EP3325597B1 - Machine dishwashing detergent with bleaching agents, builders and enzymes - Google Patents

Description

Automatic dishwashing detergent containing bleach, builders and enzymes

The present invention relates to a machine dishwashing detergent which exhibits improved cleaning performance, in particular on enzyme-sensitive soiling, the use of this dishwashing agent and a method for machine dishwashing using this dishwashing agent.

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

In the EP 2 217 690 A1 describes a composition comprising an enzyme and a bleaching compound, the enzyme and the bleaching compound being formulated in separate areas, ie spatially separated from one another, since this separation has a positive effect on the stability of the enzyme. In the formulations described, a builder is also contained in the enzyme area, the builder comprising methylglycinediacetic acid (MGDA). Other multi-phase dishwashing detergents containing MGDA are from US 2014/0018278 A1 , DE 102013225485 A1 and US 2013/0199569 A1 known.

Starting from the known prior art, the object of the present invention was to provide a, preferably phosphate-free, machine dishwashing detergent which has a further increased cleaning performance.

It has now surprisingly been found that it is advantageous for cleaning performance, especially on enzyme-sensitive soiling, in particular protease-sensitive soiling, and with regard to the storage stability of the enzymes, if the enzyme phase is largely free of organic builders, in particular MGDA, and the organic builders, especially MGDA, contained in the bleaching phase of the agent.

A first object of the present invention is therefore a machine dishwashing detergent, comprising (A) an enzyme phase, the enzyme phase containing at least one enzyme and being essentially free of bleaching agents and organic builders from the class of the aminocarboxylic acids and their salts; and (B) a bleaching phase, the bleaching phase containing at least one bleaching agent, at least one bleaching catalyst and at least one organic builder from the class of aminocarboxylic acids and their salts, in particular methylglycinediacetic acid (MGDA) or its salts.

The present invention also relates to the use of an automatic dishwashing agent according to the invention in an automatic dishwashing process, in particular the use to improve the cleaning performance of enzyme-sensitive soiling on dishes when cleaning them in an automatic dishwasher.

Finally, the present invention also relates to a machine dishwashing method in which an automatic dishwashing agent according to the invention is used in particular for the purpose of improving the cleaning performance of enzyme-sensitive soiling.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not restricted to these examples. Unless otherwise stated, all percentages are% by weight. Numerical ranges that are specified in the format "from x to y" include the values mentioned. If several preferred numerical ranges are specified in this format, it goes without saying that all ranges that result from the combination of the different endpoints are also covered.

"At least one" as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In relation to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. "At least one bleaching catalyst" thus means, for example, at least one type of bleaching catalyst, ie that one type of bleaching catalyst or a mixture of several different bleaching catalysts can be meant. Together with the weight, the information relates to all compounds of the specified type which are contained in the composition / mixture, ie that the composition contains no further compounds of this type beyond the specified amount of the corresponding compounds.

If reference is made here to molecular weights, this information always relates 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) in accordance with DIN 55672-1: 2007-08 with THF as the eluent. The mass average molecular weight M _w can also be determined by means of GPC, as described for M _n .

Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein relate to% by weight, in each case based on the mixture in question.

"Substantially free of" or "Free of" as used herein means that the ingredient in question is present in the appropriate phase or agent in a negligible amount, especially in an amount that is insufficient for the typical functionality of the ingredient is.

The enzyme phase is preferably "essentially free of MGDA or its salts". In particular, this information relates to amounts of 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.01% by weight or less , most preferably 0.001 wt% or less or 0.0001 wt% or less, each based on the weight of the enzyme phase. Corresponding amounts also apply to the expression "phosphate-free", the abovementioned proportions by weight in each case based on the total cleaning agent.

The bleaching phase is preferably “essentially free of enzymes”. In particular, this information relates to amounts of enzyme protein of 0.1% by weight or less, preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.001% by weight or less, most preferably 0.0005% or less or 0.0001% or less, each based on the weight of the bleach phase.

In the context of the present invention, unless otherwise stated, fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or their derivatives obtainable, for example, according to RoELEN's oxo synthesis can also be used accordingly.

Whenever alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is naturally only present in half the amount of the substance - sufficient to balance the charge - like the anion.

The agents of the present invention contain at least one enzyme, preferably in the form of an enzyme preparation or enzyme composition, which can contain one or more enzymes. Suitable enzymes include, but are not limited to, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred. Cleaning agents ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Proteases are among the most technically significant enzymes. They are the longest established enzymes for detergents and cleaning agents and are found in practically all modern, powerful detergents and cleaning agents. They break down protein-based soiling on the items to be cleaned. Of these, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are serine proteases due to the catalytically active amino acids. They act as non-specific endopeptidases and hydrolyze any acid amide bonds that are inside peptides or proteins. Their pH optimum is usually in the clearly alkaline range. An overview of this family can be found in the article " Subtilases: Subtilisin-like Proteases "by R. Siezen, page 75-95 in " Subtilisin enzymes ", edited by R. Bott and C. Betzel, New York, 1996 . Subtilases are naturally formed by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.

Examples of the proteases of the subtilisin type which are preferably used in washing and cleaning agents 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 subtilases, but no longer the subtilisins in the narrower sense enzymes Thermitase, Proteinase K and the proteases TW3 and TW7, and variants of the proteases mentioned which have an amino acid sequence which is different from that of the starting protease. Proteases are changed in a targeted or random manner by methods known from the prior art and are thus optimized, for example, for use in detergents and cleaning agents. This includes point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. 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, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L, T213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenol oxidases) can be used according to the invention. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.

In various embodiments of the invention, the agent contains at least one protease and, preferably, also at least one amylase.

A protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Detergents can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

Proteases and amylases that are active in cleaning are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers or other auxiliaries.

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

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

As can be seen from the previous description, 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 contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.

Particularly preferred are those compositions which, based on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations.

Unless otherwise stated, the weight information on enzymes means the amount of active enzyme protein based on the total mass of the entire composition. In a preferred embodiment, the enzyme phase contains at least 0.0001% by weight, preferably at least 0.001% by weight, in particular at least 0.01% by weight, particularly preferably at least 0.05% by weight, very particularly preferably at least 0 , 1 wt% protease per gram of total composition. In a further preferred embodiment, the enzyme phase contains at least 0.0001% by weight, preferably at least 0.0005% by weight, in particular at least 0.001% by weight, particularly preferably at least 0.005% by weight, very particularly preferably at least 0.01 % By weight of amylase per gram of the total composition.

According to a particularly preferred embodiment, the enzyme phase contains at least 0.0005% by weight, in particular at least 0.001% by weight, particularly preferably at least 0.005% by weight, very particularly preferably at least 0.01% by weight of amylase per gram of the total composition and at least 0.001% by weight, in particular at least 0.01% by weight, particularly preferably at least 0.05% by weight, very particularly preferably at least 0.1% by weight of protease per gram of the total composition.

The compositions described herein can also include enzyme stabilizers. A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this, including above all derivatives with aromatic groups, for example ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenyl-boronic acid, or the salts or Esters of the compounds mentioned. Peptide aldehydes, ie oligopeptides with a reduced C-terminus, in particular those of 2 to 50 monomers, or their hydrogen sulfite adducts are also used for this purpose. The peptide reversible protease inhibitors include, among others, ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin as well as fusion proteins from proteases and specific peptide inhibitors are also suitable for this.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Further enzyme stabilizers are known to the person skilled in the art from the prior art.

The bleaching catalysts which can be used according to the invention include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Complexes of manganese in oxidation state II, III, IV or IV are particularly preferably used, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleaching catalyst (s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 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 contain 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 ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (µ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III M _n ^IV (µ-O) ₁ (g-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (µ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (µ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Machine dishwashing detergent, characterized in that it is a bleaching catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) are preferred according to the invention, since the cleaning result can be significantly improved in particular by the aforementioned bleaching catalysts.

The aforementioned bleach-enhancing transition metal complexes, in particular with the central atoms Mn and Co, are preferably used in an amount of up to 1% by weight, in particular from 0.001% by weight to 0.1% by weight and particularly preferably from 0.01% by weight. % to 0.05 wt .-%, each based on the total weight of the agent used. In special cases, however, more bleaching catalyst can also be used.

The bleaching agents which can be used according to the invention are substances which are active in washing or cleaning. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. All other inorganic or organic peroxy bleaches known to the person skilled in the art can also be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents. Suitable materials that release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Preferably the bleach is in an amount of 1-35% by weight and more preferably 2-30% by weight, 3.5-25% by weight, 4-20% by weight and particularly preferably 5 -15% by weight in the dishwashing detergent according to the invention, based in each case on the total weight of the dishwashing detergent. Preferred dishwashing detergents are further characterized in that the dishwashing detergent, based in each case on the total weight of the dishwashing detergent, contains 2 to 20% by weight, preferably 3 to 18% by weight and in particular 4 to 15% by weight sodium percarbonate.

Particularly preferred embodiments of dishwashing detergents according to the invention are characterized in that the bleaching catalyst is selected from the group of the bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of the complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (methane TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN), and / or
the source of hydrogen peroxide is sodium percarbonate, sodium perborate tetrahydrate or sodium perborate monohydrate, or a combination thereof. The bleaching catalyst is very particularly preferably a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), in particular [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ , or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) or a mixture thereof, and the hydrogen peroxide source sodium percarbonate. In the combinations mentioned, the bleaching catalyst and the hydrogen peroxide source are preferably present in the above-mentioned amounts.

In various embodiments of the invention, the automatic dishwashing detergents additionally contain at least one bleach activator. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. All of the bleach activators known to the person skilled in the art from the prior art are acylated multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) is particularly preferably used. TAED is very particularly preferred. Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, in each case based on the total weight of the agent used. In contrast to the bleaching agent and the bleaching catalyst, the bleach activators can be formulated in the enzyme phase of the agent. In various embodiments, this is a preferred embodiment, which is used to separate bleach and bleach activator from one another in the agent.

Finally, the agents according to the invention contain at least one builder from the class of aminocarboxylic acids and their salts. A particularly preferred representative of this class is methylglycinediacetic acid (MGDA) or salts thereof, but glutamine diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS) can also be used. The content of these aminocarboxylic acids, in particular MGDA, or their salts can be, for example, between 5 and 35% by weight, preferably between 10 and 25% by weight and in particular between 10 and 20% by weight, in each case based on the total weight of the By means of make out. Aminocarboxylic acids and their salts can be used together with other builders, in particular also with the phosphate-free builders, which are described below.

The agents described herein comprise at least two separate phases, namely at least one enzyme-containing phase or at least one bleach-containing phase.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. One phase differs from another phase by different features, for example ingredients, physical properties, external appearance, etc. Different phases can preferably be distinguished optically. For the consumer, the at least one first phase must be clearly distinguished from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, these can likewise be distinguished from one another with the naked eye because they differ from one another, for example, in terms of their coloring. The same applies if there are two or more second phases. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a color or transparency difference. Phases in the sense of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye. The individual phases can have different properties when used, such as speed, with which the phase dissolves in water and thus the speed and sequence of the release of the ingredients contained in the respective phase.

The phases are typically spatially separated from one another. In various embodiments, this can be done such that if one or both of the phases are liquid phases, the liquid phase is separate from the other phase in a separate, closed area, for example the chamber of a pouch. Such forms of confection are known in the prior art. With fixed funds, i.e. If both phases are solids, the two phases are also made up spatially separated from one another, for example in the form of a multi-chamber pouch, each of the phases being present in a separate chamber. Alternatively, in the case of compacted means, such as tabs or tablets, in particular multi-phase tabs as are known in the prior art, the two phases can be arranged directly adjacent to one another in such a way that the phases are formulated separately and contact each other, but cannot mix.

The agents according to the invention preferably contain at least one further constituent, in particular at least two further constituents, selected from the group consisting of further builders, surfactants, polymers, corrosion inhibitors and glass corrosion inhibitors, disintegration aids, fragrances and perfume carriers.

Possible ingredients are described below, which can advantageously be used in the automatic dishwashing detergents according to the invention.

Additional builders can advantageously be used. The additional builders that can be used include, in particular, zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - phosphates. However, the agents are preferably phosphate-free.

Crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particular preference being used Values for x are 2, 3 or 4, and y stands for a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} .y H ₂ O are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyait), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, makatite). For the purposes of the present invention, crystalline sheet silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x represents 2, are particularly suitable. In particular, both are δ-sodium disitikate Na ₂ Si ₂ O ₅ .y H ₂ O and, above all, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite ), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3 H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but in particular Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) is preferred.

Automatic dishwashing detergents preferably contain from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0, of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O. 4 to 10 wt .-%, each based on the total weight of these agents.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is understood to mean that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle , cause.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in the compositions in amounts of 3 to 60% by weight, preferably 8 to 50% by weight. -% and in particular from 20 to 40 wt .-%, each based on the weight of the automatic dishwashing detergent, are included. The silicates are preferably formulated separately from the enzyme phase and, optionally, also the bleaching phase and can be contained, for example, in a third phase of the agent. Examples of such a packaging are the known solid dishwasher detergent tablets with 2 phases and a core, the core here being able to contain the silicate, for example.

Although it is also possible to use the generally known phosphates as builders, the agents described here are preferably phosphate-free.

The dishwashing detergents can also contain, in particular, phosphonates as additional builders, which according to the invention are not subsumed under the phosphates. A hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. Phosphonates are contained in the detergents preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, in each case based on the total weight of the dishwashing detergent. The phosphonates are preferably also formulated separately from the enzyme phase, so that in various embodiments the enzyme phase contains no phosphonates. The phosphonates can be formulated, for example, in the bleaching phase.

Other builders are the alkali carriers. Alkali carriers include, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, being preferred for the purposes of this invention. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred. Because of their low chemical compatibility with the other ingredients of machine dishwashing detergents compared to other builder substances, the optional alkali metal hydroxides are preferably only used in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent. Agents which contain less than 0.5% by weight and in particular no alkali metal hydroxides, based on their total weight, are particularly preferred.

It is particularly preferred to use carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate, in amounts of 2 to 50% by weight, preferably 5 to 40% by weight and in particular from 7.5 to 30% by weight, based in each case on the weight of the automatic dishwashing detergent. The alkali carriers mentioned are also preferably made up separately from the enzyme phase and can be contained, for example, in the bleaching phase.

Other organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder action, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

The use of citric acid and / or citrates in these agents has proven to be particularly advantageous for the cleaning and rinsing performance of agents according to the invention. According to the invention, therefore, automatic dishwashing agents are preferred, characterized in that the automatic dishwashing agent contains citric acid or a salt of citric acid and that the proportion by weight of citric acid or the salt of citric acid is preferably more than 5% by weight, in particular between 10 and 40% by weight. is. Citric acid and citrates can also be formulated in the enzyme phase.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as builders.

The agents according to the invention can contain surfactants, the group of surfactants including nonionic, anionic, cationic and amphoteric surfactants.

All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x , in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol is, which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

However, low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The dishwasher detergents particularly preferably contain nonionic surfactants from the group of the alkoxylated alcohols.

A class of nonionic surfactants that can be used, which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Preferred surfactants come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.
Davon sind insbesondere nichtionische Tenside bevorzugt, die einen C_9-15-Alkylrest mit 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten, gefolgt von 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten aufweisen.Suitable nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here are nonionic surfactants of the general formula

preferred, in which R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} 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, z independently of one another represent integers from 1 to 6.
Of these, particular preference is given to nonionic surfactants which have a C _9-15 -alkyl radical having 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.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, - CH₂-CH(CH₂-CH₃) stehen,
• w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Preferred nonionic surfactants are those of the general formula

R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² ,

in the

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 represents} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A, A ', A "and A'" independently of one another for a radical 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 stand for values between 0.5 and 120, where x, y and / or z can also be 0.

Those end group-capped, poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _× CH ₂ CH (OH) R ² , are preferred in addition to a radical R ¹ which is saturated for linear or branched or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x is from 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Particularly preferred are surfactants of the above formula in which R ^{1 is} C ₇ to C ₁₃ , x is an integer from 16 to 28 and R ^{2 is} C ₈ to C ₁₂ .

Also preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 up to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.

The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2 -hydroxydecyl ether. Those end group-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² are particularly preferred, are also preferred ² independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} selected independently of one another from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably stands for -CH ₃ , and x and y independently of one another have values between 1 and 32, nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ² for 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, isopropyl, n-butyl, 2-butyl or 2 -Methyl-2-butyl radical, x stand for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . 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 can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if 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 can be joined 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 for x has been chosen here as an example and may well be larger, 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 group-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [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 represents numbers 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 ¹ and R ^{2 has} 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht

Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proven to be particularly effective in which

• R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ^{2 represents} 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 C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

In various embodiments of the invention, the corresponding non-end-capped hydroxy mixed ethers can also be used instead of the end group-capped hydroxy mixed ethers. These can satisfy the above formulas, but R ² is hydrogen and R ¹ , R ³ , A, A ', A ", A"', w, x, y and z are as defined above.

The compositions described herein, which comprise at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in various embodiments in an amount based on the total weight of the composition of at least 2% by weight, preferably at least 5% by weight. %. The absolute amounts used per application can be, for example, in the range of 0.5-10 g / job, preferably in the range of 0.5-5 g / job.

Nonionic surfactants which have a melting point above room temperature are particularly preferred. Nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C. is / are particularly preferred .

All anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Instead of the surfactants mentioned or in conjunction with them, cationic and / or amphoteric surfactants such as betaines or quaternary ammonium compounds can also be used. However, it is preferred that no cationic and / or amphoteric surfactants are used.

The amounts given above for the surfactants and other builders described usually relate to the amounts which are used when the respective surfactant or the respective builders are used alone, unless explicitly stated otherwise. It is therefore self-evident that if several surfactants or builders are used, the quantities must be adjusted accordingly.

The agents described herein may also contain various polymers.

According to the invention, for example, homopolymers of α, β ethylenically unsaturated carboxylic acids can be used in various embodiments. Unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH are used as unsaturated carboxylic acid (s), in which R ¹ to R ³ independently of one another are -H, -CH ₃ , one 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 as defined above or for -COOH or -COOR ⁴ , where 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 (methyl maleic acid), methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof. Acrylic acid is very particularly preferred. In various embodiments of the invention, the homopolymer is therefore a polyacrylic acid.

The carboxylic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the carboxylic acid group in some or all of the carboxylic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. The use of partially or fully neutralized polymers is preferred according to the invention.

The molar mass of the homopolymers used can be varied in order to adapt the properties of the polymers to the desired use. Preferred dishwashing detergents are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M _n of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1100 to 10000 g / mol, and particularly preferably from 1200 to 5000 g / mol, can in turn be preferred from this group.

In various preferred embodiments of the invention, the agents further contain at least one sulfopolymer. The polymers which can be used in this connection are in particular copolymers which can have two, three, four or more different monomer units, at least one monomer unit carrying a sulfonic acid group. In addition to monomer (s) containing sulfonic acid groups, preferred copolymers contain at least one monomer from the group of unsaturated carboxylic acids.

The unsaturated carboxylic acids described above are used with particular preference as unsaturated carboxylic acid (s). Acrylic acid is very particularly preferred.

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H

preferably 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, with NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or represent -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents 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 (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -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

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO 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 represents 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 (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-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the copolymers too, the acid groups can be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic and / or carboxylic acid group in some or all 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 copolymers is preferred according to the invention.

The monomer distribution of the preferably used copolymers is preferably 5 to 95% by weight in each case in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from the aforementioned.

In various embodiments, the copolymers can contain, in addition to the above-described monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, further monomers, in particular monomers containing unsaturated carboxylic acid ester groups. In such terpolymers, the monomers containing carboxylic acid ester groups are, for example, those of the formula R ¹ (R ² ) C = C (R ³ ) COOR ⁴ , in which R ¹ to R ^{3 are} as defined above and R ^{4 is} a saturated or unsaturated, straight-chain or is a branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, sorbic acid, cinnamic acid or mixtures thereof. C _1-8 alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, are very particularly preferred. Ethyl acrylate is very particularly preferred.

The molecular weight of the copolymers used can be varied in order to adapt the properties of the polymers to the intended use. Preferred dishwashing detergents are characterized in that the copolymers have molecular weights M _n from 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol.

The homopolymers and copolymers described above can each be used in amounts of 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total weight of the composition. Absolute amounts are typically in the range of 0.1 to 2 g / job, preferably in the range of 0.2 to 1.0 g / job. The mass ratio of the polymers to one another, i.e. Homopolymer to copolymer, in various embodiments is 5: 1 to 1: 5, preferably 2: 1 to 1: 2.

The dishwashing detergents can alternatively or additionally contain further polymers. The group of suitable polymers includes, in particular, the cleaning-active amphoteric, zwitterionic or cationic polymers, for example the rinse aid polymers and / or polymers which act as softeners.

Preferred amphoteric polymers that can be used come from the group of alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid copolymers, alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / methacrylic acid / alkylaminoalkyl ( ) -acrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or non-ionic monomers.

Other zwitterionic polymers that can be used come from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine / methacrylate copolymers.

Cationic polymers that can be used come from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, the copolymers of vinylpyrrolidone with quaternylamino derivatives of quaternylamino derivatives and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

• die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the aforementioned amphoteric, zwitterionic or cationic polymers are present in pre-assembled form. Among other things, this is suitable for packaging the polymers

• the encapsulation of the polymers by means of water-soluble or water-dispersible coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• the encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30 ° C;
• the cogranulation of the polymers with inert carrier materials, preferably with carrier materials from the group of active washing or cleaning substances, particularly preferably from the group of builders (builders) or cobuilders.

Automatic dishwashing detergents preferably contain the aforementioned cationic and / or amphoteric polymers in amounts between 0.01 and 10% by weight, in each case based on the total weight of the automatic dishwashing detergent. In the context of the present application, however, preference is given to machine dishwashing detergents in which the proportion by weight of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0 and 01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent.

In general, the pH of the dishwashing detergent can be adjusted using conventional pH regulators, the pH being selected depending on the intended use. In various embodiments, the pH is in a range from 5.5 to 11, preferably 5.5 to 10.5, more preferably 7 to 10.5, in particular greater than 7, especially in the range 8 to 10. As pH Serving agents 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, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, volatile alkali is particularly preferred, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.

To adjust and / or stabilize the pH, the agent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate · 2H ₂ O and tripotassium citrate · H ₂ O.

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

In the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. However, mixtures of different fragrances are preferably used, which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Preservatives can also be contained in the agents. Preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable, for example such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, Thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) -bis- (1-octanamine) dihydrochloride, N, N'-bis - (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surface-active compounds, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

In general, the machine dishwashing detergents described here can be assembled in different ways. The agents can be in solid or liquid as well as a combination of solid and liquid supply forms. In particular, powders, granules, extrudates, compactates, in particular tablets, are suitable as fixed supply forms. The liquid supply forms based on water and / or organic solvents can be thickened, in the form of gels. The agents are packaged in the form of multi-phase products. The individual phases of such multiphase agents can have the same or different physical states.

The dishwashing detergents can be in the form of moldings. In order to facilitate the disintegration of such prefabricated moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into these agents in order to shorten the disintegration times. Tablet disintegrants or accelerators of disintegration are understood to mean auxiliary substances which ensure the rapid disintegration of tablets in water or other media and the rapid release of the active substances. Disintegration aids can preferably be used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, in each case based on the total weight of the agent containing disintegration aids.

The automatic dishwashing agents described herein are preferably prefabricated into dosing units. These dosing units are then also packaged as multi-phase products and preferably comprise the amount of cleaning-active substances necessary for a cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g. The volume of the aforementioned dosing units and their spatial shape are selected with particular preference such that the pre-assembled units can be dosed via the dosing chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The machine dishwashing detergents, in particular the prefabricated metering units, particularly preferably have a water-soluble coating.

The water-soluble covering is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The sheath can be formed from 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, can be the same or different. Films which, for example, can be glued and / or sealed to form packaging, such as hoses or pillows, are particularly preferred after they have been filled with an agent.

The water-soluble packaging can have one or more chambers. The agent may be contained in one or more compartments, if any, of the water-soluble envelope. The amount of agent preferably corresponds to the full or half dose required for a rinse cycle.

It is preferred that the water-soluble envelope contain polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, in particular cold water solubility.

Suitable water-soluble films for producing the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 5,000 to 1,000,000 gmol ^-1 , preferably from 20,000 to 500,000 gmol ^-1 , particularly preferably from 30,000 to 100,000 gmol ^-1 and is in particular from 40,000 to 80,000 gmol ^-1 .

Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct route of synthesis is not possible. The same applies to polyvinyl alcohol copolymers which are produced from polyvinyl acetate copolymers accordingly. It is preferred if at least one layer of the water-soluble coating comprises a 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%.

A polymer material containing polyvinyl alcohol which is suitable for producing the water-soluble covering can additionally be a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added. A preferred additional polymer is polylactic acid.

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred.

Also preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof.

It may be preferred that the film material contains further additives. The film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol or mixtures thereof. Other additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble wrappings of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the name M8630, C8400 or M8900. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

According to a preferred embodiment, the multi-phase dishwashing detergent is closely enveloped by a water-soluble film
The water-soluble film, which is preferably used in the narrow wrapping, particularly preferably comprises polyvinyl alcohol, as described above, the starting thickness preferably being from 10 μm to 100 μm, in particular from 12 μm to 60 μm, particularly preferably from 15 μm to 50 µm, especially from 20 µm to 40 µm, in particular from 22 µm to 35 µm is used.

In the case of a tight wrapping, a single serving of the detergent or cleaning agent is wrapped. For the coated detergent or cleaning agent disposable portion according to the invention, it is important that the coating lies tightly against the surface of the tablets at every point. Ideally, the casing is even under tension, but this is not absolutely necessary. This tight fit of the covering is conducive to disintegration: the first time it comes into contact with water, the covering will let a small amount of water pass through at some point, although it does not need to dissolve at first. At this point, the disintegrant contained in the tablet begins to swell. This leads to the fact that the wrapping is now due to the volume increase the tablet suddenly tears open and releases the tablet. The mechanism described here will not work if the casing is not snug, since the tablet can swell without the casing being blown up. The use of a swellable disintegration agent is superior to a gas-generating system, since its explosive effect in any case leads to the casing being torn open. In a gas-generating system, the explosive effect can "dissipate" by the gas escaping from a leak in the casing.

Preferred detergent or cleaning agent disposable portions according to the invention are characterized in that the distance between the single portion and water-soluble coating over the entire area is 0.1 to 1000 μm, preferably 0.5 to 500 μm, particularly preferably 1 to 250 μm and in particular 2.5 to 100 µm.

In a preferred embodiment, the film covering is first loosely placed around a single detergent or cleaning agent portion and welded and then shrunk onto it, so that there is close contact between the film packaging and the cleaning agent concentrate. Accordingly, disposable detergent or cleaning agent portions according to the invention are characterized in that the wrapper is a film packaging shrunk onto it.

For example, this wrapping can be carried out by placing a water-soluble bottom film on a transport chain or a mold (s), then placing one or more detergent or cleaning agent portions (s) on the bottom film; then a water-soluble top film is placed on the detergent or cleaning agent portion (s) on the bottom film and this is then fixed on the bottom film, including the detergent or cleaning agent portion (s),

Alternatively, this step can also be carried out using a single-strand film, which is then placed around the one-time portions as a tube. The foils are then sealed and optionally cut. The film can then be shrink-wrapped using hot air or infrared radiation, optionally with pressure.

Such water-soluble coatings are also in the patent applications WO 2004/031338 A such as WO 2003/099985 A , the disclosure of which is hereby incorporated by reference in its entirety, has already been described.

Exemplary formulations of the agents according to the invention in particular also include phosphate-free dishwashing agents. An exemplary recipe in which those described herein Polymers can be used as additional components in the specified amounts, the following is: Phosphate-free, solid dishwashing detergent formulation (tab): raw material Quantity (% by weight) Na citrate 15.00-20.00 Phosphonate (e.g. HEDP) 2.50-7.50 MGDA 0.00-25.00 Silicate (Na disilicate) 5.00-35.00 soda 12.50-25.00 Na percarbonate 10.00-15.00 Bleaching catalyst (Mn-based) 0.02-0.50 TAED 2.00-3.00 Nonionic surfactant 2.50-10.00 Polycarboxylate 5.00-10.00 Cationic copolymer 0.25-0.75 PVP (cross-linked) 0.00-1.50 Protease 1.50-5.00 Amylase 0.50-3.00 Benzotriazole (silver protection) 0.00-0.50 Perfume 0.05-0.15 Dye solution 0.00-1.00 Zn acetate anhydrous 0.10-0.30 Na sulfate 0.00-25.00 water 0.00-1.50 pH adjusting agent (citric acid) 1.00-1.50 Process aids 0.00-5.00

The corresponding use of the automatic dishwashing agents according to the invention is also an object of the invention. The invention also relates to a dishwashing method, in particular machine dishwashing method, in which a dishwashing agent according to the invention is used. The subject of the present application is therefore also a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher during the course of a dishwasher program before the start of the main wash cycle or in the course of the main wash cycle. The metering or entry of the invention By means of the interior of the dishwasher can be done manually, but the agent is preferably dosed into the interior of the dishwasher by means of the dosing chamber.

The embodiments described in the context of the agents according to the invention are also readily transferable to the methods and uses according to the invention and vice versa.

Examples Example 1: Cleaning performance

Table 1: Composition of the automatic dishwashing detergent (data in% by weight based on the total detergent) raw materials E1 V1 % % Bleaching phase Na citrate 3.5 3.5 HEDP 4.5 4.5 MGDA 12th - soda 15.75 15.75 Na percarbonate 14.5 14.5 Bleaching catalyst 0.03 0.03 Nonionic surfactants 5.1 5.1 Sulfopolymer 5 5 Acrylate homopolymer 0.5 0.5 Dyes 0.35 0.35 Enzyme phase Na citrate 11 11 MGDA - 12th TAED 3rd 3rd Nonionic surfactants 1.5 1.5 Sulfopolymer 2.5 2.5 PEG 4000 1 1 Enzymes (tq, proteases and amylases) 6 6 Dyes, perfume 0.6 0.6 Zn acetate 0.2 0.2 3rd phase Na citrate 1.5 1.5 HEDP 1.5 1.5 MGDA 2nd 2nd silicate 4th 4th soda 2.3 2.3 Nonionic surfactant 0.2 0.2 Sulfopolymer 1 1 Dyes 0.2 0.2 water Ad 100 Ad 100

The cleaning performance was determined in Miele GSL dishwashers in the 45 ° C program. Water hardness 21 ° dH. For this, 20 g of the above recipes (tab) were used. At the end of the wash cycle, the dishes were visually checked on a scale of 1-10. The higher the value, the better the cleaning performance. It can be seen that the formulation E1 according to the invention, which contains MGDA in the bleaching phase, shows a better cleaning performance on enzyme-sensitive soiling, such as minced meat, compared to the comparison formulation V1, which contains MGDA in the enzyme phase (Table 2). Table 2: Cleaning performance ADW product (fresh) Minced meat E1 6.3 V1 5.9 ADW product After 1 week storage at 40 ° C E1 6.6 V1 5.9

Claims (10)

1. An automatic dishwasher detergent, characterized in that the automatic dishwasher detergent comprises:

   (A) an enzyme phase, the enzyme phase containing at least one enzyme and being substantially free of bleaching agents and organic builders from the class of aminocarboxylic acids and salts thereof; and

   (B) a bleach phase, the bleach phase containing at least one bleaching agent, at least one bleach catalyst, and at least one organic builder from the class of aminocarboxylic acids and the salts thereof, in particular methylglycinediacetic acid (MGDA) or the salts thereof.
2. The automatic dishwasher detergent according to claim 1, characterized in that the at least one enzyme comprises at least one protease and preferably also at least one amylase.
3. The automatic dishwasher detergent according to claim 1 or 2, characterized in that the bleach catalyst is selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably the complexes of manganese in the oxidation state II, III, IV or IV, which contain one or more macrocyclic ligand(s) having the donor functions N, NR, PR, O and/or S, particularly preferably the 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), most preferably the ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me/Me-TACN).
4. The automatic dishwasher detergent according to one of claims 1 to 3, characterized in that the bleach catalyst is contained in an amount of from 0.001 to 0.1 wt.%, preferably 0.01 to 0.05 wt.%, based on the total weight of the automatic dishwasher detergent.
5. The automatic dishwasher detergent according to one of claims 1 to 4, characterized in that

   (1) the at least one bleaching agent is selected from the group consisting of sodium percarbonate, sodium perborate tetrahydrate, sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates, perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid, diperdodecanedioic acid, diacyl peroxides, alkylperoxy acids and arylperoxy acids, preferably sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate, even more preferably sodium percarbonate; and/or

   (2) the at least one bleaching agent is contained in the dishwasher detergent in an amount of from 1-35 wt.%, and increasingly preferably from 2-30 wt.%, 3.5-25 wt.%, 4-20 wt.%, and particularly preferably from 5-15 wt.%, based on the total weight of the dishwasher detergent in each case.
6. The automatic dishwasher detergent according to one of claims 1 to 5, characterized in that the at least one organic builder is MGDA and the enzyme phase is substantially free of MGDA.
7. The automatic dishwasher detergent according to one of claims 1 to 6, characterized in that the at least one organic builder from the class of aminocarboxylic acids and salts thereof is contained in the dishwasher detergent in an amount of from 5 to 35 wt.%, preferably 10 to 25 wt.%, and in particular 10 to 20 wt.%, based on the weight of the total agent.
8. The automatic dishwasher detergent according to one of claims 1 to 7, characterized in that

   (1) the automatic dishwasher detergent is in solid form; and/or

   (2) the automatic dishwasher detergent is in a pre-portioned form; and/or

   (3) the enzyme phase and the bleach phase are spatially separated from one another; and/or

   (4) the automatic dishwasher detergent contains at least one bleach activator, in particular in the enzyme phase; and/or

   (5) the automatic dishwasher detergent contains at least one further constituent, preferably at least two further constituents, selected from the group consisting of further builders, surfactants, polymers, corrosion inhibitors, glass corrosion inhibitors, disintegration aids, fragrances and perfume carriers.
9. The use of an automatic dishwasher detergent according to one of claims 1-8 in an automatic dishwasher method.
10. An automatic dishwasher method, characterized in that an automatic dishwasher detergent according to one of claims 1-8 is used.