 4-formylphenylboronic acid (4-FPBA), peptides, peptide derivatives, peptide adducts, in particular peptide-aldehyde and peptide-dehydrogen sulfite adducts, polyols, in particular glycerol and sorbitol, and combinations of the abovementioned, (iv) at least one surfactant, preferably in an amount up to 4% by weight, based on the total weight of the

Composition A; and (v) at least one sulfopolymer, preferably in an amount of up to 6% by weight based on the total weight of the composition A. Optionally, thickeners, dyes, perfume, corrosion inhibitors and / or preservatives and small amounts of pH adjusters may also be included be.

In various embodiments of the invention, composition B contains:

(i) HEDP as phosphonate in the amounts indicated above, in particular in amounts of up to 3% by weight, typically 2-3% by weight, based on the total weight of the composition,

(ii) Builder in the form of a combination of citrate, soda and MGDA, especially in amounts of up to 17% by weight, up to 15% by weight or up to 5% by weight, (iii) adjusting an alkali source, preferably KOH, in an amount corresponding to the pH, and optionally also (iv ) a rinse aid polymer, in particular a cationic polyacrylate (ie a copolymer which in addition to acrylic acid as a monomer and cationically charged monomers, in particular

Diallyldialkylammonium compounds). Optionally, thickeners, dyes, perfume, corrosion inhibitors and / or preservatives may be included.

The formulation of dishwashing agents described herein can take place in different ways. The liquid forms of supply based on water and / or organic

Solvents may be thickened, in the form of gels.

In various embodiments, the detergent immediately after production has a viscosity above 2000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 2000 and 10,000 mPas. After storage, the viscosity may be higher, for example greater than 10,000 mPas, for example in the range 10000-50000 mPas,

preferably around 35000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C).

The dishwashing agents described herein are preferably packaged in a multi-chamber bottle, in particular in a two-chamber bottle, and dosed out of this, preferably into the dosing chamber of the dishwasher. According to another embodiment, the dishwashing agent is preferably prefabricated into metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g. In order to achieve an optimum cleaning and rinse-aid result, preference is given to those automatic dishwashing agents which are present in the form of a prefabricated dosing unit and between 0.001 and 1 g, preferably between 0.01 and 0.1 g, particularly preferably between 0.01 and 0, 07 g and in particular between 0.01 and 0.05 g of the polymer a) or between 0.1 and 2.5 g, preferably between 0.2 and 2.2 g, particularly preferably between 0.3 and 1, 9 g and in particular between 0.4 and 1.5 g of nonionic surfactant (s) b). The volume of the aforementioned metering units and their spatial form are chosen with particular preference so that a metering of the prefabricated units on the metering a

Dishwasher is guaranteed. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The dishwashing agents in the prefabricated metering units have a water-soluble sheath with particular preference. The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent. In different

Embodiments, the films have the form of Mehrkammerpouches, wherein the

Compositions A and B are spatially separated in different chambers of a pouch made of a water-soluble film.

It is preferred that the water-soluble coating be polyvinyl alcohol or a

Contains polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose

Molecular weight in the range of 10,000 to 1,000,000 gmol ^"1 , preferably from 20,000 to 500,000 gmol, more preferably from 30,000 to 100,000 gmol ^{" 1} and in particular from 40,000 to 80,000 gmol ¹ .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

In addition, a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath

(Meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added. A preferred additional polymer is polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred. Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

It may be preferred that the film material contains further additives. The film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,

Propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further

Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.

Suitable water-soluble films for use in the water-soluble sheaths of

water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The corresponding use of the automatic dishwasher detergents according to the invention is likewise an object of the invention. The invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used. The subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the

Means according to the invention during the passage of a dishwashing program before the start of the main wash cycle or during the main wash cycle into the interior of a

Dishwasher is metered. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.

Examples

Example 1: Formulation stability

The stability of the following formulations was determined by storage at 40 ° over 4 weeks:

Table 1: Composition of the automatic dishwashing agent (% by weight of active substance)

V = comparative formulation

Alkaliphase (AP) Preparation B Rez. 26 Revis. 21 (V) Revis. 25 (V) Re. 28 (V)

Water 66 66 66 66

HEDP 2.5 2.5 2.5 2.5

Thickener (polyacrylate) 0,90 0,90 0,90 0,90

GLDA (tetrasodium salt) - 3,4 - 3,4

MGDA (tetrasodium salt) 2.9 - 2.9 - KOH 2.77 - - 2.94

NaOH - 2.10 2.15 -

Soda 9,00 9,00 9,00 9,00

Monoethanolamine - 1, 75 - -

Cationic acrylate copolymer 0.19 0.19 0.19 0.19

Sodium citrate x 2H2O 14.00 14.00 14.00 14.00

Residues (perfume, dyes, preservatives, ad 100 ad 100 ad 100 ad 100 water, etc.) (wt .-%)

pH (undiluted, 25 ° C) 10.6 1 1, 3 10.6 10.6

Stability Stable PhaseSlightly light flocculation flocculation

V = comparative recipe

Example 2: Cleaning performance in automatic dishwashing

In a Miele G698SC dishwasher at 50 ° C (program "Normal") and 21 ° dH dishes with various soils with a 1: 1 mixture of the enzyme and alkali phase (Rez.44 and 26 from Example 1, 15 ml / job ) and after each rinse cycle visually determines the cleaning performance according to IKW (evaluation of 1-10, the higher the value, the better the performance, differences of at least 1 are significant.) The results for the recipes tested are in Table 2 as arithmetic Mean values are listed Higher values mean better cleaning performance.

Table 2: Cleaning performance on enzyme-sensitive soiling

It can be clearly seen from the table that the formulation according to the invention shows a special performance on protease- and amylase-sensitive soiling.

Claims

claims

1. A phosphate-free liquid dishwashing detergent, preferably automatic dishwashing detergent, characterized in that the automatic dishwashing detergent two spatially

having separate liquid compositions A and B, wherein

(a) Composition A is phosphonate-free, has a pH of less than 8.5, preferably 8 or less, more preferably 7 to 8, especially 7.5, and comprises:

(i) at least one enzyme, preferably a protease and / or amylase;

(ii) at least one for stabilizing the at least one enzyme

suitable enzyme stabilizer, wherein the at least one

Enzyme stabilizer based on the total weight of

(Iii) at least one builder, wherein the at least one builder based on the total weight of the composition A comprises less than 9 wt .-% glutamic diacetic acid (GLDA), preferably less than 5% by weight, in particular free of GLDA, and wherein the at least one builder preferably comprises methylglycinediacetic acid (MGDA); and

(b) Composition B is enzyme- and calcium-free, has a pH greater than 9, preferably greater than 10, in particular greater than 10 to less than 11.5, and comprises:

2. Dishwashing detergent according to claim 1, characterized in that composition A at least one amylase and at least one protease and optionally at least one further enzyme selected from the group consisting of lipases, hemicellulases, in particular pectinases and / or mannanases, cellulases, perhydrolases and

Contains oxidoreductases.

3. Dishwasher according to claim 1 or 2, characterized in that

Composition A (I) as the at least one enzyme stabilizer at least one calcium salt, in particular calcium chloride (CaCk), in an amount of 0.05 to 2% by weight, in particular 0.1 to 0.6 wt .-% based on composition A contains; and or

(ii) as the at least one enzyme stabilizer one or more

Containing compound (s) selected from boronic acids, their salts and esters, peptides, peptide derivatives, peptide adducts, polyols, and combinations of the foregoing.

4. Dishwasher according to one of claims 1 to 3, characterized in that

Composition A

(I) contains at least one surfactant, preferably in an amount of up to 4 wt .-% based on the total weight of the composition A;

and or

(ii) contains at least one sulfopolymer, preferably in an amount of up to 6% by weight, based on the total weight of the composition A; and or

(iii) contains at least one thickener, preferably xanthan or a

Polyacrylate.

5. dishwashing detergent according to one of claims 1 to 4, characterized in that

Composition A contains (i) at least one amylase and at least one protease and optionally at least one further enzyme selected from the group consisting of lipases, hemicellulases, in particular pectinases and / or mannanases, cellulases, perhydrolases and oxidoreductases, (ii) at least one calcium salt, in particular Calcium chloride (CaCk), in an amount of 0.05 to 2 wt .-%, in particular 0.1 to 0.6 wt .-% based on composition A, (iii) at least one further

Enzyme stabilizer which is selected from boronic acids, their salts and esters, in particular 4-formylphenylboronic acid (4-FPBA), peptides, peptide derivatives,

Peptide adducts, in particular peptide-aldehyde and peptide-dehydrogen sulfite adducts, polyols, in particular glycerol and sorbitol, and combinations of the abovementioned, (iv) at least one surfactant, preferably in an amount of up to 4% by weight, based on the total weight of the composition A; and (v) at least one sulfopolymer, preferably in an amount of up to 6% by weight, based on the total weight of the composition A.

6. dishwashing detergent according to one of claims 1 to 5, characterized in that

Composition B (i) contains at least one alkali source, the alkali source, based on the total weight of composition B, containing less than 1.7% by weight of NaOH, preferably being free of NaOH, and preferably comprising KOH; and or

(ii) based on the total weight of the composition B contains less than 1, 75 wt .-% monoethanolamine, preferably free of

Monoethanolamine is.

7. Dishwashing detergent according to one of claims 1 to 6, characterized in that

Composition B

(I) which contains at least one phosphonate, in particular HEDP, in an amount of 0.5 to 3 wt .-%, preferably 1 to 2.6 wt .-% based on composition B, in particular in an amount of not more than 300 mg phosphorus / job; and or

(ii) the at least one builder comprises MGDA, preferably in combination with one of soda and citrate, more preferably in combination with soda and citrate, in particular in an amount of up to 5.0% by weight of MGDA, up to 17% by weight Citrate and up to 15 wt .-% soda, each based on the total weight of the composition B.

8. Dishwashing detergent according to one of claims 1 to 7, characterized in that the dishwashing detergent at least one further constituent, preferably at least two further constituents selected from the group consisting of polymers,

Contains corrosion inhibitors, glass corrosion inhibitors, fragrances and perfume carriers.

9. Use of a dishwashing detergent according to one of claims 1 to 8 in one

automatic dishwashing process.

10. Machine dishwashing method, characterized in that a dishwashing detergent according to one of claims 1 to 8 is used.